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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to air presses for a papermaking machine, and, more particularly, to end seal arrangements therefor.
[0003] 2. Description of the Related Art
[0004] Effective water removal from a paper web is essential to the papermaking process. Various types of presses, using some combination of juxtaposed rolls, have been used for some time now for water removal. Such presses rely on the hydraulic pressure created at the nip between each pair of juxtaposed rolls through which the paper web travels in a given press configuration to drive water from the paper web.
[0005] Various press have been developed which have attempted to add an element of a positive air pressure within the press assembly to more effectively force the water from the paper web. With respect to roll presses specifically, the rolls of the press have been configured to form a chamber with a positive air pressure being supplied therewithin.
[0006] However, the effectiveness of a multi-roll air presses is limited by the degree to which the air chamber thereof can be sealed. The areas of the press where sealing becomes quite crucial are those areas where the paper web and the membrane(s) carrying it do not pass, as the web/membrane(s) combination inherently acts to seal the region of each nip through which it passes. Those regions of the air press through which the paper web/membrane(s) combination does not pass are the opposed lateral ends of each nip and the opposed chamber ends defined by the two sets of roll end associated with the air press. Consequently, an end seal mechanism is provided at each chamber end, each such mechanism having a seal member which contacts each of the roll ends associated with that particular chamber end.
[0007] The ability of the end seal mechanism to efficiently seal a chamber is predicated on the application of a sufficient sealing force so that the seal member thereof maintains sealing contact with each of the roll ends of that chamber end. On the other hand, applying a force thereto that is greater than that needed to maintain a seal will cause the seal member to wear out quicker than is necessary.
[0008] Additionally, current end seal mechanisms do not facilitate adjustments in the positioning thereof or in the force ultimately applied on the seal member thereof. With such systems, retraction of the end seal mechanisms for start-up and/or maintenance is not readily achieved. Additionally, it is difficult to optimize the forces applied to the seal member during start-up to initially achieve a sufficient seal therewith and yet promote a long life thereof.
[0009] What is needed in the art is an end seal mechanism in which the sealing force applied to the seal member thereof can be readily adjusted in order to achieve sufficient sealing while minimizing the rate of wear of the seal member; and an end seal mechanism which permits adjustments in the positioning thereof and in the amount of force placed upon the seal member thereof during various operational stages.
SUMMARY OF THE INVENTION
[0010] The present invention provides an end seal mechanism for an air press of a papermaking machine in which the force applied upon the end seal mechanism is independent of the air pressure inside the air press, the sealing force placed thereupon and the position thereof instead being controlled by an adjustable bias mechanism.
[0011] The invention comprises, in one form thereof, an air press for pressing a fiber web, the air press including a plurality of rolls and a pair of end seal arrangements. Of the plurality of rolls, each pair of adjacent rolls forms a nip therebetween. Further, each roll has a pair of roll ends, the plurality of rolls together forming two sets of roll ends. Each end seal arrangement coacts with one set of roll ends, the plurality of rolls and the pair of end seal arrangements together defining an air press chamber having an air chamber pressure. Each end seal arrangement is composed of at least one roll seal, including a first roll seal, and an adjustable bias mechanism. Each roll seal forms a seal with at least one roll end, and one side of the first roll seal being exposed to the air chamber pressure. The adjustable bias mechanism is configured for controlling a position of each roll seal relative to a respective at least one roll end and for adjusting a seal force between the roll seal and the respective at least one roll end.
[0012] In another form, the present invention comprises a method of achieving an end seal in an air press for pressing a paper web. The method includes a series of steps, the first of which is providing a plurality of rolls, each pair of adjacent rolls forming a nip therebetween. Each roll has a pair of roll ends, the plurality of rolls together forming two sets of roll ends. An end seal arrangement is positioned adjacent a respective set of roll ends, the plurality of rolls and the respectively positioned end seal arrangements together defining an air press chamber having an air chamber pressure. Each end seal arrangement is composed of at least one roll seal, including a first roll seal, and an adjustable bias mechanism. Each roll seal forms a seal with at least one roll end, and one side of the first roll seal being exposed to the air chamber pressure. The adjustable bias mechanism is configured for controlling a position of each roll seal relative to a respective at least one roll end and for adjusting a seal force between the roll seal and the respective at least one roll end. The seal force provided by the adjustable bias mechanism is increased to seat the set of roll ends within the end seal arrangement. Then, the seal force provided by the adjustable bias mechanism is decreased upon seating of the set of roll ends within the end seal arrangement. Finally, a substantially constant low net force is maintained on each roll seal upon the seating and during operation of the air press, the substantially constant low net force being maintained using the adjustable bias mechanism.
[0013] an end seal mechanism in which the sealing force applied to the seal member thereof can be readily adjusted in order to achieve sufficient sealing while minimizing the rate of wear of the seal member; and an end seal mechanism which permits adjustments in the positioning thereof and in the amount of force placed upon the seal member thereof during various operational stages.
[0014] An advantage of the present invention is the seal force applied to the seal member of the end seal mechanism can be readily adjusted in order to achieve sufficient sealing while minimizing the rate of wear of the seal member.
[0015] Another advantage is the end seal mechanism permits adjustments in the positioning thereof and in the amount of force placed upon the seal member thereof during various operational stages, thereby facilitating the optimization of both the forces applied to the seal member during start-up to initially achieve a sufficient seal therewith and the force needed to promote a long life thereof
[0016] Yet another advantage is that the end seal mechanism can be designed so that the total force applied on a seal member is independent of the air chamber pressure in the air press and thus not subject to potential fluctuations in the air chamber pressure.
[0017] An even further advantage is that biasing springs can be eliminated from the design of the end seal mechanism due to the presence of the adjustable bias mechanism.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] 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 embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
[0019] [0019]FIG. 1 is a schematic, side view of an embodiment of a papermaking machine of the present invention;
[0020] [0020]FIG. 2 is a schematic, partially-sectioned, fragmentary view of the end seal arrangement of FIG. 1; and
[0021] [0021]FIG. 3 is a schematic, partially-sectioned, fragmentary view of another embodiment of an end seal arrangement which can be employed in the papermaking machine shown in FIG. 1.
[0022] Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate at least one preferred embodiment of the invention, in one form, and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Referring now to the drawings, and more particularly to FIG. 1, there is shown a papermaking machine 10 for processing a paper web 12 which generally includes an air press assembly 14 and a plurality of conveyor rolls 16 .
[0024] Air press assembly 14 is constituted of a plurality of press rolls 18 juxtaposed with one another so as to define a plurality of nips 20 therebetween and an air chamber 22 thereamongst. Contacting a set of end faces 24 of press rolls 18 is an end seal arrangement 26 for closing off what would otherwise be an open end of air chamber 22 .
[0025] End seal arrangement 26 is composed of a piston holder 28 (FIG. 2), a seal piston 30 , a seal holder 32 , at least a first seal member 34 and an adjustable bias mechanism 36 . Each end seal arrangement 26 , by closing off an open end of air chamber 22 , further defines air chamber 22 , air chamber 22 having an air chamber pressure associated therewith. Piston holder 28 , seal piston 30 , seal holder 32 and first seal member 34 , by each specifically helping to define the boundary of air chamber 22 , are all exposed to the air chamber pressure.
[0026] Piston holder 28 acts as an outer structural member for end seal arrangement 26 . Piston holder 28 has a holder side wall 38 within which seal piston 30 is movably mounted. A gasket 40 is provided in seal piston 30 adjacent holder side wall 38 to ensure sealing contact therebetween. Seal piston 30 is movably mounted within piston holder 28 so to facilitate both the positioning of and the adjustment of a biasing force B applied on at least first seal member 34 .
[0027] Seal holder 32 extends from seal piston 30 opposite piston holder 28 and holds at least first seal member 34 therein. Seal holder 32 may either be integral with seal piston 30 , as shown in FIG. 2, or attached thereto. First seal member 34 is configured for directly contacting and sealing with end faces 24 . If only first seal member 34 is employed, first seal member 34 would advantageously made of a hard seal material and would be bonded directly to seal holder 32 , in addition to being exposed to air chamber 22 .
[0028] In the embodiment shown in FIG. 2, a further second seal member 42 is provided between and bonded to each of first seal member 34 and seal holder 32 . First and second seal members 34 , 42 can be considered roll seals as each seals with end faces 24 of press rolls 18 . In this instance where two roll seals are employed, second seal member 42 is advantageously made of a hard seal material, while first seal member 34 is favorably made of a soft seal material. The soft seal material deforms to form an efficient seal interface between end seal arrangement 26 and corresponding end faces 24 . Meanwhile, a hard seal material offers increased stiffness and wear resistance in comparison to a soft seal material. It is thus favorable for at least one of first and second seal members 34 , 42 to be made of a hard seal material in order to ensure sufficient seal stability and to minimize the rate at which seal wear occurs, as that wear rate is set by the hardest seal material present and in contact with each end face 24 . First and second seal members 34 , 42 may advantageously be made of a carbon fiber (CF) composite and/or polytetrafluoroethylene (PTFE) (commonly known by its trade name “Teflon®”), respectively.
[0029] First seal member 34 and, if present, second seal member 42 are sized and configured to maintain a separation distance 44 between each end face 24 and seal holder 32 to avoid wearing of seal holder 32 . As such, the time between seal member changes is dictated by the wear time needed to cause separation distance 44 to reach zero.
[0030] In the embodiment of FIG. 2, first seal member 34 and second seal member 42 together define a seal boundary 48 , seal boundary 48 encompassing a pressurized seal area 50 (schematically shown) therewithin. Similarly, inner holder face 52 of holder side wall 38 bounds and thereby defines a pressurized piston area 54 (schematically shown). Since, in the embodiment shown in FIG. 2, pressurized seal area 50 is approximately equal to pressurized piston area 54 , the pressures are balanced throughout seal boundary 48 , advantageously resulting in essentially no net chamber seal force F being applied upon first seal member 34 and/or second seal member 42 , regardless of the air chamber pressure. Under balanced pressure conditions, chamber seal force F is independent of the air chamber pressure.
[0031] In the embodiment of FIG. 2, both seal boundary 48 and holder side wall 38 define a similar dog-bone shape (FIG. 1). It is contemplated that those shapes could differ (e.g., seal boundary 48 could define a dog-bone shape and holder side wall 38 , a circle) as long as the areas encompassed thereby were essentially the same.
[0032] By achieving no net chamber seal force F regardless of air chamber pressure, the risk is avoided of underloading first seal member 34 and/or second seal member 42 in the case of a drop in air chamber pressure and of thus inviting possible leakage and/or slow seal breakage. Likewise, the risk of overloading first seal member 34 and/or second seal member 42 in the case of a rise in air chamber pressure and thus wearing out first seal member 34 and/or second seal member 42 at an even greater rate is also avoided when pressures are balanced. If, for example, pressurized piston area 54 were instead greater than pressurized seal area 50 , chamber seal force F would exist on first seal member 34 and/or second seal member 42 due to the air chamber pressure, chamber seal force F increasing with increasing air chamber pressure. In certain instances, it may prove desirable to have pressurized piston area 54 be slightly greater than pressurized seal area 50 so that a small chamber seal force F and, thus, a sealing function would exist in all operational situations.
[0033] Adjustable bias mechanism 36 is configured for controlling a position of first seal member 34 and, if present, second seal member 42 relative to a respective set of end faces 24 and for providing a biasing force B between each of first seal member 34 and second seal member 42 , if present, and respective end faces 24 . Adjustable bias mechanism 36 is capable of generating the smallest possible biasing force B needed to create a suitable seal between each of first seal member 34 and second seal member 42 , if present, and respective end faces 24 . It is advantageous to apply the smallest possible biasing force B needed to create a suitable seal as seal wear can be minimized thereby.
[0034] Adjustable bias mechanism 36 is advantageously capable of ensuring that first seal member 34 and second seal member 42 , if present, are engaged when air chamber 22 is pressurized; retracting end seal arrangement 26 for startup and maintenance; and regulating biasing force B such that biasing force B is increased during seal break in and decreased once seated to maximize seal life. The ability to retract end seal arrangement 26 when nips 20 are being closed avoids the possibility of first seal member 34 and/or second seal member 42 being broken by end faces 24 catching thereon. Further, since biasing force B is independent of chamber seal force F, even if chamber seal force F is not zero, end seal arrangement 26 can be closed and loaded independently of air chamber pressure. As a result of such independence, such a design can advantageously eliminate the need for springs in the end seal arrangement.
[0035] In the embodiment shown in FIG. 2, adjustable bias mechanism 36 includes an air cylinder 56 and an air cylinder shaft 58 . Air cylinder 56 may either be mounted outside of piston holder 28 (as shown in FIG. 2) or inside thereof (not shown). Air cylinder shaft 58 is selectively driven by air cylinder 56 and operably connects air cylinder 56 with seal piston 30 . If air cylinder 56 is mounted outside of piston holder 28 with air cylinder shaft 58 accordingly extending therethrough, appropriate seals (not shown) are advantageously provided between air cylinder shaft 58 and piston holder 28 to minimize leakage therebetween.
[0036] In operation, end seal arrangement 26 is positioned adjacent a set of end faces 24 of press rolls 18 . Air cylinder 56 of adjustable biasing mechanism 36 is first used to apply an increased biasing force B during break in of first and second seal members 34 , 42 . Biasing force B is then decreased once seated to a minimum force needed to maintain a sufficient seal between end faces 24 and first and second seal members 34 , 42 to maximize seal life thereof.
[0037] End seal arrangement 60 , shown in FIG. 3, is a second embodiment of the end seal arrangement of the present invention. End seal arrangement 60 is composed of a piston holder 62 , a seal piston 64 , a seal holder 66 , a first seal member 68 , a second seal member 70 (optional in the same manner as the first embodiment, requiring first seal member 68 to be bonded directly to seal holder 66 if not used) and an adjustable bias mechanism 72 . Each end seal arrangement 60 , by closing off an open end of air chamber 22 , further defines air chamber 22 , air chamber 22 having an air chamber pressure associated therewith. Piston holder 62 , seal piston 64 , seal holder 66 and first seal member 68 , by each specifically helping to define the boundary of air chamber 22 , are all exposed to the air chamber pressure.
[0038] Only those features which differ from those of the first embodiment will be discussed in detail with respect to this second embodiment.
[0039] Piston holder 62 , seal piston 64 and o-rings 74 together define adjustable bias mechanism 72 . Adjustable bias mechanism 72 has an adjustable biasing pressure therein, a net biasing force B 1 produced thereby being a function of the difference between the biasing pressure therein and the atmospheric pressure outside of end seal arrangement 60 . In a manner similar to that for the first embodiment, piston holder 62 encompasses a pressurized piston area 76 , and the combination of first and second seal members 68 , 70 bounds and thereby defines pressurized seal area 78 , and pressurized piston area 76 is essentially equal to pressurized seal area 78 , thereby producing no net chamber seal force F 1 .
[0040] As such, the only net force placed on first and second seal members 68 , 70 is one generated by adjustable bias mechanism 72 , i.e., biasing force F 1 . Thus, if the biasing pressure is equal to atmospheric pressure, biasing force B 1 is equal to zero, resulting in no downward force on first and second seal members 68 , 70 . However, a biasing pressure in excess of atmospheric produces a positive biasing force B 1 , resulting in a downward force on first and second seal members 68 , 70 . Conversely, first and second seal members 68 , 70 can be retracted from end faces 24 by applying a less than atmospheric pressure (e.g., a vacuum) within adjustable bias mechanism 72 .
[0041] Other features of the second embodiment which differ from the first are apparent in FIG. 3. Seal holder 66 is separate from seal piston 64 and is attached thereto via a holder attachment mechanism 80 (e.g., a bolt or screw). Using a separate seal holder 66 eases seal member replacement but introduces the requirement of attaining a sufficient seal between seal holder 66 and seal piston 64 .
[0042] Both lateral and vertical movement of seal piston 64 relative to piston holder 62 is limited by piston attachment mechanism 82 (e.g., a bolt or other attachment pin). Piston attachment mechanism 82 extends through seal piston 64 and is mounted in piston holder 62 . Piston attachment mechanism 82 is supplied with a head 84 , head 84 acting as a vertical movement stop for seal piston 64 .
[0043] Additionally, an indicator light 86 (e.g. an LED) is provided on head 84 to act as a visual indicator of a gap and thus a potential leak site between end faces 24 and end seal arrangement 60 . Such an indicator light 86 could also be advantageously employed within the first embodiment.
[0044] Operation of end seal arrangement 60 is similar to that of end seal arrangement 26 with the exception of using a variable biasing pressure within adjustable bias mechanism 72 to produce the desired biasing force B 1 .
[0045] While this invention has been described as having a preferred design, 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.
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An air press for pressing a fiber web includes a plurality of rolls and a pair of end seal arrangements. Of the plurality of rolls, each pair of adjacent rolls forms a nip therebetween. Further, each roll has a pair of roll ends, the plurality of rolls together forming two sets of roll ends. Each end seal arrangement coacts with one set of roll ends, the plurality of rolls and the pair of end seal arrangements together defining an air press chamber having an air chamber pressure. Each end seal arrangement is composed of at least one roll seal, including a first roll seal, and an adjustable bias mechanism. Each roll seal forms a seal with at least one roll end, and one side of the first roll seal being exposed to the air chamber pressure. The adjustable bias mechanism is configured for controlling a position of each roll seal relative to a respective at least one roll end and for adjusting a seal force between the roll seal and the respective at least one roll end.
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PRIORITY
[0001] This application claims the priority of U.S. Provisional application No. 60/396,779, filed Jul. 17, 2002 titled “Optical Lithography Fluoride Crystal Annealing Furnace”.
BACKGROUND OF INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to methods and apparatus for producing optical crystals. In particular, the invention relates to a method and an apparatus for annealing optical crystals, particularly optical lithography fluoride crystals for transmitting below 250-nm UV light.
[0004] 2. Background Art
[0005] Optical crystals are commonly grown using the Stockbarger-Bridgman method. In the Stockbarger-Bridgman method, the optical crystals are grown in a vertical furnace by moving molten crystal material through a temperature gradient zone in the furnace. The method is further explained below with reference to FIGS. 1A and 1B .
[0006] FIG. 1A shows a vertical furnace 1 having an upper zone 2 and a lower zone 3 . Heating jackets 4 , 5 are provided in the upper and lower zones 2 , 3 , respectively. The heating jackets 4 , 5 are operated such that a temperature gradient zone 6 is created between the upper and lower zones 2 , 3 . At the start of the growth process, a crucible 7 containing a crystal raw material F is mounted in the upper zone 2 . The crystal raw material F is melted by heat from the heating jacket 4 . After melting the crystal raw material F, the crucible 7 is lowered into the lower zone 3 , as shown in FIG. 1B . As the crucible 7 passes from the upper zone 2 into the lower zone 3 , the molten material M goes through the temperature gradient zone 6 . On passing through the temperature gradient zone 6 , the temperature transition inside the molten material M creates a crystallization front CF. The crystallization front CF propagates inside the crucible 7 , within the molten material M, as long as the crucible 7 continues to move downwardly.
[0007] Crystals grown using the method described above are exposed to sharp localized cooling as they are translated through the temperature gradient zone into the lower zone. Sharp localized cooling induces permanent thermal strain (or stress) in the crystals, which can result in unacceptably elevated values in birefringence of the crystals. To reduce the permanent thermal strain in the crystal, the crystal is annealed in the lower zone of the growth furnace. The annealing cycle includes re-heating the crystal to a temperature below the melting temperature of the crystal, holding the crystal at this temperature until the thermal strain induced in the crystal by the sharp localized cooling is dissipated, and then slowly cooling the crystal to a temperature below which any strain due to additional cooling to room temperature will result only in temporary strain in the crystal.
[0008] The duration of the annealing cycle depends on the volume of the crystal. As the volume of the crystal increases, the ability to completely anneal the crystal inside the growth furnace such that the birefringence of the crystal meets the specification reduces. For instance, exposure systems in microlithography processes require optical crystals, mainly fluoride crystals, with birefringence values of 3 nm/cm or lower. To meet such stringent specifications for large-volume crystals, the growth furnace would have to be tied up for extended times, which would have a great impact on the ability to meet market demands. Therefore, the current practice is to anneal the crystal for a relatively short time in the growth furnace. The birefringence of the crystal is then measured. If the crystal has an unacceptably high birefringence value, the crystal is further annealed in a separate furnace from the growth furnace. This process is typically referred to as post-annealing.
[0009] A typical annealing furnace is a vertical furnace in which a vertical stack of individual hermetically-sealed containers can be supported during post-annealing. The furnace includes heaters for creating a desired temperature profile inside the furnace. In operation, the crystals to be annealed are loaded into the sealed containers, and the sealed containers are loaded into the annealing furnace. A vacuum, inert, or fluorinating atmosphere may be provided inside the sealed containers. The annealing process starts by heating the crystals to a temperature below the melting point of the crystals. The crystals are held at this temperature for a predetermined length of time before being slowly cooled to room temperature. Typically, the heaters used in the process are circumferential heaters, which are arranged in the furnace so as to circumscribe the individual containers. In addition, heaters or thermal insulators can be placed at the top and bottom of the stack of containers.
[0010] The annealing cycle can be relatively short if the crystals in the stack have small diameters, e.g., less than 150 mm. This is because the path of conduction from the circumference of the crystals, where the heat is applied, to the center of the crystals is relatively short. Thus, the heating rates from room temperature to annealing temperature and the cooling rates from annealing temperature to room temperature can be relatively high. However, as the diameters of the crystals increase, the path of conduction from the circumference of the crystals to the center of the crystals increases. As a result, the time required to complete the annealing process such that a desired birefringence level in the crystal is achieved also increases. Currently, there are demands for optical fluoride crystals with diameters of 300 mm or greater. Therefore, a process of annealing multiple large-diameter (crystal blank disk diameter>150 mm, preferably ≧250 mm, more preferably ≧300 mm) crystals within a reasonable time frame is desirable.
SUMMARY OF INVENTION
[0011] In one aspect, the invention relates to a method of making below 250-nm UV light transmitting optical fluoride lithography crystals which comprises (a) applying heat along a shortest path of conduction of a selected optical fluoride disk crystal, (b) heating the optical fluoride crystal to an annealing temperature, (c) holding the temperature of the optical fluoride crystal at the annealing temperature, and (d) gradually cooling the optical fluoride crystal to provide a low-birefringence optical fluoride crystal for transmitting below 250-nm UV light.
[0012] In another aspect, the invention relates to a method of making below 250-nm UV light transmitting optical fluoride lithography crystals which comprises (a) arranging a plurality of selected optical fluoride disk crystal in a single layer in a furnace, (b) applying heat along a shortest path of conduction of the selected optical fluoride crystals, (c) heating the optical fluoride crystals to an annealing temperature, (d) holding the temperature of the optical fluoride crystals at the annealing temperature, and (e) gradually cooling the optical fluoride crystals to provide low-birefringence optical fluoride crystals for transmitting below 250-nm UV light.
[0013] In another aspect, the invention relates to a method of making below 250-nm UV light transmitting optical fluoride lithography crystals which comprises (a) providing optical fluoride disk crystals having birefringence values above 3 nm/cm, (b) applying heat along a shortest path of conduction of the optical fluoride disk crystals, (c) heating the optical fluoride crystals to an annealing temperature, (d) holding the temperature of the optical crystals at the annealing temperature, and (e) gradually cooling the optical fluoride crystals to provide optical fluoride crystals having birefringence value not higher than 3 nm/cm.
[0014] In another aspect, the invention relates to an apparatus for making low birefringence optical fluoride crystals which comprises a furnace, a chamber supported inside the furnace for containing at least one optical fluoride disk crystal, and at least one heater disposed external to the chamber, the heater being arranged to apply heat along a shortest path of conduction of the optical fluoride disk crystal.
[0015] In another aspect, the invention relates to an apparatus for annealing optical crystals which comprises a furnace, a chamber supported inside the furnace for containing at least an optical crystal, and at least a pair of heaters disposed external to the chamber, the heaters being arranged to provide heat along the shortest path of conduction of the optical crystal.
[0016] In another aspect, the invention relates to an apparatus for annealing optical crystals which comprises a furnace, a plurality of chambers supported inside the furnace for containing a plurality of optical crystals, and at least a pair of heaters disposed external to each chamber, the heaters being arranged to provide heat along the shortest path of conduction of the optical crystals.
[0017] In another aspect, the invention relates to an apparatus for annealing an optical crystal which comprises a chamber having a surface for supporting an optical crystal, at least one heater disposed external to the chamber, the heater being arranged to apply heat along a shortest path of conduction of the optical crystal, and means for enhancing exchange of radiation energy between the heater and the optical crystal.
[0018] Other features and advantages of the invention will be apparent from the following description and the appended claims.
BRIEF DESCRIPTION OF DRAWINGS
[0019] FIGS. 1A and 1B illustrate a prior-art process for growing an optical crystal.
[0020] FIG. 2A shows a vertical cross-section of an annealing apparatus according to an embodiment of the invention.
[0021] FIG. 2B shows multiple heating elements mounted parallel to the top and bottom surfaces of a horizontal annealing chamber.
[0022] FIG. 2C shows heaters mounted parallel to the top, bottom, and side surfaces of a horizontal annealing chamber.
[0023] FIG. 2D shows a spiral heater circumscribing a horizontal chamber.
[0024] FIG. 3 shows depressions formed on the inside surfaces of a horizontal annealing chamber.
[0025] FIG. 4A shows heaters having concave surfaces mounted parallel to the top and bottom surfaces of a horizontal annealing chamber.
[0026] FIG. 4B shows heaters having convex surfaces mounted parallel to the top and bottom surfaces of a horizontal annealing chamber.
[0027] FIG. 5 shows a disk spacer interposed between the optical crystals and an inside surface of a horizontal annealing chamber.
[0028] FIG. 6 shows multiple spherical spacers interposed between the optical crystals and a horizontal annealing chamber.
[0029] FIG. 7A shows optical crystals arranged in an edgewise (vertical) orientation within a furnace.
[0030] FIG. 7B shows a vertical cross-section of the annealing apparatus shown in FIG. 7A .
[0031] FIG. 7C shows optical crystals arranged in a vertical orientation within a furnace with the circumferential edges of the optical crystals having the same orientation as the round portion of the furnace.
[0032] FIG. 8A shows a uniform temperature distribution within an optical crystal.
[0033] FIG. 8B shows a temperature distribution near the edge of an optical crystal.
[0034] FIG. 9 shows a process gas system for use in an annealing process.
[0035] FIG. 10 shows an annealing cycle illustrating gas selection.
DETAILED DESCRIPTION
[0036] Embodiments of the invention provide a method and an apparatus for annealing large-diameter crystals, particularly optical fluoride disk crystals. For example, crystals with a diameter of 300 mm or greater and diameter-to-thickness ratios of 3.0 or greater can be treated using the method and apparatus of the invention, preferably optical fluoride crystal disks. Smaller-diameter crystals can also take advantage of the benefits offered by the method and apparatus of the invention. The invention includes applying heat uniformly to and removing heat uniformly from the optical crystals along their shortest path of conduction. The shortest path of conduction is along the shortest dimension of the crystal. For a circular crystal having a diameter-to-thickness ratio greater than 1, the shortest path of conduction is along the thickness of the crystal. The following is a description of specific embodiments of the invention.
[0037] FIG. 2A shows an annealing apparatus 10 according to one embodiment of the invention. The apparatus 10 includes a horizontal chamber (or vessel) 12 having a surface 14 for supporting one or more disk crystals 16 . The horizontal chamber 12 is preferably unsealed, including not sealed hermetically, and can be gas permeable. The horizontal chamber 12 is made of an inert material, such as graphite, boron nitride, silicon carbide, or silicon nitride. The crystals 16 could be any type of optical fluoride crystal. For applications such as microlithography, fluoride crystals, such as single crystals of CaF 2 , BaF 2 , SrF 2 , LiF, MgF 2 , or NaF or mixed fluoride crystals made from solid solutions of these materials, are of interest.
[0038] For discussion purposes, the crystals 16 are assumed to be disk-shaped. However, the invention is not limited to disk-shaped crystals. In a preferred embodiment of the invention the optical fluoride crystals are disks. The crystals 16 are arranged in a single layer on the surface 14 . The single-layer arrangement is preferred when the crystals 16 have large diameters, i.e., greater than 150 mm, and have a diameter-to-thickness ratio greater than 1. If the crystals 16 have small diameters, i.e., smaller than 150 mm, or have a diameter-to-thickness ratio less than 1, then it may be possible to arrange the crystals in more than one layer on the surface 14 . In general, the crystals 16 should be arranged such that the majority (preferably at least 90%) of the heat that would be applied to them would be conducted along their shortest path of conduction, i.e., along their shortest dimension (diameter or thickness).
[0039] In the illustration, the bottom surfaces 18 of the crystals 16 are in direct contact with the surface 14 of the horizontal chamber 12 . In alternate embodiments, the crystals 16 could be placed in crystal containers (not shown), which can then be supported on the surface 14 of the horizontal chamber 12 . In alternate embodiments, as will be further described below, the bottom surfaces 18 of the crystals 16 may be spaced from the surface 14 of the horizontal chamber 12 to reduce or avoid contamination of the crystals 16 with the material used in constructing the horizontal chamber 12 .
[0040] The horizontal chamber 12 is supported inside a furnace 20 . Preferably, the support structure (not shown) for the horizontal chamber 12 is such that it does not cast thermal radiation “shadows” that can be detected on the inside of the horizontal chamber 12 . Preferably, the furnace 20 is a vacuum furnace. The furnace 20 may be constructed of a water-cooled stainless steel casing or other suitable material. Preferably, the furnace 20 includes one or more ports (not shown) through which the atmosphere in the furnace 20 can be controlled. For example, the ports may be used for introducing atmosphere-controlling gases into the furnace 20 and for measuring the temperature and pressure in the furnace 20 . Preferably, a gas purification/dryer system (not shown) is provided for removal of oxygen and moisture from process gases supplied into the furnace 20 . Preferably, the moisture level in the furnace 20 is controlled to less than 1 ppb. Catalyst/Absorber/Getter systems may be used to remove moisture from the furnace atmosphere.
[0041] Inside the furnace 20 , the horizontal chamber 12 is supported between heaters 22 , 24 . The heaters 22 , 24 are generally parallel to the top and bottom surfaces 26 , 28 , respectively, of the horizontal chamber 12 . The heaters 22 , 24 may be resistance heating elements made of graphite or other suitable inert material. The heaters 22 , 24 may be single heating elements. In other embodiments, such as shown in FIG. 2B , multiple heating elements 22 a , 24 a may be mounted parallel to the top and bottom surfaces 26 , 28 , respectively, of the horizontal chamber 12 . Multiple heating elements allow for flexibility in controlling the temperature along the length of the horizontal chamber 12 . In other embodiments, such as shown in FIG. 2C , heaters 30 , 32 may be mounted parallel to the side surfaces 34 , 36 of the horizontal chamber 12 . In other embodiments, such as shown in FIG. 2D , the horizontal chamber 12 may be placed within one or more spiral heaters 34 .
[0042] Returning to FIG. 2A , the heaters 22 , 24 provide the majority of the heat used in bringing the crystals 16 from room temperature to annealing temperature. If the diameter-to-thickness ratio of the crystals 16 is greater than 1 and the crystals 16 are arranged in a single layer, then the heat generated by the heaters 22 , 24 would be conducted along the shortest path of conduction of the crystals 16 . Providing the majority of the heat along the shortest path of conduction of the crystals 16 would result in increased heating rates in comparison to the case where the crystals are arranged in a vertical stack. Also, the single-layer arrangement of the crystals 16 would allow the crystals 16 to be cooled evenly at increased cooling rate throughout the entire cooling portion of the annealing cycle. The single-layer arrangement of the crystals 16 would also allow for even distribution of process gases around the crystals 16 .
[0043] Radiation enhancements can be used to increase the radiation view factors on the crystals 16 and improve the overall temperature uniformity within the crystals 16 . The term “radiation view factor” refers to the fraction of thermal energy leaving the surface of a first object and reaching the surface of a second object, determined entirely from geometrical considerations. In other words, the term “radiation view factor” on the crystal 16 refers to the fraction of the crystal 16 visible from the horizontal chamber 12 . In one embodiment, the radiation enhancements include textures or shapes formed on the inside surfaces of the horizontal chamber 12 . For example, FIG. 3 shows cup-shaped depressions 36 formed on the inside surfaces of the horizontal chamber 12 . The sides of the depressions 36 would be at an angle sufficient to increase the radiation view factors on the crystals 16 .
[0044] Radiation enhancements can also be used to apply more radiation energy to specific portions of the crystals 16 such that more uniform heating or cooling of the crystals 16 is achieved. As in the embodiment above, these radiation enhancements could be textures or shapes formed on the inside surfaces of the horizontal chamber 12 and/or heaters 22 , 24 . As an example, the radiation enhancements could be concave or convex shapes formed on the inside surfaces of the heaters 22 , 24 . FIG. 4A shows concave shapes 40 formed on the inside surface of the heaters 22 , 24 . The concave shapes 40 apply more radiation energy toward the center of the crystals 16 , promoting even heating. FIG. 4B shows convex shapes 38 formed on the inside surface of the heaters 22 , 24 . The convex shapes 38 , when centered over the crystals 16 , apply more radiation energy toward the circumference of the crystals 16 , promoting even cooling.
[0045] The annealing process starts with loading of the optical fluoride crystals 16 into the horizontal chamber 12 , as shown in FIG. 2A . The horizontal chamber 12 is then loaded into the furnace 20 . Typically, the horizontal chamber 12 is not sealed so that process gases can be passed over the crystals 16 as necessary. After loading the horizontal chamber 12 into the furnace 20 , the furnace 20 is sealed, and the required atmosphere such as vacuum, inert, or fluorinating environment, is created inside the furnace 20 . After creating the required atmosphere inside the furnace 20 , the heating elements 22 , 24 are operated such that the crystals 16 are heated to annealing temperature, typically a temperature below the melting point of the crystals 16 . The heating process may include multiple heating and thermal hold segments. The crystals 16 are held at the annealing temperature for a predetermined length of time and then cooled at a controlled rate to room temperature. Typically, this cooling process involves slowly reducing the heat provided by the heaters 22 , 24 . During annealing, a control system (not shown) monitors and controls the atmosphere in the furnace 20 to a programmed level.
[0046] The following is an outline of an annealing process for calcium fluoride crystals using the apparatus of the invention. In particular, various modifications can be made to the heating and cooling schedules depending on the type of optical fluoride crystal treated and the birefringence level desired. The outline of the annealing process is as follows:
Load the horizontal chamber 12 inside the furnace 20 and seal the furnace 20 . Pump vacuum into the furnace 20 until vacuum pressure of 10 −5 Torr is achieved. Hold the furnace 20 at the vacuum pressure of 10 −5 Torr for 30 minutes. Backfill the furnace 20 with preheated nitrogen or argon or a mixture of nitrogen and argon at a continuous programmed rate of 5 volume exchanges per hour, where the temperature of the gas supplied matches the temperature of the furnace 20 . Heat the furnace 20 from room temperature to 300° C. in 5.5 hours with ±10° C. difference at any point outside of the chamber 12 . Hold the temperature of the furnace 20 at 300° C. for 1 hour with ±5° C. at any point outside of the chamber 12 by the start of the thermal hold. At the beginning of the thermal hold, start pumping vacuum into the furnace 20 until vacuum pressure of 10 −5 Torr is achieved. Hold the furnace 20 at the vacuum pressure of 10 −5 Torr for 30 minutes. Backfill the furnace 20 with preheated nitrogen or argon or a mixture of nitrogen and argon at a continuous programmed rate of 5 volume exchanges per hour, where the temperature of the gas supplied matches the temperature of the furnace 20 . Heat the furnace 20 from 300° C. to 1200° C. in 18 hours with +2.5° C. at any point on the outside of the chamber. Hold the temperature of the furnace 20 at 1200° C. for 72 hours with ±1° C. difference at any point on the outside of the chamber 12 within 4 hours of the start of the thermal hold and continuing through the end of the hold at the same ±1° C. difference. Cool the furnace 20 to 800° C. in 200 hours with ±1° C. difference at any point on the outside of the chamber 12 throughout this cooling range. Hold the temperature of the furnace 20 at 800° C. for 24 hours with ±1° C. difference at any point on the outside of the chamber 12 through the end of the hold. Cool the furnace 20 to room temperature in 150 hours with ±2.5° C. difference at any point on the outside of the chamber 12 throughout this entire cooling range.
[0061] Large-diameter crystals have large surface areas, which may result in increased friction drag between the crystals and the support surface of the horizontal chamber as the crystals expand and contract during the annealing process. Embodiments of the invention provide a method for reducing friction drag between the crystals and the support surface of the horizontal chamber during the annealing process.
[0062] FIG. 5 shows one method for reducing friction drag between the crystals 16 and the horizontal support surface 14 of the horizontal chamber 12 according to one embodiment of the invention. The method includes interposing sacrificial disks or spacers 42 between the crystals 16 and the support surface 14 of the horizontal chamber 12 . Preferably, the spacers 42 are made of the same or similar fluoride crystal material as the optical fluoride crystals 16 . The thickness of the spacers 42 can range from 0.125 to 1 in. or more. In general, the surface friction between the crystals 16 and the fluoride crystal material spacers 42 is much less than would have been observed if the crystals 16 were in direct contact with the support surface 14 of the horizontal chamber 12 .
[0063] One of the benefits of having the fluoride crystal material disks 42 between the crystals 16 and the support surface 14 of the horizontal chamber 12 is better cooling uniformity within the crystals 16 . Better cooling uniformity is achieved because the crystals 16 are raised off the support surface 14 of the horizontal chamber 12 . Raising the crystals 16 also reduces the effect of hot and cold temperature spots of the support surface 14 on the internal temperature of the crystals 16 , allowing an overall uniform temperature within the crystals 16 . The spacers 42 also eliminate or reduce contamination of the crystal surface by preventing direct contact between the crystals 16 and the horizontal chamber 12 .
[0064] FIG. 6 shows another method for reducing friction drag between the crystals 16 and the support surface 14 of the horizontal chamber 12 according to an embodiment of the invention. The method includes placing loosely-packed round cross-section spheres 44 between the crystals 16 and the support surface 14 of the horizontal chamber 12 . In general, spacers with round cross-sections, such as cylinders, could be packed between the crystals 16 and the support surface 14 . The round cross-section spheres spacer rollers 44 could be made of high-grade, high-density inert material, such as graphite, or the same or similar fluoride crystal material as the optical crystals 16 .
[0065] The round cross-section spheres spacer 44 reduce the contact area between the crystals 16 and the support surface 14 of the horizontal chamber 12 , thus significantly reducing the surface friction and allowing the crystals 16 to thermally expand and contract freely. The spheres 44 also allow process gases to flow under the crystals 16 to provide a more homogeneous atmosphere environment to the surfaces of the crystals 16 . This potential flow of gases under the crystals 16 mimics two-sided cooling, which allows for shorter cooling cycles and increased throughput. The increased surface area of the spheres 44 also increases the radiation view factors on the crystals 16 , greatly reducing the impact of slight hot or cold temperature spots of the support surface 14 on the internal temperature of the crystals 16 . The spheres 44 also reduce contamination of the crystal surface by preventing direct contact between the crystals 16 and the chamber 12 .
[0066] Those skilled in the art will appreciate that other crystal arrangements are possible which would allow heat to be conducted along the shortest path of conduction of the crystals. In other words, the invention is not limited to mounting the crystals 16 facedown (in a horizontal orientation) inside the horizontal chamber 12 . For example, FIG. 7A shows an alternative arrangement where the crystals 16 are mounted in an edgewise (vertical) orientation inside vertical chambers 48 . The crystals 16 are mounted on supports 46 inside the chambers 48 . The circumferential edges 50 of the chambers 48 are in turn mounted on supports 52 inside the furnace 20 . The vertical chambers 48 are shown as having a circular cross-section, but this is not a requirement for supporting the crystals 16 in an edgewise fashion. The vertical chambers 48 could be box-shaped, for example.
[0067] FIG. 7B shows a vertical cross-section of the arrangement shown in FIG. 7A . As illustrated, heating elements 54 are placed adjacent the vertical faces 56 of the chamber 48 to allow heat to be conducted along the shortest path of conduction of the crystal 16 , i.e., along the thickness of the crystal 16 . This assumes that the diameter-to-thickness ratio of the crystal 16 is greater than 1. The vertical faces 56 of the chamber 48 and/or the heaters 54 could include radiation-enhancing surfaces, such as previously described.
[0068] Preferably, the material used in making the chamber 48 is an inert material and is heat-resistant. In one embodiment, the vertical faces 56 of the chamber 48 are made of a material having a high thermal conductivity, and the circumferential edge 50 of the chamber 48 is made of a material having a low thermal conductivity. An example of a suitable material for making the vertical faces 56 is a graphite material having a thermal conductivity of 139 W/m.k. An example of a suitable material for making the circumferential edge 50 is a graphite material having a thermal conductivity of 50 W/m.k. The combination of low thermal conductivity and high thermal conductivity materials ensures that the majority of the heat applied to the chamber 48 is conducted along the shortest path of conduction of the crystal 16 .
[0069] The chamber 48 is mounted within an insulated chamber 64 inside the furnace 20 to allow for greater control of the heating and cooling rates of the crystal 16 . It should be noted that the insulated chamber 64 does not have to be sealed. In the illustration, the crystal 16 and heating elements 54 are arranged such their circumferential edges 16 a , 54 a , respectively, are rotated 90 degrees with respect to the round portion 21 of the furnace 20 . In another embodiment, such as shown in FIG. 7C , the crystal 16 and heating elements 54 could be rotated such that their circumferential edges 16 a , 54 a , respectively, have the same orientation as the round portion 21 of the furnace 20 . In this way, heat will still be conducted along the shortest path of conduction of the crystal 16 . This arrangement generally provides better heat uniformity across the crystal 16 .
[0070] It is desirable to have uniform heat distribution throughout the crystal 16 . FIG. 8A shows the desired uniform temperature gradient field within the crystal 16 . In reality, there will be some variation in the temperature distribution within the crystal 16 , particularly near the circumferential edge 60 of the crystal 16 . FIG. 8B shows the temperature gradient field “tailing off” near the circumferential edge 60 of the crystal 16 . In one embodiment, this tailing off can be minimized by placing a crystal edge insulator insulation material 62 , such as high purity graphite fiber, between the circumferential edge 50 of the chamber 48 and the circumferential edge 60 of the crystal 16 . The insulation material 62 would prevent rapid heat loss at the circumferential edge 60 of the crystal 16 as well as assist in the distribution of the gases introduced into the chamber 48 at port 66 . In another embodiment, localized heating can be applied near the circumferential edge 60 to minimize the tailing off.
[0071] Returning to FIG. 7A , the chamber 48 includes a port 66 through which process gases can be communicated to the crystal 16 . In one embodiment, a fluid line 67 is connected to the port 66 . The fluid line 67 passes through a port 68 in the furnace 20 to the exterior of the furnace 20 . The fluid line 67 can be connected to a process gas system (not shown) external to the furnace 20 , allowing independent control of the atmosphere within the chamber 48 . For example, fluorinating gases are typically used to scavenge oxides from crystals. Instead of filling the furnace 20 with the fluorinating agent and having the agent then flow into the interior of chamber 48 , the invention provides for the flow of the fluorinating agent first into the chamber 48 , where the crystal 16 resides, to be filled with the fluorinating agent, with the fluorinating agent and any contaminant reaction products to gaseously exit the chamber 48 and into the furnace interior outside chamber 48 , preferably so that there is a positive pressure of the fluorinating agent gas inside chamber 48 to sweep away gaseous reaction products (particularly scavenged oxides) to the exterior of chamber 48 and away from the optical fluoride crystals being annealed. Where multiple chambers 48 are loaded into the furnace 20 , the connections 67 between the ports 66 in the chambers 48 and the exterior of the furnace 20 allow different atmospheric conditions to be maintained within the multiple chambers 48 . Preferably chambers 48 are non-hermetic thereby allowing fluid communication between an interior of the chamber and an interior of the furnace.
[0072] FIG. 9 shows a process gas system where the chamber 48 is connected to gas tanks 70 , 72 . The gas tanks 70 , 72 could be sources of fluorinating gases, for example, or other process gases. The fluorinating gases could be mixed with inert gases. Mass flow controllers 71 , 73 are used to control flow from the gas tanks 70 , 72 into the chamber 48 . A purifier 74 is provided to maintain a desired moisture level in the chamber 48 .
[0073] The furnace 20 is connected to a gas tank 78 . The gas tank 78 could be a source of an inert gas, such as argon. This would allow an inert atmosphere to be maintained inside the furnace 20 during the annealing process. A mass flow controller 79 is used to control flow from the gas tank 78 into the furnace 20 . A purifier 80 is provided to maintain a desired moisture level in the furnace 20 . A vacuum pump 76 maintains vacuum in the furnace 20 as necessary.
[0074] Although not shown, the process gas system also includes various valves and regulators to control gas flow through the system. A control system (not shown) may be used to control the mass flow controllers, valves, regulators, purifiers, and vacuum pump such that the desired atmospheric conditions are achieved inside the furnace 20 and chamber 48 . A purge vent 82 allows gas to be purged out of the chamber 48 and furnace 20 as necessary. A purge gas supply line 84 carries purge gas to the chamber 48 and furnace 20 as necessary.
[0075] The process gas system shown in FIG. 9 allows gases to be supplied to and purged from the chamber 48 and furnace 20 independently. FIG. 10 shows an example of an annealing cycle for calcium fluoride crystals using the process gas system shown in FIG. 9 . The annealing cycle shows various types of gases that may be selected and introduced into the chamber 48 and furnace 20 at various times during the annealing process. Fluorinating gases, such as SF 6 and CF 4 , are introduced into the chamber 48 at temperatures where they are most effective in scavenging oxides from the calcium fluoride crystal. Other examples of fluorinating gases that may be used include NF 3 , BF 3 , C 2 F 4 , and F 2 .
[0076] As can be appreciated from the discussion above, the invention provides one or more advantages. Specifically, the invention allows heat to be distributed uniformly to one or more crystal disks, e.g., optical fluoride crystals, along the shortest path of conduction of the crystals during an annealing process. The invention also allows heat to be removed uniformly from the crystals during the annealing process. The results are annealed crystals having low birefringence values and shorter annealing cycles.
[0077] While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims.
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A method of making below 250-nm UV light transmitting optical fluoride lithography crystals includes applying heat along a shortest path of conduction of a selected optical fluoride crystal, heating the optical fluoride crystal to an annealing temperature, holding the temperature of the optical fluoride crystal at the annealing temperature, and gradually cooling the optical fluoride crystal to provide a low-birefringence optical fluoride crystal for transmitting below 250-nm UV light.
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This is a continuation of application Ser. No. 06/882,228, filed July 7, 1986, now U.S. Pat. No. 4,683,965.
BACKGROUND OF THE INVENTION
The present invention relates to oil well drill bits, and more particularly relates to an improved unitary drill bit having particular utility when drilling in soft to medium unconsolidated formations.
When drilling for oil in soft to medium unconsolidated formations such as those formations found along the Louisiana and Texas Gulf Coast areas of the United States, and in offshore waters of the Gulf of Mexico, "bit balling" is a very common problem. This problem relates to a heavy accumulation of the clay-like unconsolidated formation material around the bit as it rotates through the formation. The formation material actually adheres to the bit rather than flowing away after being cut.
Several patents relate to drill bits used in oil and gas well drilling operations. For example, U.S Pat. No. 2,169,223 to Christian entitled "Drilling Apparatus" relates to a drill bit which is used for flushing fluid into the bore along with the drill. The Christian device uses a flushing fluid that is forced down through the drill stem and passes through openings at the lowermost end portion of the drill bit. Flushing fluid will then return around the drill and the drill stem removing clogging material from the well bore. The Christian devices uses a drill having an axial bore extending from the upper to the lower end of the drill and having an inside seat around the bore. A discharge channel leads downwardly from the bore above the seat and of a tubular barrel shaped to fit through the bore. The Christian device uses two blades which are a fish tail type bit construction. Because of the outwardly extending enlarged fish tail type cutters of Christian, excessive torque can be generated in the drill string. Further, these outwardly extending fish tail type cutters can ball up in unconsolidated type formations known in the industry as "gumbo mud" or like formations.
Another fish tail type bit is the Scott U.S. Pat. No. 1,733,241 entitled "Method of Producing A Hard Surface on Tools and the Like." Scott discusses applying tungsten carbide using an atomic hydrogen torch to generate enough heat to melt the carbide itself. The tungsten carbide in molten condition then forms an alloy with the blade of the cutter according to the Scott patent.
U.S. Pat. No. 2,490,208 issued to H. E. Conklin and entitled "Soft Formation Core Bit Cutter Head" shows a tubular drill bit having outwardly extending cutter blades mounted upon a conically shaped bit which is round in cross-section.
Other patents showing various constructions for drill bits include U.S. Pat. Nos. 2,169,223; 1,887,372; 2,838,284; 2,673,716; and 2,756,023.
SUMMARY OF THE INVENTION
The present invention is an improvement over prior art drill bits, providing a unitary drill bit having a generally triangularly shaped cross-section which also narrows at its tip portion, providing three cutting blade portion at the apex of the triangular cross-section of the bit and three flat surfaces spanning between the cutting blades which enhance flow characteristics, i.e., the removal of cuttings using drilling fluids as the cuttings are removed from the well bore. Jets are provided between the blades and positioned on the flow surface areas to blast and remove cuttings instantly as they are removed from the well bore. The generally triangular shape of the drill bit body minimizes bit balling, swabbing, and surging while thrusting the tool into and out of the well bore with the drill string. The device can even be used for directional drilling by using jets of different sizes such as, for example, two small jets on two sides and one large jet on the third side. Thus, the direction and angle of the hole can be controlled by the jetting procedure. The apparatus as will be described more fully hereinafter thus provides a drill bit of one-piece construction which does not have cones that can come off of the tool or ball up while drilling. The apparatus is thus stronger than common cone-type drill bits and as aforedescribed has enhanced hydraulic and flow characteristics for instantaneous removal of cuttings even in soft or unconsolidated formations such as gumbo mud as is is termed in the industry.
BRIEF DESCRIPTION OF THE DRAWINGS
For a further understanding of the nature and objects of the present invention, reference should be had to the following detailed description, taken in conjunction with the accompanying drawings, in which like parts are given like reference numerals and wherein:
FIG. 1 is a side view of the preferred embodiment of the apparatus of the present invention;
FIG. 2 is an end view of the preferred embodiment of the apparatus of the present invention;
FIG. 3 is a sectional view taken along lines 3--3 of FIG. 1;
FIG. 4 is a sectional view taken along lines 4--4 of FIG. 3;
FIG. 5 is an end view of the preferred embodiment of the apparatus of the present invention; and
FIG. 6 is a fragmentary view illustrating the jetting assembly portion of the apparatus of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1 and 2 illustrate generally the preferred embodiment of the apparatus of the present invention designated generally by the numeral 10. Drill bit 10 includes a tubular body 12 having at its upper end portion threaded section 14 which is adapted to threadably attach to a drill string D shown in phantom lines in FIG. 1. The tool body 12 can provide indentations 13 with flat surfaces, for example, so that a wrench, power tongue or the like can be attached to the tool body 12 so that the tool body 12 can be tightened with respect to the drill string D. The central longitudinal axis of tool body 12 is designated as X--X in FIG. 1. The center of cylindrical bore 11 (FIG. 3) would coincide with the central longitudinal axis of tool body 12.
The lowermost end portion of tool body 12 carries the drill bit cutting portions. An enlarged head 14 has multiple flat surfaces which intersect as will be described more fully hereinafter. Drilling head 14 includes three uppermost generally flat surfaces 16, 17, 18 which are tangent outer surface of tool body 12 (see FIGS. 3 and 4). If tool body 12 were positioned vertically, surfaces 16-18 would define vertical planes tangent the tool body 12 outer surface. The flat sides 16, 17, 18 of bit 14 define a generally triangular shape as shown by dotted lines in FIG. 3, the vertices of the triangle being schematically shown in FIG. 3 as 19, 20, 21.
A plurality of three cutting blades 22, 23, 24 are mounted generally at each of the vertices 19, 20, 21 as shown in FIG. 3. Each cutting blade 22-24 is covered with a layer of carbide chips, for example, 25, 26, 27. In FIG. 5, arrows 28, 29, 30 show the direction of rotation of drill bit 10 during operation. Notice that each cutting blade 22-24 provides a cutting edge generally perpendicular to the direction of rotation 28-30 of drill bit 10. In FIG. 5, the leading or cutting edge of blades 22-24 are designated by the numerals 31, 32, 33. In FIG. 5, the well bore is designated by the curved dotted circular line WB. One skilled in the art will recognize that a well bore WB of the size and configuration shown in FIG. 5 will be cut when bit 10 is rotated in the direction shown by arrows 28-30 of FIG. 5.
The bottom tip of bit 10 provides a flat hexagonal surface 34 (FIGS. 2 and 5). Six generally flat surfaces form an obtuse angle with lowermost surface 34, including the surfaces 35-40. Notice that surfaces 35, 37, 39 are smooth and uncoated surfaces having jet openings 41-43 which outcrop at surfaces 35, 37, 39. Each surface 35, 37, 39 is an inclined surface that forms an acute angle with horizontal. In FIG. 4, for example, the inclination of surface 35 is designated as angle 35a.
Openings 41-43 communicate with jets 44-46 (see FIGS. 4-6). Surfaces 36, 38, 40 are covered with a layer of carbide chips.
FIG. 6 shows more particularly the construction of each jet assembly 44-46. Each jet assembly 44-46 comprises a cylindrical sleeve 50 having a bore 51 communicating with end portions 52, 53 of sleeve 50. A plurality of internal threads 54 allow insertion of a threaded jet thereinto. The end portion 52 of sleeve 50 can have a frustroconical bore section 55 as well as a cylindrical bore section 56 which is positioned inwardly and communicates with the bore 11 of tool body 12 as shown in FIG. 4. In FIG. 4, the arrows 60 schematically illustrate the flow of fluid through the jetting assembly 44.
FIG. 3 shows the communication of each jetting assembly 44-46 with the central bore 11 of tool body 12. Tool body 12 is preferably of a uniform cylindrical cross-section (see FIG. 3) between threaded section 15 and enlarged head 14. Similarly, central longitudinal bore 11 of tool body 12 is generally cylindrical as shown in FIG. 3, along its length, terminating at jetting assemblies 44-46.
The lowermost tip portion of drill bit 10 at surface 34 is seen in FIG. 5. Note that blades 22, 23, 24 extend to surface 34 with one of the blades (blade 24) preferably extending across the surface 34 in a transverse direction as shown in FIG. 5.
In the preferred embodiment, each blade 22, 23, 24 terminates at smooth surfaces 62, 63, 64. Thus, each blade 22, 23 is inclined an acute angle with respect to vertical as best seen in FIG. 1. Surfaces 65, 66, 67 extend from the cylindrical portion of tool body 12 toward the surfaces 62, 63, 64, and define the uppermost limits of the enlarged head 14 portion of tool body 12.
The entire drill bit 10 can be manufactured of any suitable structural material such as, for example, structural steel with carbide chips covering each blade 22, 23, 24 as shown in FIGS. 1, 2, 3, and 5.
In FIG. 5, three flow zones are defined by the circular dotted line designated as well bore WB and the flat surfaces 16, 17, 18 as well as the flat inclined surfaces 35, 37, 39. During rotation of the drill bit 10, these "zones" will allow fluid to flow from jet assemblies 44, 45, 46 up to the surface and along the tool body 12 and drill string D. Because the tool is triangularly shaped, the area between the well bore wall which is designated by the dotted lines in FIG. 5 and the flat surfaces 16, 17, 18 and 35, 37, 39 will be unoccupied by structure and thus filled with fluid. This fluid is injected through the bore 11 of the tool body 12 and exits as shown in FIG. 4 thorugh orifices 41-43. The fluid then travels upwardly carrying with it cut formation material which is removed from the well bore so that cutting will continue downwardly.
The above construction and operation provides an improved oil well drill bit that has particular utility in unconsolidated formations, commonly called "gumbo mud."
Because many varying and different embodiments may be made within the scope of the inventive concept herein taught, and because many modifications may be made in the embodiments herein detailed in accordance with the descriptive requirements of the law, it is to be understood that the details herein are to be interpreted as illustrative and not in a limited sense.
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A drill bit for use in unconsolidated formations includes a generally triangular cross-section that tapers toward the lower tip end of the tool. The vertices of the triangular cross-section carry blade members that cut and define the size of the bore hole. Nozzles positioned between the blades and upon the tapered portion of the tool break up unconsolidated formation material that has been cut.
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FIELD OF THE INVENTION
This invention relates to electronic circuits, and, more particularly, to a neuro-fuzzy network architecture having self-training or on-line learning capabilities.
BACKGROUND OF THE INVENTION
The invention particularly relates to a self-training neuro-fuzzy network architecture including at least one fuzzy microcontroller (fuzzyfier/defuzzyfier) dedicated for calculating fuzzy rules. The fuzzy microcontroller may be integrated monolithically in a semiconductor along with a non-volatile memory, for example. The invention also relates to a method of electronically controlling semiconductor-integrated electronic devices using self-training.
Of the currently available electronic devices integrated monolithically in a semiconductor, the fuzzy logic products typically fall in the category of processors, microcontrollers, or general purpose fuzzy co-processors. However, these products are unsuitable for operation in an on-line learning and self-training mode. For example, there exist no commercially available devices which include circuit portions adapted to process dedicated self-training instructions.
The unavailability of integrated devices with self-training processing features makes prior art approaches ill-suited to address problems requiring a capability to accommodate process variations and changing environmental conditions. Such is the case, for example, with the control of fuel injection systems in internal combustion engines and in other automotive applications.
The present invention is directed to a semiconductor integrated electronic device for enabling processing of predetermined instructions or data processing procedures by self-training. The technical problem addressed by the present invention is to provide a programmable device as described above which is of the neuro-fuzzy type.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a programmable integrated device of the neuro-fuzzy type with dedicated hardware appropriate for on-line learning capabilities. In essence, the invention provides a fuzzy neural system (hereinafter Fuzzy Neural Network or FNN) which uses the properties of neural networks to automatically learn the variations of a process to be controlled, as well as to adjust its behavior accordingly by adaptation of the fuzzy rule system parameters for increased efficiency throughout.
Based on this concept, the objects are achieved by a self-training neuro-fuzzy network including at least one fuzzy microcontroller dedicated to fuzzy rules computing, a non-volatile memory integrated monolithically with the at least one fuzzy microcontroller on a semiconductor and connected thereto, a microprocessor, a volatile memory, and a bus interconnecting the fuzzy microcontroller. The microprocessor, the volatile memory, and an arbiter circuit are connected to the bus. The arbiter circuit controls access to the volatile memory by the microprocessor and the fuzzy microcontroller.
More specifically, the self-training neuro-fuzzy network may also include a fuzzy co-processor connected between the fuzzy microcontroller and the microprocessor for performing fuzzy logic operations. The fuzzy co-processor may be a slave to the microprocessor. Furthermore, an arithmetic logic unit may be connected to the microprocessor, and the arithmetic logic unit may include a sequential machine including a plurality of internal registers.
Additionally, the volatile memory may be a dual port random access memory. The self-training neuro-fuzzy network may further include an interface connected between the volatile memory and the non-volatile memory for exchanging data therebetween. Also, an input/output (I/O) module may be connected to the microprocessor for interfacing with external peripherals.
The invention also relates to a method of electronically controlling an electronic device by self-training where the electronic device is monolithically integrated on a semiconductor and includes at least one fuzzy microcontroller for fuzzy rule computing and a non-volatile memory connected thereto. The method includes writing data from the non-volatile memory to a volatile memory, reading data from the volatile memory and executing predetermined sequences of instructions on the data, connecting an arbiter circuit to a bus interconnecting the fuzzy microcontroller, the microprocessor, and the memory unit, and activating a fuzzy co-processor with the arbiter circuit. The fuzzy co-processor is activated upon receipt and recognition of a fuzzy logic instruction from the volatile memory. Additionally, the fuzzy co-processor may be operated as a slave to the microprocessor.
BRIEF DESCRIPTION OF THE DRAWINGS
The features and advantages of the architecture and method according to the invention will become apparent from the following description of embodiments thereof, given by way of illustration and non-limitative example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a neuro-fuzzy network architecture according to the present invention;
FIG. 2 is a schematic diagram of an exemplary memory word including learning instructions for the architecture of FIGS. 1;
FIG. 3 is a schematic diagram of another exemplary memory word including fuzzy logic information for the architecture of FIG. 1;
FIG. 4 is a schematic diagram illustrating an arbiter block incorporated into the architecture of FIG. 1;
FIG. 5 is a schematic diagram of four-bit flag registers for use with the architecture of FIG. 1 .
FIGS. 6A, 6 B and 6 C show respective diagrams of fuzzy logic membership functions used in the architecture of FIG. 1;
FIG. 7 is a schematic diagram illustrating the construction of a fuzzy microcontroller of the architecture of FIG. 1;
FIG. 8 is a schematic diagram illustrating an alternate embodiment of the construction of a fuzzy microcontroller of the architecture of FIG. 1;
FIGS. 9 and 10 diagrammatically illustrate the membership functions used in the architecture of FIG. 1;
FIG. 11 is a schematic diagram illustrating a component of the architecture of FIG. 1;
FIG. 12 is a schematic diagram illustrating another component of the architecture of FIG. 1;
FIG. 13 is a plot of fuzzy logic membership functions used in the architecture of FIG. 1; and
FIG. 14 is a schematic diagram illustrating yet another component of the architecture of FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to the drawing figures, a circuit architecture 1 according to the present invention for implementing an on-line self-training neuro-fuzzy network in a single integrated electronic device is generally shown in schematic form. The architecture 1 may be conceptualized as a complex integrated system including a number of functional blocks. The inner construction and interconnections of these blocks with one another will now be described.
The inner construction of the system is shown schematically in FIG. 1 and includes a memory unit 2 , preferably (but not exclusively) a dual port random access memory (DPRAM). An arbitration block or circuit ARBITER 3 is adapted to manage the arbitration of a bus 4 interlinking the components of the system 1 . Further, a microprocessor 5 represents the decision or master portion of the system 1 . A dedicated fuzzy co-processor or fuzzyfier/defuzzyfier 11 calculates the fuzzy rules. A core fuzzy 6 is also included, which is a dedicated co-processor adapted to manage the fuzzy operations.
Moreover, the system includes a dedicated arithmetic logic unit (ALU) 7 for carrying out algebraic operations between various internal registers of the microprocessor 5 and the ALU 7 itself. A peripheral unit handling input/output (I/O) module 8 interfaces with certain external peripheral units. A non-volatile memory 9 , such as an EEPROM or other type of non-volatile memory unit, is also included. Additionally, an interface 10 is provided for exchanging data between the DPRAM unit 2 and the non-volatile EEPROM 9 .
The method of electronic control by self-training implemented by the architecture 1 of the present invention will now be explained. To provide the neuro-fuzzy network with improved interpreting capabilities, sigmoid and triangular activation functions are used, as explained hereinafter. The operational code for the action to be taken, i.e., the code containing the fuzzy rules, learning rules, and other calculation instructions to be used, is stored in the EEPROM 9 . The latter are loaded into the DPRAM 2 at power-on. It is from this memory that the microprocessor 5 receives the set of instructions to be interpreted and executed.
When the instruction is of the fuzzy type, the microprocessor 5 supplies the arbiter block 3 with a signal enabling the core fuzzy 6 to read from the DPRAM unit 2 . The core fuzzy 6 will then control the fuzzy co-processor 11 to execute the various rules. When the instructions are not of a fuzzy type, the instructions are executed directly by the microprocessor 5 or by the ALU 7 where algebraic operations are involved.
The construction, interconnections and operation of the individual functional blocks of the architecture 1 will now be described.
Microprocessor Block 5
The microprocessor 5 is the “heart” of the system 1 , and it decides on the action to be taken for each instruction read from the DPRAM unit 2 . The microprocessor 5 is enabled by a signal START from outside the integrated architecture 1 . For example, the signal START could be issued from a sensing device mounted on the same supporting board as the architecture 1 . Upon receiving the signal START, the microprocessor 5 begins to read, from the memory 2 , the number of fuzzy rules and the addresses where the parameters W, X, Y, MU are respectively stored or will be stored in the memory. In an initial state, the microprocessor 5 enables the arbiter block 3 by a signal SEL=0 enabling it to read from the DPRAM unit 2 . At the same time, the core fuzzy 6 is temporarily disconnected.
Simultaneously, the address bus 4 allows the first location in the memory unit 2 (being 0000 in the hexadecimal code) to be addressed, thereby placing the unit 2 in a read condition by enabling the signals RNW and NOTCS.
Upon receiving the signal START, the microprocessor 5 moves to a next state. Otherwise, it is kept in the initial state. In the states that come immediately thereafter, the microprocessor 5 will be respectively input with the parameters WPOS, XPOS, YPOS, MUPOS and ADDRULES. These parameter represent the addresses of the locations in the memory unit 2 where the weightings of the connections, the fuzzy inputs, defuzzyfied outputs from the fuzzy co-processor, activating values of the fuzzy rules, and address of the fuzzy rule calculation subroutine are respectively stored or will be stored. For example, there may be 256 addresses for the fuzzy rule calculation subroutine, with 8 inputs and 4 outputs per rule.
Directly after loading the parameters, the commands (i.e., the instructions) are interpreted. In addition to being fuzzy types, these instruction may be arithmetic or interrupt management types, in both hardware and software, such as INT 1 relating to the FNN network learning. The appearance of the hexadecimal code 0036 in the code stored in the DPRAM 2 results in the microprocessor 5 entering and being held in a wait state until it receives an interrupt signal (INT 0 , INT 1 , INT 2 , or NMI).
On the other hand, when a hexadecimal code FF 80 is read, a learning step is to be carried out. The microprocessor 5 jumps to a relative state in which it acquires the sign of the weighting variations and the learning coefficient, as explained hereinafter. This information is always included in the DPRAM unit 2 , and is set forth below to make the invention more clearly understood.
The information relating to learning has the format shown in FIG. 2 . Op may have a logic value of 0 or 1. When 0, it indicates a subtract operation, and when 1, it indicates an add operation. The bits from the seventh to the 14th (shown shaded) are not used. Therefore, the above memory word will include the numerical value expressed by the following number in binary form:
32768* Op+δ
where the numerical value 32768 results from the bit Op being at the fifteenth location and having, accordingly, the weighting 2 15 .
The learning step is carried out while taking account of the error which exists between the actual output from the FNN network (designated y FNN ) and the target output for the type of input pattern designated y target . That is:
w ( t+ 1)= w ( t )±(δ*μ)*(y FNN −y target )
In actual practice, the following empirical relationship is more frequently used:
w ( t+ 1)= w ( t )±(δ*μ)1/1024
To execute it, the microprocessor 5 must have received the values of the current weightings and the activation values, effect the division through 1024 (which is merely a ten-position rightward shift of the word δ*μ), execute the operation contained in Op with the weightings loaded from the DPRAM unit 2 , and store these values at the locations of the previously used weightings (i.e., overwriting them).
The weightings are located in the memory and stored as bytes within a word including two bytes so that one word will include two weightings W. The format of these weightings is shown in FIG. 3 . Thus, a word of weighting W 1 will have the binary value of the following number stored in it:
w 1 *256+ w 0
The same applies to the weightings W 2 and W 3 , and the operation is iterated for all the fuzzy rules. The iteration is performed by comparing the cumulative value in a counter CURRUL, which specifies the current rule, with the number of rules NRULES stored in the DPRAM unit 2 . As long as CURRUL<NRULES, the microprocessor 5 will iterate the comparison. Otherwise, it goes into the next state.
Arbiter Block 3
The arbiter block 3 is a circuit block designed to prevent possible clashes from occurring between the core fuzzy 6 and the microprocessor 5 when both try to access the DPRAM unit 2 . Initially, only the microprocessor 5 is enabled to read from the DPRAM unit 2 , and it will interpret instructions found therein and decide on the operations to be effected. In fact, if the microprocessor 5 encounters a fuzzy rule code at a given address in the DPRAM unit 2 , it then enables the core fuzzy 6 and simultaneously allows the arbiter block 3 to handle the access to the DPRAM unit 2 as appropriate. Conversely, if the microprocessor 5 reads non-fuzzy instructions, the arbiter block 3 will just enable the microprocessor 5 . The arbiter block is shown diagramatically in FIG. 4 .
ALU (Arithmetic Logic Unit) 7
The arithmetic logic unit 7 may be optionally included to allow the architecture 1 to perform computational operations not only of the fuzzy type but also of the mathematical type. This unit 7 will excute, as directed by the microprocessor 5 , arithmetic operations (addition, subtraction, multiplication, division), logic operations (AND, OR, NOT, XOR, etc.), as well as other data manipulations. Such data manipulations may include exchanging the contents of internal registers with memory locations, right and leftward shifts, single-bit testing, etc.
The ALU 7 includes internal circuitry arranged to perform the above-listed functions, and at least three sixteen-bit internal registers, designated A, B, C, a thirty-two-bit calculation block Alucalc, and four-bit flag registers, shown in FIG. 5 . The flag registers are modified by the ALU 7 according to the type of the computation result. The internal representation of the numbers is as follows:
The operations that the ALU 7 can effect include loading a memory location into a register and vice-versa, having two registers exchange their contents, additions, subtractions, divisions, multiplications, RCR and LCR shifts, logic operations, etc. The ALU 7 is a ten-state sequential machine adapted, in each of its states, to execute a given operation and prepare to retrieve the next. It includes an intelligent portion that allows it to interpret instructions and perform operations of the A*(B+C) type at once by its three internal registers.
Core Fuzzy 6
The core fuzzy 6 is a second dedicated microprocessor for handling and controlling the fuzzy co-processor, also called the fuzzyfier/defuzzyfier. This microprocessor supplies the fuzzyfier/defuzzyfier with properly timed control signals and handles the defuzzyfied outputs and the activation values of the “if” parts of the fuzzy rules. The core fuzzy 6 is a sequential machine working with sixteen bits and is basically a slave to the microprocessor 5 , which acts as the master. This core fuzzy 6 is enabled by the microprocessor 5 which issues a signal START. The signal START is brought to a high logic value only upon the instruction START FUZZY RULES being read from the DPRAM 2 or from an interrupt INT 0 . The machine language code of the fuzzy rules is located in a dedicated area of the DPRAM unit 2 extending from the address ADDRULES.
Initially, the core 6 is in its initial state in which it clears the outputs, and the address bus includes the address of the memory location ADDRULES where the fuzzy routines are stored. In this starting condition, a step of retrieving these routines is carried out. In this state, the core 6 will be waiting for the signal START to be enabled to the next state by the microprocessor 5 . Otherwise, the core fuzzy 6 retains its initial state.
Fuzzy Co-processor 11
This module comes in two possible versions, namely one for membership functions or fuzzy activation functions of the triangular type and the other for fuzzy activation functions of the sigmoid type. The triangular membership functions, shown in the example of FIG. 6A, are those most frequently used in fuzzy logics because they are easy to implement in hardware form.
The parameters that must be transferred to the inferential calculation block 12 (also present with the sigmoid membership functions), which calculates the degree of activation, are the vertices of the triangle representing the membership function. Its internal layout is shown in FIG. 7 . The inferential calculation block 12 calculates the activation values and their products by the fuzzy logic “then” parts. The block 12 includes blocks AlfaCalc and Defuzzifier, whose functions are specified herein below.
The AlfaCalc calculates the activation value of the input x associated with a given membership function. To outline the technique used for executing this calculation, by way of non-limitative example, each membership function is identified by three, eight-bit encoded parameters ‘a’, ‘b’ and ‘c’ forming its left, center and right coordinates, respectively. Based on this postulate, it becomes possible to represent either membership functions of triangular form or membership functions with saturation. For the latter, either the parameters ‘a’ and ‘b’ or the parameters ‘b’ and ‘c’ can be taken to coincide, thereby obtaining a left trapezoidal or a right trapezoidal membership function, respectively. This situation is illustrated schematically by FIGS. 6C and 6B.
The Defuzzifier stores the summation of the activation values, as supplied by the block AlfaCalc, and calculates the four summations of their product by the respective fuzzy logic “then” parts. In view of the fuzzyfying and defuzzyfying methods used, only the minimum or maximum “if” part activation value should be stored for each fuzzy rule processed, according to the type of the operation being executed, and subsequently be multiplied by its “then” part. In order to extend the summation to just the minimum or maximum calculated values for each rule, a comparator 15 is used to compare the currently stored value with the next value from the block AlfaCalc. This value is only stored if it is found to be smaller than the current value.
This solution has the advantage of requiring less area and being faster, since none of the internal memories and other modules needed in the sigmoid membership function approach are used here. A disadvantage is a limited fuzzy system performance in terms of non-linearity and FNN learning.
The Fuzzy Core for Sigmoid Membership Functions
The internal layout Fuzzy Core for Sigmoid Membership Functions is shown in FIG. 8 . It comprises a fuzzyfier block 20 , and a defuzzyfier block 30 inside two macroblocks. The sigmoid activation function is obtained as the difference between two membership functions having different centers and the same or different slopes, according to whether symmetrical or asymmetrical membership functions are sought. For this purpose, a read-only memory is used, such as a ROM 19 wherein the values of a normalized sigmoid of the following type are stored: y = 1 + tanh k 2
where the parameter k is given as:
k =α( x−c )
Once the value of k has been calculated based on the slope a and the center c, it is used through the block AlfaCalc as the address in the ROM 19 from which the corresponding ordinate value of the activation function can be read. By way of example, the inputs a, x, c are 8-bit inputs, thus they may represent values within the 0-255 range.
The architecture chosen being serial, the address is selected by the following logic. The first function parameters are passed first, and the second function parameters are then passed using input multiplexers whose outputs are caused to switch over by a control signal SEL. When SEL=0, a 1 and c 1 are loaded and the first parameter k 1 is calculated based on the current abscissa x. Simultaneously therewith, SEL=1 is assumed, and a 2 and c 2 are loaded to calculate the parameter k 2 using the same abscissa.
At k 1 and k 2 , which represent the addresses in the ROM 19 , the ordinate values of the activation function are read and the difference between these values is found. By iterating this process for all the combinations of the parameters a and c, the overall membership function is constructed. Advantageously, the solution proposed in the present invention takes into account the possibility of producing membership functions with a higher or lower slope than one.
Fuzzyfier Block 20
This module is used for the so-called fuzzyfication of the system inputs X, and therefore, to calculate inferential fuzzy rules of the “if” parts, of the following type:
If x 1 is A 11 AND/OR x 2 is A 12 AND/OR . . . x n is A 1n
The operation Og block 20 will now be described. Each fuzzy set A ij is represented by the parameters a 1 , c 1 , a 2 , c 2 indicating the slopes of the sigmoid branches and their centers. These parameters, expressed in an eight-bit binary code, are passed according to the type of the rule and along with a crisp input x to be fuzzyfied.
Before initiating a new set of fuzzy rules, the fuzzy block 20 should be reset so that the signal not_reset becomes zero. In this way, the system is placed in its initial state with the outputs and the internal registers all cleared. When fuzzy rules are to be executed, the signal not_reset must take a value of one. This is mandatory for the architecture 1 to be made ready to execute all the operations included in the following states. In order to move one state forward and execute the calculation of the activation value of the instruction x i is A i , it is necessary that the start signal be brought to a value of one. As the first instruction x i is A i of a generic rule is encountered, the signal Op (FIG. 2) must be brought to one, indicating that the first operation is a logic OR sum.
This condition is necessary for the fuzzyfier block 20 to yield a correct result for the activation value. In fact, all the internal registers are initially cleared. When the first instruction is presented, the OR operation (i.e., the calculation of the maximum value) is executed between the activation value just calculated and the value included in the register ATTIVAZIONEINT, which is zeo, thereby providing the correct value. If, during this first step, the operation had been a logic AND multiplication (i.e., the calculation of the minimum value), the result would be zero (i.e., erroneous).
As previously mentioned, the membership functions are represented by two sigmoid branches, and only one of them is stored in the ROM 19 and normalized to the value k. To construct the membership function, the difference is found between two sigmoid branches having either different or the same slopes and centers. The result of this difference represents the corresponding activation value to the input x. One example is shown in FIG. 13, where two sigmoid branches A, B have different parameters.
The architecture 1 is serial, and accordingly, the signal SEL=0 causes the parameters a 1 , c 1 and x to be passed, which are used by the block range 1 to calculate k 1 =a 1 (x−c 1 ). This value represents the address in the ROM 19 where the corresponding activation value stored therein can be read. This value is used as an address bus add for the ROM 19 . Reading from the latter is always enabled by the ROM 19 , which has its input CS and OE at ground value GND. The stored value is read at the address location k 1 , which is at once loaded into an internal register SIGMA 0 of the inference block via a data bus 21 linked to the ROM 19 .
During this operation, the output signal ready takes a zero value, indicating that the fuzzy block 20 is processing a fuzzy instruction x is A. Subsequently, the signal SEL is brought to one (SEL=1) by the inference block enabling the input multiplexers 25 of a module RANGE 1 to select a 2 , c 2 . The parameter k 2 =a 2 (x−c 2 ) is calculated at x, and the same operation is executed as previously described for a 1 and c 1 , except that the data is now loaded into a register SIGMA 1 , also inside the inference block.
Thereafter, during the activation step, the difference is calculated between the contents of SIGMA 0 and SIGMA 1 , which difference represents the activation value for the fuzzy instruction x 1 is A 11 . Upon completion of this calculation, the signals SEL and READY are again brought down to zero to prepare for the calculation of a new instruction.
The foregoing is iterated as many times as are the number of fuzzy instructions x i is A ij , while also passing each time the type of the composition rule (OR or AND) between them through the signal Op being either 0 or 1, respectively. The activation output will include the partial value of the activation value so far calculated, which will only become definitive upon the signal fine_regola taking the value of one. This indicates the arrival of the instruction “then” that marks the end of a rule to the fuzzyfier block 20 .
The Inference Block
This block is represented in FIG. 12 and carries out the fuzzyfication of the inputs.
ROM 3
The read-only memory or ROM 28 , also designated tan h, stores the values of one branch of a normalized sigmoid to the parameter k.
Block ADDMEM
This module acquires the parameters relating to the sigmoid membership functions sought and the input fuzzy sets. It also outputs the address of the location in the ROM 28 tan h where the input activation values or degrees of membership corresponding to the fuzzy sets can be read.
Defuzzyfier Block 30 This module calculates the “then” parts of the fuzzy rules and fuzzyfier them by the centroid method, once the fuzzyfier block has output the degree of activation of the inputs. As previously mentioned, the number of rules is 256 at most, with eight inputs and four outputs per rule. However, larger numbers of these rules and the fuzzy instructions x i is A ij could be provided at the expense of computational speed.
The degree of activation of the inputs is dependent upon the operation that has been selected in the inference block by the signal Op. In fact, for a given input x i , its value of activation to the fuzzy set is calculated using a membership function, designated μ i (x i ). This operation is carried out for all the inputs, and on its completion the degree of activation (designated μ(R i ), with R i being the i-th fuzzy rule) is calculated as AND, OR, product, scaling product, etc. of all μ i (x i )'s. The defuzzyfier module 30 is indeed intended to convert the fuzzyfied outputs of the fuzzy rules into crisp values using the centroid method as given by the following relationship: N°REGOLE y j = ∑ i = j N°REGOLE ( μ ( R i ) * W j ) ∑ i = 1 N°REGOLE μ ( R i )
FIG. 14 shows the internal architecture of the defuzzyfier block 30 . At the start of each fuzzy subroutine, the architecture 1 must be reset by enabling the signal not_reset to zero in order to clear all the internal registers and the outputs. Directly after this, the signal not_reset is brought to one. It is only then that the defuzzyfier block 30 will be input with the eight-bit degree of activation of the fuzzy rules from the fuzzyfier block 20 . The eight-bit weightings W 1 , W 2 , W 3 , W 4 of the FNN network connections, coming from the system input dual-port RAM unit 2 , are multiplied with the modules MULT 8 to yield a sixteen-bit result.
This operation is carried out in parallel with four multipliers 24 to obtain four defuzzyfied outputs per fuzzy rule. Since the activation signal contains the degree of partial activation of the fuzzy rules, which is to become definitive only when the signal end_rule is one (the equivalent of the instruction “then”), it becomes necessary to provide twenty four bit internal registers, initially reset. This is to include the sum of the signals OUTMOLI being the product of the activation by W i . These outputs represent the numerators NUMI of relationship 6.6, the denominator DE being calculated using a sixteen bit adder and a register of the same dimension. The dimensions, twenty four and sixteen, are from the former instance where 256 iterations must be provided (i.e., for the largest possible number of rules).
Effecting the ratii with four twenty-four-bit divisors between NUMI and DE, the outputs y 1 , y 2 , y 3 , y 4 are obtained. These outputs also have twenty four bits (of which only the sixteen least significant bits are meaningful since the eight most significant bits are always zeroes) and represent the four defuzzyfied outputs per fuzzy rule. The defuzzyfier block is a sequential machine.
The fuzzy neural network of this invention is designed to process sequentially any number of inputs. The maximum number of rules in the example is 256, but it may easily be raised above this value by increasing the number of bits of the internal modules (adders, multipliers and dividers) of the defuzzyfier block 30 . Furthermore, the architecture of this invention can provide several parallel outputs (in the example, only four such outputs have been illustrated).
The operational code relating to the fuzzy instructions includes encoding the set of fuzzy learning instructions and other operations in binary form. In general, it would be the coding of the following rule format:
if x 1 ( t k ) is A 11 AND/OR, . . . , x n ( t k ) is A 1n then y 1 ( t k+1 ) is W 11 , y 2 ( t k+1 ) is W 12 , y 3 ( t k+1 ) is W 13 , and y 4 ( t k+1 ) is W 14
- - - learning rule - - -
w i ( t+ 1)= w i ( t )±(δ*μ)*1/1024
If any abnormality or an interrupt signal occurs (e.g., from the supply system being turned off), the data momentarily in the DPRAM unit 2 is at once loaded into the EEPROM. This preserves the last weighting values, as modified by the learning process, of the FNN connections as well as the activation values and the defuzzyfied outputs.
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A neuro-fuzzy integrated architecture which permits on-line self-training includes at least one microcontroller of the fuzzy type dedicated to fuzzy rules computing and integrated monolithically on a semiconductor together with a non-volatile memory. Also included within the same integrated circuit are a microprocessor, a volatile memory unit, and an arbiter block linked to a bus interconnecting the fuzzy microcontroller, the microprocessor, and the volatile memory unit. The arbiter block controls access to the memory unit by the microprocessor or the fuzzy microcontroller. An additional fuzzy co-processor may be connected between the fuzzy microcontroller and the microprocessor for performing the fuzzy logic operations.
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FIELD OF INVENTION
[0001] This invention relates to novel compounds having S1P receptors modulating activity and the use of such compounds to treat diseases associated with inappropriate S1P receptor/s activity.
BACKGROUND
[0002] Sphingosine 1-phosphate (S1P) is a natural sphingolipid that functions as an intramolecular messenger in many types of cells and as an extracellular signalling molecule (for a recent review see Cooke et al, Annual Reports in Medicinal Chemistry, 2007, 42, pp 245-263 and references therein). The cellular effects induced by S1P are associated with platelet aggregation, cell morphology and proliferation, tumour cell invasion, endothelial cell chemotaxis and in vitro angiogenesis. The extracellular signalling occurs through interaction of S1P with G-protein-coupled receptors S1P1, S1P2, S1P3, S1P4 and S1P5. The intracellular activity of S1P and modulators has not been fully explored. S1P and its target have an essential role in lymphocyte migration through secondary lymphoid organs such the spleen, lymph nodes and mucosa-associated tissues such as the tonsils and Peyer's patches. The lymphocytes move from the peripheral circulation into the lymph nodes and mucosa associated tissues in order to generate immune responses. T and B lymphocytes are effectively sequestered within the thymus and secondary lymphoid tissue. Essentially, S1P and its receptor subtype −1 are required for lymphocytes to move out of the thymus and secondary lymphoid organs.
[0003] S1P type molecular modulators have been shown to be effective in multiple animal disease models. The S1P signalling, mainly through its receptor subtype-1, is important in halting the T reg response and has been recommended for immunotherapy of cancer and infectious disease (Liu, G., et al, Nature Immunology, 2009, 10, 769-777; Wolf, A. M., et al, J. Immunology, 2009, 183, 3751-60). The S1P mediated trans-activation of insulin receptor has been reported to help treating insulin resistance and type 2 diabetes (Rapizzi E. et al, Cell Mol Life Sci, 2009, 66, 3207-18). S1P1 receptor axis has a role in the migration of neural stem cells toward the site of spinal cord injury (Kimura, A., et al, Stem Cells, 2007, 25, 115-24). The S1P and its modulators supports the trafficking of hematopoietic progenitor cells and are helpful in tissue repair in myocardial infarction (Seitz, G., et al, Ann. N.Y. Acad. Sci., 2005, 1044, 84-89; Kimura, et al, Blood, 2004, 103, 4478-86) and a have great potential applications in regenerative medicines. S1P receptors play critical role in endothelial barrier enhancement and vasculature maturation (McVerry, B. J., et al, Journal of Cellular Biochemistry, 2004, 1075-85; Allende, M. L., et al, Blood, 2003, 102, pp 3665-7; Paik, J., et al, Genes and Development, 2004, 18, 2392-2403; Garcia, J. G. N., et al, J. Clinical Investigation, 2001, 689-701). The vasculature normalization helps the cytotoxic T cells to access the remote and inner part of the tumour (Hamzah J. et al, Nature, 2008, 453, pp 410-414). The lymphocyte egress and endothelial barrier function is mediated through S1P1 receptor (Brinkmann, et al, American J. of transplantation, 2004, 4, 1019-25; McVerry B. J. et al, Cellular Signalling, 2005, 17, pp 131-39). S1P type modulation reduces ischemia reperfusion injuries (Lein, Y. H., et al, Kidney International, 2006, 69, 1601-8; Tsukada, Y. T. et al, J Cardiovascular Pharmocol, 2007, 50, 660-9). S1P1 signalling is critical in preventing inflammation induced vascular leakage (Niessen, F. et al; Blood, 2009, 113, 2859-66; Wang L et al, Microvascular Research, 2009, 77, 39-45; Lee, J. F., et al, Am. J. Physiol Heart Circ Physiol, 2009, 296, H33-H42). It also reduces a vascular leakage in models of acute lung injury (McVerry, B. J., et al, Am J of Respiratory and Critical Care Medicine, 2004, 170, 987-93). The S1P vasculo-protection effect, mediated by nitric oxide and prostacyclin (Rodriguez C et al, Thromb Haemost, 2009, 101, 66-73), prevents the development of atherosclerotic lesions (Nofer, J. R. et al, Circulation, 2007, 115, 501-8; Tolle, M., et al, European J Clin Inv, 2007, 37, 17-9; Keul, P., et al, Arterioscler. Thromb. Vasc. Biol, 2007, 27, 607-13). S1P prevents tumour necrosis factor alpha mediated monocyte adhesion to endothelial cells, implicated in the pathology of arthrosclerosis and inflammatory diseases (Bolick, D. T. et al, Arterioscler. Thromb. Vasc. Biol, 2005, 25, 976-81). Recently reported target of S1P includes the family of Histone Deacylases (HDACs) (Hait, N. C., et al, Science, 2009, 325, 125-7), which are known for their role in epigenetic. The S1P has been reported to help treatment of the latent mycobacterium tuberculosis infection by promoting the processing and presentation of antigens (Santucci, M. B. et al, Biochem Biophys Res Comm, 2007, 361, 687-93). Additionally, the S1P and its modulators have cardio protective effects (Means, C. K., et al, Cardiovascular Research; 2009, 82, 193-200; Hofmann, U., et al, Cardiovascular Research, 2009, 83, 285-93; Tao, R., et al, J Cardiovasc Pharmacol, 2009, 53, 486-94) and the signalling axis of S1P are important in the treatment of myocardial infarction (Yeh, C. C., et al, Am J Physiol Heart Circ Physiol; 2009, 296, H1193-9). Thus S1P like molecular modulators have a great developmental potential in wide range of cardiovascular medicines. Role of S1P receptor subtype-1 in modulating nociception have recently been described (Selley S M J et al, Journal of Neurochemistry, 2009, 110, pp 1191-1202).
[0004] Fingolimod (2-amino-2-(2-[4-octylphenyl]ethyl)-1,3-propanediol) (FTY-720) is metabolised to a structural analogue of S1P and has been found to effect S1P receptors. The discovery of FTY-720 and its efficiency in animal models and clinical studies, related to many autoimmune diseases and cancer treatment, has resulted in research efforts into S1P receptors.
[0000]
[0005] FTY-720 decreases peripheral blood lymphocyte counts (lymphopenia) reversibly, without impairing the effector function of the immune cells (Pinschewer, D. et al, J. Immunology, 2000, 164, 5761-70). FTY-720 is an emerging novel drug for Multiple Sclerosis (MS) (Kieseier, B. C., et al, Pharmacological Research, 2009, 60, 207-11; Brown, B. A., The Annals of Pharmacotherapy, 2007, 41, 1660-8) and has a direct cyto-protective and process extension effect in oligodendrocyte progenitors (Coelho, R. P. et al, J. Pharmacology and Experimental Therapeutics, 2007, 323, 626-35; Miron, V. E. et al, Ann Neurol, 2008, 63, 61-71). It is effective against autoimmune related pathologies such as type-1 diabetes (Yang, Z., et al, Clin Immunology, 2003, 107, 30-5), arthritis (Matsuura, et al, Inflamm Res, 2000, 49, 404-10) and oxazolone stimulated colitis (Daniel, et al, Molecular Immunology, 2007, 44, 3305-16). FTY-720 interaction with cytosolic Phospholipase A2 and modulation the eicosanoids synthesis (Payne S. G. et al; Blood, 2007, 109, pp 1077-1085) indicates its potential as anti-inflammatory and antinociceptive agents and a safe pain killer (Coste, O., et al, J. Cell Mol. Med., 2008, Vol 12, 995-1004). The anticancer activity of FTY-720 is well documented by in vitro apoptotic activity studies as well as numerous animal model studies. The apoptotic mechanism observed in hepatocellular carcinoma cell lines is linked to the activation of protein kinase C delta (PKC-δ) (Hung, J. H., et al, 2008, 68, 1204-12). The apoptotic activity of FTY-720 against chronic myelogenous leukaemia and Philadelphia chromosome positive acute lymphocytic leukaemia was reported to be due to its control of Protein Phosphates 2A (PP2A) (Neviani et al, J of Clinical Investigation, 2007, 117, 24-21). Phosphorylated form of FTY-720 is speculated to be an anti-metastasis drug (Meeteren, et al, Cancer Lett., 2008, 266, 203-8). FTY-720 inhibits vascular endothelial cell growth factor induced vascular permeability (Sanchez, T., et al, J. Biological Chem., 2003, 278, 47281-90), linked to an anticancer and anti-metastatic effect in animal models (Azuma, H., et al, Cancer Res, 2002, 1410-19; Chua, C-W., at al, Int. J. Cancer, 2005, 117, 1039-48; LaMontange, K. et al, 2006, 66, 221-31). The anti-angiogenic effect of FTY-720 through its interaction with S1P receptor subtype −1, was described recently (Schmid, G., et al, J Cellular Biochem, 2007, 101, 259-70). FTY-720 helps favourable central nervous system (CNS) gene expression and improves the blood brain barrier function (Foster, C. A., et al, Brain Pathology, 2009, 19, 254-66). Few days of treatment with FTY-720 leads to complete eradication of chronic viral infection of lymphocytic choriomeningitis (Lanier, et al, Nature, 2008, 894-899). Its anti-fibrotic activity was reported recently (Brunati, A. M., et al, Biochem Biophys Acta, 2008, 1783, 347-59; Delbridge, M. S., et al, Transplantation Proceedings, 2007, 39, 2992-6). FTY 720 inhibits development of atherosclerosis in low density lipoprotein receptor deficient mice (Nofer, J. R., et al, Circulation, 2007, 115, 501-8; Tolle, M. et al, European J Clinical Investigation, 2007, 37, 171-79). FTY720 was effective in the treatment of cerebral ischemia in the mouse model (Czech, B., et al, Biochem Biophys Res Comm, 2009, online), indicating the great potential of S1P receptors modulators in the wide range of cardiovascular medicine. The derivatives of FTY-720 were reported as pulmonary barrier enhancers and thus potential agents for the development of critical care medicines (Camp, S. M., et al, J Pharmacol Experimental Therapeutics, 2009, online).
[0006] Of the classical mimics of S1P, the amino alcohols and their respective monophosphates, amino phosphonates, amino acids, alkoxyamino alcohols, alkyl carboxylates appear to be the most effective S1P receptors modulators. While an in vivo phosphorylation of the hydroxyl group of FTY 720 appears to be necessary for the most effective extracellular signalling and agonistic effect upon binding to S1P1-5, the apoptotic effect is limited to its non-phosphorylated form.
[0007] It is desirable to provide alternatives to FTY-720 and in particular alternative compounds with improved properties and/or activity. For example, this could include compounds with greater range of activity, altered or enhanced specificity, improved pharmacological properties or reduction in side effects.
[0008] Throughout this specification, use of the terms “comprises” or “comprising” or grammatical variations thereon shall be taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof not specifically mentioned.
SUMMARY OF INVENTION
[0009] In one aspect of the present invention there is provided a compound of formula (I)
[0000]
[0010] wherein G represents an organic substituent comprising in any combination one or more nitrogen, oxygen or sulphur atom(s). In one embodiment of this aspect of the invention, G is a group selected from the following:
[0000]
[0011] wherein R is independently selected from H, deuterium, CN, amino, alkylamino, CH 2 OH, alkoxy, CF 3 , an alkyl chain optionally containing one or more of deuterium, O, NR′R″ (wherein R′ and R″ are independently selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, heterocycle and substituted heterocycle) S, SO, SO2, halogen, a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-heteroatom double bond or a carbon-hetero atom triple bond, carbocycle, heterocycle, amide, sulphonamide, hydroxyl, —CH 2 COOH, —COOH, —OPO 3 H 2 , —PO 3 H 2 , cyclic phosphate, cyclic phosphonates and/or salts, tetrazole, and n is 0-4, with the proviso that if an amino group is present on the same carbon atom as R in group G, R is not hydroxyl,
[0000]
[0000] represents an optional bridging group;
the asterisks indicating the attachment within formula (I).
[0012] In the compound of formula (I), Z represents an organic moiety comprising at least one aromatic centre. X and Y separately, or in combination, are alkyl, alkyl-amino, alkoxy, an alkyl chain containing one or more of O, N, S, SO, SO 2 , halogen, a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-heteroatom double bond, carbocycle, heterocycle or a group selected from the following:
[0000]
[0013] wherein R 1 is selected from H or alkyl, the asterisks indicating the attachment within formula (I).
[0014] In an alternative or further preferred embodiment of this aspect of the invention, X, Y and Z separately, or in any combination, are selected from the following
[0000]
[0015] wherein the asterisks indicate the attachment within formula (I), R 2 is selected from halogen, H, deuterium, CN, amino, alkylamino, alkoxy, CF 3 , an alkyl chain (up to 20 carbon atom) optionally containing one or more of deuterium, OH, NR′R″ (wherein R′ and R″ are independently selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, heterocycle and substituted heterocycle) O, N, S, SO, SO 2 , halogen, a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-heteroatom double bond or a carbon-hetero atom triple bond, carbocycle, heterocycle, amide, sulphonamide and A represents one or more ring atoms or groups independently selected from the group consisting of C, N, O, S, CO, C═NR, SO or SO 2 , R 3 may be a linking group or alkyl, aryl, heterocycle or an optionally substituted alkyl chain.
[0016] In a further alternative embodiment of this aspect of the invention Z and G, in combination, are selected from the following groups:
[0000]
[0017] wherein R is as defined for group G, wherein A is defined as above and X is independently selected from the group consisting of heteroatom or heteroatom containing species such as O, N, S, SO, SO2, CO or C═NR and R 2 is as defined above, the asterisks indicating the attachment within formula (I).
[0000]
[0018] wherein A is defined as above, X and Y are independently selected from the group consisting of heteroatom or heteroatom containing species such as O, N, S, SO, SO2, CO or C═NR and R 2 is as defined above, the asterisks indicating the attachment within formula (I).
[0019] In the compound of Formula (I), the groups J, m and D separately, or in any combination, are selected from hydrogen, deuterium, alkyl, alkoxy, alkylamino, halogen, amino, hydroxy, oxo (═O), imino (═NR), cyano, aryl, variously substituted aryl, variously substituted heterocycle, variously substituted carbocycle, alkyl chain of 1-15 carbon atom optionally containing carbon-carbon multiple bond, carbon-hetero multiple bond wherein one or more carbon atoms can be independently replaced with oxygen, sulphur, SO, SO 2 , NR (wherein R is a substituent), aryl, carbocycle and heterocycle.
[0020] In one embodiment the group D, when present, is selected from H, deuterium, alkyl, aryl, heterocycle or cycloalkyl. In a further embodiment the group m, when present, is selected from unsubstituted or substituted aryl, carbocycle or heterocycle. In a yet further embodiment, the group J, when present, is selected from H, alkyl or one of the following groups:
[0000]
[0021] wherein n is 0-10, A is as defined above, R 4 is halogen, CN, amino, alkylamino, alkoxy, CF 3 , an alkyl chain containing one or more of O, N, S, SO, SO 2 , a carbon-carbon double bond, a carbon-carbon triple bond, a carbon-heteroatom double bond or a carbon-hetero atom triple bond.
[0022] In a further aspect of the invention there is provided compounds having S1P receptor modulating activity and/or expression against target cells.
[0023] A yet further aspect of the invention provides a pharmaceutical preparation comprising at least one compound described herein in any of its stereoisomeric and/or isotopic forms or physiologically tolerable and/or therapeutically effective salts or mixtures thereof in any ratio together with a pharmaceutically acceptable carrier(s) and/or excipient(s).
[0024] In a further aspect the invention provides the use of a compound of the invention in any one of its stereoisomeric and/or isotopic forms or physiologically tolerable and/or therapeutically effective salts or mixtures thereof in any ratio, for the production of a pharmaceutical for modulation of S1P receptor activity and/or expression against target cells.
[0025] In a further aspect the invention provides the use of a compound of the invention in any one of its stereoisomeric and/or isotopic forms and mixtures thereof in any ratio and/or physiologically tolerable and/or therapeutically effective salts for the production of a pharmaceutical for modulation of S1P receptor (extracellular and/or intracellular binders) activity and/or expression.
[0026] S1P receptors are cell surface receptors which include known receptor subtypes 1, 2, 3, 4, 5 and are regarded herein as S1P receptors. These extracellular S1P receptors may be present inside the cell on Golgi bodies, etc. There are other intracellular receptor/s, target/s, protein/s, enzyme/s where S1P interacts and are regarded as S1P receptor/s. The compounds of the invention could function as substrates of Sphingosine Kinases like SK1 and SK2 which are responsible for phosphorylation of S1P and are regarded as S1P receptor/s. Histone Deacylase/s (HDACs) are known intra-nuclear receptors of S1P and thus are regarded as S1P receptors. In broad terms, the invention includes any receptor binder, agonists or antagonists, or inverse agonists of the S1P receptor family including S1P1, S1P2, S1P3, S1P4 and S1P5, which is responsible for direct and or indirect effect of S1P and regards them as S1P receptor/s.
[0027] Further, the invention relates to the use of a pharmaceutical comprising at least one compound of the invention in any of its stereoisomeric and/or isotopic forms or physiologically tolerable and/or therapeutically effective salts or mixtures thereof in any ratio.
[0028] Further, the invention relates to the use of a pharmaceutical comprising at least one compound of the invention in any of its stereoisomeric and/or isotopic forms or physiologically tolerable and/or therapeutically effective salts or mixtures thereof in any ratio for the treatment of diseases and/or conditions caused by or associated with inappropriate S1P receptor modulating activity or expression, for example, autoimmune disease.
[0029] A further aspect of the invention relates to the use of a pharmaceutical comprising at least one compound of the invention in any of its stereoisomeric or isotopic forms or physiologically tolerable and/or therapeutically effective salts or mixtures thereof in any ratio for the manufacture of a medicament for the treatment of diseases and/or conditions caused by or associated with inappropriate S1P receptor modulating activity or expression such as autoimmune disease.
[0030] In yet a further aspect of the invention, the compounds of the invention can be used for the prevention and/or prophylaxis and/or treatment and/or immunotherapy of infectious diseases including any infection caused by viruses, bacteria, fungi, parasites, prions and/or any other pathogens.
[0031] Viral infections including but not limited to human immunodeficiency virus, Hepatitis (HAV, HBV, HCV), H1N1 influenza, chickenpox, cytomegalovirus infection, dengue fever, Ebola hemorrhagic fever, hand foot and mouth disease, herpes simplex, herpes zoster, HPV, influenza (Flu), Lassa fever, measles, Marburg Hemorrhagic fever, infectious mononucleosis, mumps, norovirus, poliomyelitis, progressive multifocal Leu-encephalopathy, rabies, rubella, SARS, smallpox (Variola), viral encephalitis, viral gastroenteritis, viral meningitis, viral pneumonia, west Nile disease and yellow fever.
[0032] Bacterial Infections including but not limited to actinomycosis, anaplasmosis, anthrax, bacterial meningitis, botulism, brucellosis, burkholderia infections, campylobacteriosis, cellulitis, chlamydiaceae infections, cholera, clostridium infections, coccidiomycosis, diphtheria, ehrlichiosis, empyema, gonorrhea, impetigomelioidosis legionellosis, leprosy (Hansen's Diseases), leptospirosis, listeriosis, lyme disease, bacterial endocarditis, endophthalmitis, pseudomembranous enterocolitis, erysipelas, Escherichia coli infections, necrotizing fasciitis, Fournier gangrene, furunculosis, fusobacterium infections, gram negative bacterial infections, gram positive bacterial infections, granuloma inguinale, hidradenitis suppurativa, histoplasmosis, hordeolum, impetigo, Klebsiella infections, ludwig's angina, lymphogranuloma venereum, maduromycosis, mycobacterium infections, MRSA infection, Mycoplasma infections, nocardia infections, onychomycosis, osteomyelitis, paronychia, pelvic inflammatory disease, plague pneumococcal infections, pseudomonas infections, psittacosis, puerperal infection, respiratory tract infections, retropharyngeal abscess, rheumatic fever, rhinoscleroma, rickettsia infections, rocky mountain disease, salmonella infections, scarlet fever, scrub typhus, sinusitis, shigellosis, spotted fever, bacterial skin disease, staphylococcal infections, streptococcal infections, syphilis, tetanus, trachoma, tick borne disease, epidemic typhus, tuberculosis, tularaemia, typhoid fever, urinary tract infections, whipple disease, whooping cough, vibrio infections, Yersinia infections, zoonoses, and zygomycosis,
[0033] Fungal infections including but not limited to aspergillosis, blastomycosis, candidiasis, coccidioidomycosis, cryptococcosis, tinea pedis and histoplasmosis.
[0034] Prion infections including but not limited to transmissible spongiform encephalopathy, bovine spongiform encephalopathy, Creutzfeldt-Jakob disease, Kuru fatal Familial insomnia and Alpers Syndrome.
[0035] In a further aspect of the invention, the compounds of the invention can be used for the prevention and/or prophylaxis and/or treatment and/or immunotherapy of cancer and immune mediated diseases which include immune related and inflammatory diseases; autoimmune diseases; allergic conditions; pain; central nervous system diseases; neurodegenerative diseases, cardiovascular diseases; haematological pathologies. For example, Multiple Sclerosis, Alzheimer's, dementia, Parkinson's, Huntington's, Amyotrophic Lateral Sclerosis, Coeliac, inflammatory bowel, Crohn's, ulcerative colitis, Lupus Erythematosus, Lupus Nehritis, osteoarthritis, psoriasis, pruritus, arthritis, rheumatoid arthritis, osteoporosis, Sjogren Syndrome, uveitis, asthma, hay fever, sleep disorders, macular degeneration, glaucoma, typel and 2 diabetes, myasthenia gravis, non-glomerular nephrosis, autoimmune hepatitis, Behcet's, glomerulonephritis, chronic thrombocytopenia purpure, haemolytic anaemia, Wegner's granuloma and fibrosis, nervous system (spasticity), spinal cord injury, spinocerebellar ataxia, tardive dyskinesia, cognitive disorders.
[0036] The compounds of the invention can be used for the prevention and/or prophylaxis and/or treatment and/or immunotherapy of or in, Down's syndrome, schizophrenia, bipolar disorder, drug dependence, Wernicke-Korsakoff syndrome, eating disorders, depression resulting from infection, hepatic encephalopathy, lung diseases such as grain handler's, Hermansky-Pudlak Syndrome, and adult respiratory distress syndrome (ARDS, obesity, digestive tract disease, anxiety, hyperalgesia, migraine, epilepsy and neuromuscular disorder.
[0037] In another embodiment the compounds of the invention can be used for prevention and/or treatment of vascular and/or cardiovascular diseases including, but not limited to, hypoxia, atherosclerosis, diabetic blood vessel disease like inflammation, hyper vascularisation related disorders such as cancer and neoplasm, heart failure, myocardial infarction, myocarditis, ischemia, hypotension, hypertension, reperfusion injury, angina pectoris, coronary artery disease, stroke, thrombosis, artery/vein blockage or obstruction, diabetic retinopathy, sepsis and kidney failure, reperfusion or injury.
[0038] In another embodiment the compounds of the invention can be used for prevention and/or prophylaxis and/or treatment and/or immunotherapy of liver diseases including but not limited to liver cirrhosis, viral liver infections, autoimmune hepatitis, liver failure, portal hypertension, hemochromatosis, Wilson's diseases, Gaucher disease, hepatoma, primary biliary cirrhosis, primary sclerosing cholangitis, sarcoidosis and Zwellweger syndrome.
[0000] In another embodiment the compounds of the invention can be used for the prevention and/or treatment and/or immunotherapy of solid and/or haematological cancers and tumor metastasis, including but not limited to acute B-cell leukaemia, lymphoma, chronic lymphocytic leukaemia, chronic myeloid leukaemia, hairy cell leukaemia, multiple myeloma, acute lymphocytic leukaemia, acute granulocytic leukaemia, acute myelogenous leukaemia, lung cancer, adrenal gland cancer, astrocytoma, glioma, brain cancer, bile duct cancer, bladder cancer, bone cancer, bowel cancer, colorectal cancer, breast cancer, cervical cancer, endometrial cancer, oesophageal cancer, melanoma, gallbladder cancer, Kaposi sarcoma, renal cancer, laryngeal cancer, liver cancer, mesothelioma, prostate cancer, sarcoma, skin cancer, stomach cancer, testicular cancer, uterine cancer, thyroid cancer, and pancreatic cancer.
[0039] In another embodiment the compounds of the invention can be used for prevention and/or treatment and/or immunotherapy of pain including chronic pain, which could either be somatogenic (organic) or psychogenic. The somatogenic pain may be of nociceptive, inflammatory and or neuropathic origin. The pain related to nociceptive pain, peripheral neuropathy, central neuropathy, neuralgia, migraine, psychotic, inflammatory and or neurological disorders.
[0040] In another embodiment the compounds of the invention can be used for organ transplant and/or allograft and/or autograft, for example, kidney, liver, lung, heart, skin, stem cell or bone marrow transplant and in the treatment of graft versus host disease.
[0041] In another embodiment the disclosed molecules can be used for prevention and/or treatment and/or immunotherapy for the pathologies caused by bioterrorism agents.
[0042] In another embodiment the compounds of the invention can be used as a vaccine adjuvant to boost and/or enhance the action of a vaccine and/or immune agent and/or for immunization; for example antigen, tumour cell lysate, B cell vaccine, T cell vaccine, dendritic cell vaccine boosting the immune response of cytotoxic cells, helper T cells and dendritic cells and for eradication and immunotherapy of immune related diseases and other preventable diseases such as chickenpox, cholera, diphtheria, whooping cough, meningococcal disease, hepatitis, Hemophilus influenzae type B (HIB), measles, mumps, rubella, poliomyelitis and tetanus.
[0043] In another embodiment the compounds of the invention can be used to mobilize the progenitor/stem cells preferably towards the site of injury, ischemia, stroke etc. The compounds can be used as cyto-protective agents, cardioprotective agent, neuro-protective agents and regenerative agents that may help host/patient to repair any organ damage, grow organs like muscle, nerve, blood vessel etc and to increase immune cells number.
[0044] As used herein, “treatment” includes any effect such as lessening, reducing, modulating and/or eliminating resulting in the improvement of the condition, disease or disorder to be treated.
[0045] An appropriate concentration level in treatment is from 0.01 nM to 1 Molar.
[0046] The compounds and compositions of the invention may be administered in combination with a variety of pharmaceutical excipients, including stabilizing agents carriers and/or encapsulation formulations known in the art.
[0047] In case of treatment of autoimmune and inflammatory diseases, the compounds of the present invention can be used alone or in combination with any suitable adjuvant, non limiting examples of which include, known immunosuppressants such as cyclosporine, tecrolimus, rapamycin, azathioprine, cyclophosphamide, dexamethasone, flunisolide, prednisolone, prednisone, amcinomide desonide, methylprednisolone, triamcinolone and alclometasone.
[0048] In case of treatment of infection and or cancer the compounds of the present invention can be administered alone or in any combination with any suitable adjuvant, non limiting examples of which include, other anticancer, antiviral, antibacterial, antifungal, and/or any anti-pathogen agent, a compound which could make a delayed type hypersensitivity response.
[0049] During vaccination/s and or immunization/s the molecule/s or compounds of the present invention may be used with T cell, B cell, dendritic cell, antigen, protein, protein conjugate and or like which could be used for such immunization purpose.
BRIEF DESCRIPTION OF THE FIGURES
[0050] FIG. 1 illustrates post-treatment lymophocyte counts
DETAILED DESCRIPTION OF THE INVENTION
[0051] The terms “compound”, “agent”, “active agent”, “chemical agent”, “pharmacologically active agent”, “medicament”, “active”, “molecule” and “drug” are used interchangeably herein to refer to a chemical compound that induces a desired pharmacological and/or physiological effect. The terms also encompasses pharmaceutically acceptable and pharmacologically active ingredients of those active agents/compounds specifically mentioned herein and compounds of the invention including but not limited to salts, esters, amides, prodrugs, active metabolites, analogs and the like. When the terms “compound”, “agent”, “active agent”, “chemical agent” “pharmacologically active agent”, “medicament”, “active” and “drug” are used, then it is to be understood that this includes the active agent per se as well as pharmaceutically acceptable and/or, pharmacologically active salt/s, esters, amides, prodrug/s, metabolites, analogs and the like.
[0052] The terms “effective amount” and “therapeutically effective amount” of an agent/s/compounds and compounds of the invention as used herein mean a sufficient amount of the compound to provide the desired therapeutic or physiological effect or outcome. A practitioner balances the potential benefits against the potential risks in determining what an appropriate “effective amount” is. The exact amount required will vary from subject to subject, depending on the species, age and general condition of the subject, mode of administration and the like.
[0053] A “pharmaceutically acceptable” carrier, excipient or diluent may include a pharmaceutical vehicle comprised of a material that may not be biologically active or otherwise undesirable, i.e. the material may be administered to a subject along with the selected active agent without causing any and/or a substantial adverse reaction. Carriers may include excipients and other additives such as diluents, detergents, colouring agents, wetting or emulsifying agents, pH buffering agents, preservatives, and the like.
[0054] The compositions and combination therapies of the invention may be administered in combination with a variety of pharmaceutical excipients, including stabilizing agents, carriers or encapsulation formulations. Effective combinations are those which provide favourable synergistic effect which assist in treatment and/or prevention and/or immunotherapy better than the agents alone.
[0055] As used herein, the term “optionally substituted” means that one or more hydrogen atoms may be replaced by a group or groups selected from: -D, —F, —Cl, —Br, —I, —CF3, —OH, —OR7, —NH2, —NHR7, —NR7R8, —CN, —NO2, —SH, —SR7, —SOR7, —SO2R7, ═O, ═S, ═NOH, ═NOR7, —NHOH, —NHOR7, —CHO, where R7 and R8 are independently (C1-C18)alkyl, typically (C1-C12)alkyl; (C3-C18)cycloalkyl, typically (C3-C12)cycloalkyl; (C3-C18)cycloalkyl(C1-C18)alkyl, typically (C3-C12)cycloalkyl(C1-C6)alkyl; (C6-C24)aryl, typically (C6-C16)aryl; (C7-C25)aralkyl, typically (C7-C16)aralkyl; (C2-C18)alkenyl, typically (C2-C12)alkenyl; (C8-C26)aralkenyl, typically (C8-C16)aralkenyl; (C2-C18)alkynyl, typically (C2-C12)alkynyl; (C8-C26)-aralkynyl, typically (C 8 -C 16 )aralkynyl; or heterocyclic.
[0056] As used herein, the term “alkyl” includes within its meaning straight and branched chain alkyl groups. Examples of such groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1-dimethyl-propyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethyl-pentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyl-octyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5,6- or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1- or 2-pentylheptyl, and the like.
[0057] A used herein, the term “cycloalkyl” refers to mono- or polycyclic alkyl groups, or alkyl substituted cyclic alkyl groups. Examples of such groups include cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, decahydronaphthyl, bicyclo[2.2.1]heptanyl, bicyclo[2.2.2]octanyl, bicyclo[3.3.2]decyl, bicycleo4.4.3]dodecyl, bicyclo[4.4.0]octyl and the like.
[0058] As used herein, the term “cycloalkylalkyl” refers to an alkyl group substituted with a cycloalkyl group as defined above.
[0059] As used herein, the term “alkenyl” includes within its meaning ethylenically mono-, di- or poly-unsaturated alkyl or cycloalkyl groups as previously defined. Examples of such alkenyl groups are vinyl, allyl, 1-methylvinyl, butenyl, isobutenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-headienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3 cycloheptadienyl, 1,3,5-cycloheptatrienyl and 1,3,5,7-cyclooctatetraenyl.
[0060] As used herein, the term “alkynyl” includes within its meaning acetylenically unsaturated alkyl groups as previously defined. Examples of such alkynyl groups are ethynyl, propynyl, n-butynyl, n-pentynyl, 3-methyl-1-butynyl, n-hexynyl, methyl-pentynyl, (C7-C12)alkynyl and (C7-C12)cycloalkynyl.
[0061] As used herein, the term “alkylidene” refers to optionally unsaturated divalent alkyl radicals. Examples of such radicals are —CH2—, —CH2CH2—, —CH═CH—, —CH2CH2CH2—, —C(═CH2)CH2—, —CH2CH═CH—, —(CH2)4—, —CH2CH2CH═CH—, —CH2CH═CHCH2—, and —(CH2)r- where r is 5-8. The term also refers to such radicals in which one or more of the bonds of the radical from part of a cyclic system. Examples of such radicals are groups of the structures
[0000]
[0062] and similar groups wherein any N or O atom is replaced by S or Se.
[0063] As used herein, the term “aryl” refers to single, polynuclear, conjugated and fused residues of aromatic hydrocarbons or aromatic heterocyclic ring systems. Examples of such groups are phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl, fluorenyl, pyrenyl, indenyl, azulenyl, chrysenyl, pyridyl, 4-phenylpyridyl, 3-phenylpyridyl, thienyl, furyl, pyrryl, indolyl, pyridazinyl, pyrazolyl, pyrazinyl, thiazolyl, pyrimidinyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, purinyl, quinazolinyl, phenazinyl, acridinyl, benzoxazolyl, benzothiazolyl and the like. In all cases, any available position of the fused or conjugated bicyclic system can be used for attachment to the remainder of the molecule of formula (I).
[0064] As used herein, the term “aralkyl” refers to alkyl groups substituted with one or more aryl groups as previously defined. Examples of such groups are benzyl, 2-phenylethyl and 1-phenylethyl.
[0065] As used herein, the terms “aralkenyl” and “aralkynyl” refer to alkenyl and alkynyl groups respectively, substituted with one or more aryl groups as previously defined. Examples of such groups are styryl, phenylacetylenyl and 2-phenyl-2-butenyl.
[0066] As used herein the term “saturated or unsaturated cyclic, bicyclic or fused ring system” refers to a cyclic system of up to 16 carbon atoms, up to 3 of which may be replaced by O, S or N, which ring system may be substituted with one or more of R, —NH2, —NHR, —NR2, —CHO, —C(O)R, —CN, halo, —CF3, —SR, —S(O)R, —S(O)2R, —CONH2, —CONHR, —CONR2, —NHOH, —NHOL, —NO2, ═O, ═S or —NHNH2; wherein each R are independently as previously defined. Examples of such ring systems are those cyclic alkylidene groups exemplified above and
[0000]
[0067] As used herein, the term “heterocyclic” refers to any 3- to 16-membered monocyclic, bicyclic or polycyclic ring containing, for 3- and 4-membered rings, one heteroatom; for 5-membered rings, one or two heteroatoms; for 6- and 7-membered rings, one to three heteroatoms; for 8- and 9-membered rings, from one to four heteroatoms; for 10- and 11-membered rings, from one to five heteroatoms; for 12- and 13-membered rings, from one to six heteroatoms; for 14- and 15-membered rings, from one to seven heteroatoms; and for 16-membered rings, from one to eight heteroatoms; the heteroatom(s) being independently selected from oxygen, nitrogen and sulphur. The term “heterocyclic” includes any group in which a heterocyclic ring is fused to a benzene ring. Examples of heterocyclics are pyrryl, pyrimidinyl, quinolinyl, isoquinolinyl, indolyl, piperidinyl, pyridinyl, furyl, thiophenyl, tetrahydrofuryl, imidazolyl, oxazolyl, thiazolyl, pyrenyl, oxazolidinyl, isoxazolyl, isothiazolyl, isoxazolidinyl, imidazolidinyl, morpholinyl, pyrrolidinyl, pyrazolyl, pyrazolinyl, furfuryl, thienyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzoisothiazolyl, benzothiadiazolyl, tetrazolyl, triazolyl, thiadiazolyl, benzimidazolyl, pyrrolinyl, quinuclidinyl, azanorbornyl, isoquinuclidinyl and the like. Nitrogen-containing heterocyclics may be substituted at nitrogen with an oxygen atom. Sulfur-containing heterocyclics may be substituted at sulfur with one or two oxygen atoms.
[0068] Configurations which result in unstable heterocyclics are not included within the scope of the definition of “heterocyclic” or “saturated or unsaturated cyclic, bicyclic or fused ring system”.
[0069] As used herein, the term “alkylheterocyclic” refers to a heterocyclic group as defined above, which is substituted with an alkyl group as defined above.
[0070] As used herein, the term “heterocyclic-oxy-alkyl” refers to a group of the formula heterocyclic-O-alkyl, wherein the heterocyclic and alkyl are as defined above.
[0071] As used herein, the term “alkoxy” refers to a group of the formula alkyl-O—, wherein the alkyl group is as defined above.
[0072] As used herein, the term “aryloxy” refers to a group of the formula aryl-O—, wherein the aryl group is as defined above.
[0073] As used herein, the term “alkanoyloxy” refers to a group of the formula alkyl-C(O)O—, wherein the alkyl group is as defined above.
[0074] As used herein, the term group (a) refers to five member saturated or unsaturated cyclic or heterocyclic ring systems. Examples of such ring systems are:
[0000]
[0075] As used herein, the term group (b) refers to five member unsaturated cyclic or heterocyclic ring systems. Examples of such ring systems are:
[0000]
[0000] wherein each Ar and R are independently as previously defined and S and Se can be in the oxidized form S(O), S(O) 2 and Se(O) and Se(O) 2 respectively.
[0076] As used herein, the term group (c) refers to five-six bicyclic member ring systems. Examples of such ring systems are:
[0000]
[0077] wherein each R, R 1 and Q 1 are independently as previously defined and S and Se can be in the oxidized form such as S(O), S(O) 2 and Se(0) and Se(O) 2 respectively.
[0078] As used herein, the term group (d) refers to six-six hetero-bicyclic member ring system. Examples of such ring systems are:
[0000]
[0000] wherein each R, R 1 and Q are independently as previously defined.
[0079] The compound preparations illustrated can be carried out by generally known methods as exemplified hereinafter. The starting materials and intermediates used in the synthesis of compounds of this invention are generally commercially available or may be prepared by conventional methods of organic chemistry. Suitable methods for the synthesis of compounds of this invention and intermediates thereof are described, for example, in Houben-Weyl, Methoden der Organischen Chemie ; J. March, Advanced Organic Chemistry, 3rd Edition (John Wiley & Sons, New York, 1985); D. C. Liotta and M. Volmer, eds, Organic Syntheses Reaction Guide (John Wiley & Sons, Inc., New York, 1991); R. C. Larock, Comprehensive Organic Transformations (VCH, New York, 1989), H. O. House, Modern Synthetic Reactions 2nd Edition (W. A. Benjamin, Inc., Menlo Park, 1972); N. S. Simpkins, ed. 100 Modern Reagents (The Royal Society of Chemistry, London, 1989); A. H. Haines Methods for the Oxidation of Organic Compounds (Academic Press, London, 1988) and B. J. Wakefield Organolithium Methods (Academic Press, London, 1988).
[0080] Representative compounds in accordance with the invention are described in the following Tables.
[0000] TABLE 1 Compounds of formula S. N. R X—Y G1 G2 1 CF3 —CH2—CH2 2 Me —O—(CH2)3— 3 CH2CF3 —CH2—O— 4 Ph —CH2—O— 5 —CH2—CH2 6 CH2—CH2— 7 —CH2—O— 8 —CH2—O— 9 —CH2—O— 10 —CH2—O— 11 —CH2—O— 12 —CH2—O— 13 —CH2—O— 14 —CH2—O— 15 —CH2—CF3 —NH—SO2— 16 —CF3 17 —CH2—CF3 —C≡C— 18 Me 19 —C≡C— 20 —C≡C— 21 —C≡C— 22 —C≡C— 23 —C≡C— 24 —C≡C— 25 —C≡C— 26 —C≡C— 27 —C≡C— 28 —C≡C— 29 OMe —CH2—O— 30 OCH2CF3 —CH2—O— 31 OMe 32 OCH2CF3 33 OMe 34 OMe 35 OCH2CF3 36 CF3 —OCH2—CH2O— 37 CN —CH2O— 38 N(Me)2 —CH2—CH2— 39 OEt —CH2O— 40 OPr —CH2O— 41 OPr —CH2O—, —CH2CH2—
and variations thereof.
G1 and G2 represent alternative groups for G
[0000] TABLE 2 Compounds of Formula S. N. R1 R2 G 1 —CH3 2 —CH2CH2CH3 3 —CH3 4 —CH3 5 6 7 —CH2CF3 Ph 8 —Me Ph 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 —CH2CF3 27 —CH2CF3 28 —CH2CF3 29 —CH2CF3 30 —CH2CF3 31 H, Me 32 H, Me 33 H, Me
and variations thereof.
[0000] TABLE 3 Compounds of formula S. N. R1 R2 X Y G 1 —CH2— Ph 2 CH2 Ph 3 CH2 4 —SO2— Ph 5 —CO— Ph 6 —CH2— —CH2CH2— 7 —CH2CF3 —CH2— Ph 8 —Me —CH2— Ph 9 —CH2— 10 —CH2— 11 —CH2— 12 —CO— 13 —CH2— —CH2CH2— 14 —CO— —CH2CH2— 15 —CH2— 16 —CH2— —CH2CH2— 17 —CH2— 18 —CH2— —CH2CH2— 19 —CH2— —CH2CH2— 20 —CH2— 21 —CH2— 22 —SO2— Ph 23 —CH2— —CH2CH2— 24 —CH2— 25 —CH2— —CH2CH2— 26 —CH2CF3 —CO— —CH2CH2— 27 CH2CF3 —CH2— 28 —CH2CF3 —SO2— Ph 29 —CH2CF3 —CH2— 30 —CH2CF3 —CH2— Ph 31 Me —CH2— —CH2— 32 n-Hexyl Me CH2— CH2—
and variations thereof.
[0000] TABLE 4 Compounds of formula Compound No. R X R1 G 1 —CH 2 — H 2 —CH 2 — Cl 3 —CH 2 — CF3 4 —CH 2 — CF3 5 —O— iPr 6 —S— H 7 —O— 8 —CH 2 — Me 9 —O— H 10 —CH 2 — H 11 —O— CF 3 12 —O— —CH 2 — —S— H 13 —O— Cl 14 —O— F 15 —O— CF 3 CF 2 16 —O— F
and variations thereof.
[0000] TABLE 5 Compounds of formula Compound No. R R1 R2 G 1 iPrO— H 2 iPrO— H 3 iPrO— 3-CF3 4 MeO— Cl 3-F 5 Cl Cl 2-Me 6 Me CF3 CF3 7 i-Pr CF3 H 8 n-Bu F 3-Cl 9 Br H 10 iPrO— H 11 Cl Cl 2-Me 12 i-Pr CF3 2-Me 13 CF3 H 14 n-Pr CN 3-Me 15 nPr H 2-isoPr
and variations thereof.
[0000] TABLE 6 Compounds of formula Compound No. X R1 R2 R3 1 O OEt OEt H 2 N OEt OEt H 3 O —OEt —OEt —OP(O)(OH) 2 — and or salt of choice 4 O —OiPr —Cl —H 5 S —O—Et —OEt —H 6 O —O—Pr —OMe —H 7 O —OEt —CN —H 8 O —OPr —CF3 —H 9 O —OPr —Br —H 10 O —OPr —Me —H 11 O —OBut —H —H 12 O —O-pentyl —H —H 13 O -cyclohexyl —H —H 14 O —N(Et)2 —H —H 15 O —OEt —H 16 O —OMe —H 17 O —H —H 18 S -nPr —H —H
and variations thereof.
[0000] TABLE 7 Compound of formula Compound No. Ar X R3 1 O H 2 N H 3 O H 4 O H 5 S H 6 O H 7 O H 8 O H 9 O H 10 O H 11 O H 12 O H 13 O H 14 O H 15 O H 16 O H
and variations thereof.
[0000] TABLE 8 Compound of formula Compound No. T R R′ 1 OH 6-Cl 2 OH 7-isoprpyl 3 OH 6-Cl 4 OH H 5 OH 7-Me 6 OH 7-Et 7 OH 8 OH 6-Cl 9 OH 6-Cl 10 OH H 11 OH H 12 OH H 13 n-Octyl OH n-Octyl
And variations thereof.
s represents a ring subsituent.
[0000] TABLE 9 Compound of formula X , Y and G are as defined for formula (I). Compound No. T R R′ 1 OH 6-Cl 2 OH 7-isoprpyl 3 OH 6-Cl 4 OH H 5 OH 7-Me 6 OH 7-Et 7 OH 8 OH 6-Cl 9 OH 6-Cl 10 OH H 11 OH H 12 OH H 13 n-Octyl OH n-Octyl
And variations thereof.
s represents a ring substituent.
Methods of Synthesis:
[0081] The examples (28) to (30) were prepared by the use of following procedure as in Scheme-1
[0000]
[0082] The examples (36) to (52) were prepared by the use of following procedure as in Scheme-2 (a-b).
[0000]
[0000]
[0083] The other compounds of invention including intermediates were prepared by using various known synthesis methods like reductive amination etc. The compound preparations illustrated can be carried out by generally known methods as exemplified hereinafter. The starting materials and intermediates used in the synthesis of compounds of this invention are generally commercially available or may be prepared by conventional methods of organic chemistry. Suitable methods for the synthesis of compounds of this invention and intermediates thereof are described, for example, in Houben-Weyl, Methoden der Organischen Chemie; J. March, Advanced Organic Chemistry, 3rd Edition (John Wiley & Sons, New York, 1985); D. C. Liotta and M. Volmer, eds, Organic Syntheses Reaction Guide (John Wiley & Sons, Inc., New York, 1991); R. C. Larock, Comprehensive Organic Transformations (VCH, New York, 1989), H. O. House, Modern Synthetic Reactions 2nd Edition (W. A. Benjamin, Inc., Menlo Park, 1972); N. S. Simpkins, ed. 100 Modern Reagents (The Royal Society of Chemistry, London, 1989); A. H. Haines Methods for the Oxidation of Organic Compounds (Academic Press, London, 1988) and B. J. Wakefield Organolithium Methods (Academic Press, London, 1988). Some important Lit ref are Kim S et al, Synthesis, 2006, 5, 753-755.
EXAMPLES
[0084] The following Examples describe the preparation of compounds according to the invention and are intended to illustrate the invention. The Examples are not be construed as limiting in any way the scope of the present invention. Proton NMR spectra were recorded at 300 MHz on a Bruker EM 300 spectrometer in CDCl3 unless otherwise stated. Chemical shifts for proton NMR are ppm downfield from tetramethylsilane.
[0000]
Example 1
5-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-carboxylic acid
[0085] Step A: Step A: 4-Hydroxy-3-iodobenzonitrile: To a solution of 4-hydroxybenzonitrile (0.5 g; 4.18 mmol) in 25% NH 4 OH (22 ml) a solution of I 2 (1.06 g; 4.18 mmol) and KI (3.41 g; 20.54 mmol) in H 2 O (5 ml) was added at once with stirring. The stirring was continued for 6 h, during which time the mixture turn from black into colourless. The precipitate formed was filtered off and filtrate was evaporated to dryness under reduced pressure. The residue was treated with H 2 O (3 ml). The precipitate formed was filtered off, washed with cold H 2 O (3×2 ml), and dried in vacuo to give the title compound (0.82 g; 80%), as colourless solid. 1 H-NMR (CDCl 3 ) 7.96 (d, 1H, 1.9 Hz); 7.53 (dd, 1H, J=1.9 Hz, 8.5 Hz); 7.03 (d, 1H, J=8.5 Hz); 6.03 (s, 1H);
[0086] Step B: 2-(Hydroxymethyl)benzofuran-5-carbonitrile: Propargyl alcohol (0.24 ml; 5.2 mmol) was added drop wise during 30 min to a refluxed suspension of the product of Step A (0.48 g; 1.96 mmol) and Cu 2 O (0.28 g; 1.96 mmol) in anhydrous pyridine (4 ml) with stirring under N 2 . After additional reflux for 15 min, the mixture was cooled to room temperature, diluted to 20 ml with ethyl acetate (EtOAc) and insoluble material was removed by filtration. The filtrate was evaporated to dryness under reduced pressure and the residue was diluted to 20 ml with EtOAc, washed with diluted HCl (10 ml). The insoluble material formed was filtered off and the organic phase was washed with H 2 O (5 ml), brine, dried over anhydrous MgSO 4 , filtered and the filtrate evaporated to dryness. The residue was purified by flash column chromatography (FCC) (SiO 2 , CH 2 Cl 2 and EtOAc, 9:1) to give the title compound (0.23 g; 67%) as a colourless solid. 1 H-NMR (CDCl 3 ) 7.86 (m, 1H); 7.49-7.55 (m, 2H); 6.72 (d, 1H, J=3 Hz); 4.8 (d, 2H, J=3 Hz); 2.18 (broad s, 1H);
[0087] Step C: N-Hydroxy-2-(hydroxymethyl)benzofuran-5-carboximidamide: A mixture of the product of Step B (0.22 g; 1.27 mmol) and HCl×NH 2 OH (0.18 g; 2.59 mmol) and N,N-diisopropylethylamine (DIPEA) (0.67 ml; 3.82 mmol) in ethanol (EtOH) (2 ml) was stirred for 3 h at ˜71° C. The solvents were removed in vacuo and the residue was treated with H 2 O (3 ml) and the product was taken up by EtOAc (3×15 ml). The combined organic phase was washed with brine, dried over anhydrous MgSO4, filtered and filtrate evaporated to dryness to give the title compound (0.2 g; 76%), as colourless solid, which was used in the next step without further purification.
[0088] Step D: (5-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)ethanol: A mixture of 3,4-diethoxybenzoic acid (0.21 g; 1 mmol), the product of Step C (0.2 g; 0.97 mmol) and hydrochloride salt of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) (0.22 g; 1.15 mmol) in anhydrous dimethylsulfoxide (DMSO) (2 ml) was stirred for 20 min at ˜40° C. under N 2 . To it 1 M tetra-n-butylammonium fluoride (TBAF) in terahydrofuran (THF) (0.4 ml) was added and the resulting mixture was stirred for 1 h at ˜120° C., then overnight at room temperature. The solvents were removed in vacuo and the residue was partitioned between EtOAc (15 ml) and H 2 O (5 ml). The organic phase was washed with brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was purified by FCC (SiO 2 ; CH 2 Cl 2 ) to give the title compound (0.13 g; 34%), as greyish solid. 1 H-NMR (CDCl 3 ) 8.36 (d, 1H, J=3 Hz); 8.09 (dd, 1H, J=3, 9 Hz); 7.79 (dd, 1H, J=3, 9 Hz); 7.68 (d, 1H, J=3 Hz); 7.55 (d, 1H, J=9 Hz); 6.98 (d, 1H, J=9 Hz); 6.73 (s, 1H); 4.8 (s, 2H); 4.2 (m, 4H); 2.02 (s, 1H); 1.51 (m, 6H);
[0089] Step E: 5-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-carbaldehyde: A suspension of the product of Step D (0.13 g; 0.34 mmol) and MnO 2 (0.15 g; 1.7 mmol) in dioxane (4 ml) was refluxed for 1 h with stirring. After cooling to room temperature, the insoluble material was removed by filtration, washed with EtOAc (20 ml) and combined filtrates were evaporated to dryness to give the title compound (0.13 g; 100%), as greyish solid. 1 H-NMR (CDCl 3 ) 9.91 (s, 1H); 8.59 (s, 1H); 8.33 (dd, 1H, J=2, 9 Hz); 7.63-7.82 (m, 4H); 6.99 (d, 1H, J=9 Hz); 4.14-4.26 (m, 4H); 1.4-1.57 (m, 6H+H 2 O).
[0090] Step F: 5-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-carboxylic acid; To a suspension of the product of Step E (0.009 g; 0.024 mmol) and AgNO 3 (0.06 g; 0.14 mmol) in EtOH (0.2 ml) H 2 O (0.1 ml) was added at room temperature, followed by 10% KOH (0.1 ml). The resulting black suspension was stirred for 1 h at ˜50° C. and cooled to room temperature and filtered. The insoluble material was washed with H 2 O (2×0.2 ml). The combined filtrates were acidified to pH=1 with HCl and the product was taken up by extraction with EtOAc (2×5 ml). The organic phase was washed with brine, dried over anhydrous MgSO 4 , filtered and filtrate evaporated to dryness. The residue was purified by FCC (SiO 2 , CH 2 Cl 2 /acetic acid (AcOH) 98/2) to give the title compound (0.00012 g; 12.8%), as a creamy solid. 1 H-NMR (CDCl 3 +CD 3 OD) 8.48 (s, 1H); 8.22 (m, 1H); 7.77 (m, 1H); 7.64-7.66 (m, 2H); 7.58 (s, 1H); 6.96 (d, 1H, J=6 Hz); 4.19 (m, 4H); 1.4-1.54 (m, 6H).
Example 2
1-((5-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)methyl)azetidine-3-carboxylic acid
[0091] Step A: Methyl 1-((5-(5-(3,4-diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzo furan-2-yl)methyl)azetidine-3-carboxylate: A mixture the product of Example 1, Step E (0.07 g; 0.85 mmol), azetidine-3-methylcarboxylate hydrochloride (0.03 g; 0.199 mmol) and DIPEA (0.035 ml, 0.2 mmol) in 1,2-dichloroethane (1 ml) and methanol (MeOH) (3 ml) was sonicated for 30 min at room temperature, then evaporated to dryness. The yellowish residue was suspended in 1,2-dichloroethane (1 ml) and NaBH(OAc) 3 (0.12 g; 0.57 mmol) was added, followed by AcOH (0.01 ml). This was stirred for 1 h at room temperature and diluted to 15 ml with EtOAc, washed with 10% KOH (2×3 ml); brine, dried over anhydrous MgSO 4 , filtered and the filtrate evaporated to dryness. The residue was purified by FCC (SiO 2 , EtOAc) to give the title compound (0.06 g; 68%), as creamy syrup. 1 H-NMR (CDCl 3 ) 8.33 (d, 1H, J=3 Hz); 8.06 (dd, 1H, 3, 9 Hz); 7.78 (dd, 1H, J=3, 9 Hz); 6.87 (d, 1H, J=2 Hz); 6.63 (s, 1H); 4.14-4.22 (m, 4H); 3.6-3.7 (m, 5H); 3.48-3.34 (m, 2H); 1.49 (m, 6H).
[0092] Step B: 1-((5-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)methyl)azetidine-3-carboxylic acid: A mixture of the product of Step A (0.06 g; 0.126 mmol) and 10% KOH (0.1 ml) in dioxane (2 ml) was refluxed for 1 h and solvents were evaporated to dryness. The residue was treated with AcOH (0.5 ml) and evaporated to dryness in vacuo. The residue was purified by FCC (SiO 2 , CH 2 Cl 2 saturated with concentrated NH 4 OH and MeOH, 85:15) to give the title compound (0.032 g; 55%), as a colourless solid. 1 H-NMR (CD 3 OD+CDCl 3 ) 8.37 (d, 1H, J=3 Hz); 8.09 (dd, 1H, J=3, 6 Hz); 7.77 (dd, 1H, J=3, 9 Hz); 7.68 (s, 1H); 7.6 (d, 1H, J=9 Hz); 7.02-7.07 (m, 2H); 4.38 (s, 2H); 4.05-4.21 (m, 8H); 1.44-1.49 9m, 6H).
Example 3
N-(1H-Tetrazol-5-yl)methyl-4-octylbenzylamine
[0093] Step A: 4-n-Octylbenzaldehyde: A mixture of n-octylbenzene (1.2 g; 6.3 mmol) hexamethylenetetramine (0.97 g; 6.93 mmol) in trifluoroacetic acid (TFA) was refluxed for 4 h, cooled to room temperature and evaporated to dryness under reduced pressure. The residue was neutralized with 5% NaHCO 3 and extracted with diethyl ether (Et 2 O) (3×5 ml). The combined organic phase was washed with H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane) to give the title compound (0.4 g; 29%) as a colourless oil and starting n-octylbenzene (0.8 g; 67%). 1 H-NMR (CDCl 3 ) 9.96 (s, 1H); 7.77 (d, 2H, J=8.1 Hz); 7.31 (d, 2H, J=8.1 Hz); 2.67 (t, 2H, J=7.9 Hz); 1.6 (m, 2H); 1.26 (m, 10H); 0.86 (t, 3H, J=6.9 Hz);
[0094] Step B: 2-(4-Octylbenzylamino)acetonitrile: T a suspension of the product of Step A (0.17 g; 0.78 mmol) and aminoacetonitrile bisulphate (0.18 g; 1.17 mmol) and NaBH(OAc) 3 in 1,2 dichloroethane (3 ml), DIPEA (0.2 ml; 1.17 mmol) was added at room temperature followed by AcOH (0.045 ml; 0.78 mmol). The resulting mixture was stirred over a weekend at room temperature under N 2 and quenched by an addition of 1 M NaOH (0.5 ml). This was diluted to 15 ml with Et 2 O, washed with H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was diluted to 3 ml with anhydrous MeOH and to it NaBH 4 (0.1 g; 2.6 mmol) was added portion wise at room temperature with stirring. After stirring overnight, the mixture was evaporated to dryness and the residue was diluted to 15 ml with Et 2 O, washed with 1N NaOH, H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc 6:4) to give the title compound (0.07 g; 28%) as a colourless syrup. 1 H-NMR (CDCl 3 ) 7.23 (d, 2H, J=8.01 Hz); 7.14 (d, 2H, J=8.01 Hz); 3.88 (s, 2H); 3.55 (s, 2H); 2.58 (t, 2H, J=7.94 Hz); 1.6 (m, 3H); 1.27 (m, 10H); 0.86 (t, 3H, J=6.93 Hz).
[0095] Step C: N-(1H-Tetrazol-5-yl)methyl-4-n-octylbenzylamine: A mixture of the product of Step B (0.07 g; 0.271 mmol) and Me 3 SiN 3 (0.36 ml; 2.71 mmol) and 1M TBAF in THF (0.27 ml; 0.271 mmol) was stirred at 75±5° C. for 8 h in sealed flask. After cooling to room temperature, the mixture was diluted to 1 ml with MeOH, refluxed for 30 min under N 2 and left overnight in refrigerator. The precipitate formed was filtered off, washed with Et 2 O and dried to give a title compound (0.069 g; 84%) as colourless solid. 1 H-NMR (CD 3 OD) 7.32 (d, 2H, J=8.0 Hz); 7.21 (d, 2H, J=8.0 Hz); 4.72 (s, CD 3 OH); 4.34 (s, 2H); 4.16 (s, 2H); 2.59 (t, 2H, J=7.76 Hz); 1.57 (t, 2H, J=7.19 Hz); 1.25 (m, 10H); 0.84 (t, 3H, J=6.93 Hz);
Example 4
N-((1H-Tetrazol-5-yl)methyl)-4-n-octylaniline
[0096] Step A: 2-(4-Octylphenylamino)acetonitrile: A mixture of 4-n-octylaniline (0.21 g; 1 mmol), BrCH 2 CN (0.156 mmol; 1.3 mmol) and K 2 CO 3 (0.28 g; 2 mmol) in anhydrous CH 3 CN (3 ml) was stirred overnight at ˜60° C. under N 2 , then concentrated under reduced pressure. The residue was partitioned between CH 2 Cl 2 (20 ml) and H 2 O (10 ml). The organic phase was dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was purified by crystallization from hexane to give the title compound (0.18 g; 74%) as creamy solid. 1 H-NMR (CDCl 3 ) 7.06 (d, 2H, J=8.48 Hz); 6.63 (d, 2H, J=8.48 Hz); 4.06 (d, 2H, J=5.75 Hz); 3.83 (broad m, 1H); 2.51 (t, 2H, J=7.92 Hz); 1.55 (m, 3H); 1.27 (m, 10H); 0.86 (t, 3H, J=6.87 Hz).
[0097] Step B: N-((1H-Tetrazol-5-yl)methyl)-4-n-octylaniline: When the product of Step A was substituted for 2-(4-octylbenzylamino)acetonitrile in Example 3, Step C, the identical process afforded the title compound in 77% yield, as creamy solid. 1 H-NMR (CDCl 3 ) 6.94 (d, 2H, J=8.37 Hz); 6.61 (broad s, 2H); 6.49 (d, 2H, J=8.37 Hz); 4.68 (m, 2H); 2.44 (t, 2H, J=7.94 Hz); 1.49 (t, 2H, J=7.55 Hz); 1.24 (m, 10H); 0.85 (t, 3H, J=6.95 Hz).
Example 5
2-(4-Octylphenylamino)propane-1,3-diol
[0098] Step A: 2,2-Dimethyl-N-(4-octylphenyl)-1,3-dioxan-5-amine: To a mixture of 4-n-octylaniline (0.205 g; 1 mmol) and 2,2-dimethyl-1,3-dioxan-5-one (Helvetica Chimica Acta, 2003, 86, 2467; 0.13 g; 1 mmol) and NaBH(OAc) 3 in 1,2 dichloroethane (3.5 ml), AcOH (0.06 ml; 1 mmol) was added and the mixture was stirred for 2 h at room temperature under N 2 , diluted to 20 ml with Et 2 O and washed with 1N NaOH, H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified crystallization from hexane to give the title compound (0.2 g; 63%) as a colourless solid. 1 H-NMR (CDCl 3 ) 6.97 (d, 2H, J=8.4 Hz); 6.54 (d, 2H, J=8.4 Hz); 4.1 (dd, broad s, 3H, J=4.2, 11.9 Hz); 3.74 (dd, 2H, J=4.2, 11.9 Hz); 3.4 (m, 1H); 2.47 (t, 2H, J=7.91 Hz); 1.55 (m, 2H+H 2 O); 1.46 (s, 3H); 1.43 (s, 3H); 1.25 (m, 10H); 0.86 (m, 3H).
[0099] Step B: 2-(4-octylphenylamino)propane-1,3-diol: To a solution of the product of Step A (0.1 g; 0.31 mmol) in MeOH (1 ml) Me 3 SiCl (0.5 ml) was added at room temperature. After stirring for 1 h, the mixture was evaporated to dryness under reduced pressure to give a hydrochloride salt of the title compound (0.1 g; 100%) as a colourless solid. 1 H-NMR (CDCl 3 ) 10.66 (bs, 2H); 7.53 (d, 2H, J=7.98 Hz); 7.18 (d, 2H, J=7.98 Hz); 4.82 (broad s, 2H); 3.98 (broad m, 4H); 3.51 (broad m, 1H); 2.58 (t, 2H, J=7.68 Hz); 1.56 (m, 2H); 1.43 (s, 3H); 1.27 (m, 10H); 0.86 (t, 3H, J=6.96 Hz).
Example 6
2-((4-n-Octylbenzylamino)methyl)propane-1,3-diol
[0100] Step A: 4-n-Octylbenzyl alcohol: NaBH 4 (0.04 g; 1.06 mmol) was added portion wise to a solution of the product of Example 3, Step A in MeOH (5 ml) at room temperature, with vigorous stirring. After 30 min of stirring, the mixture was evaporated to dryness, diluted to 10 ml with Et 2 O and washed with 1N NaOH, H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure to give the title compound (0.082 g; 100%), as colourless syrup, which was used in next step without further purification. 1 H-NMR (CDCl 3 ) 7.26 (d, 2H, J=8 Hz); 7.15 (d, 2H, J=8 Hz); 4.64 (s, 2H); 2.58 (t, 2H, J=7.9 Hz); 1.56 (m, 3H); 1.26 (m, 10H); 0.86 (t, 3H, J=6.9 Hz).
[0101] Step B: 4-n-octylbenzyl bromide: PBr 3 (0.23 ml) was added drop wise to a stirred solution of the product of Step A (0.082 g; 0.37 mmol) in Et 2 O (2 ml) at −15° C. The mixture was allowed to warm up to room temperature and the stirring was continued for 4 h. This was poured onto ice (5 g) and the product was extracted with fresh Et 2 O (2×10 ml). The combined extracts were washed with 5% NaHCO 3 , H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane) to give the title compound (0.04 g; 40%) as a colourless solid. 1 H-NMR (CDCl 3 ) 7.28 (d, 2H, J=8 Hz); 7.13 (d, 2H, J=8 Hz); 4.48 (s, 2H); 2.57 (t, 2H, J=7.9 Hz); 1.57 (m, 2H); 1.26 (m, 10H); 0.86 (t, 3H, J=7 Hz).
[0102] Step C: 4-n-Octylbenzylamine: To a solution of the product of Step B (0.13 g; 0.459 mmol) in anhydrous hexamethylenedisilazane (HMDSA) 1M NaHMDSA in THF was added at room temperature under N 2 with stirring. After stirring overnight at room temperature solvents were removed under reduced pressure and the residue was diluted to 5 ml with MeOH and 1 drop of concentrated HCl was added. This was evaporated under reduced pressure, diluted to 15 ml with Et 2 O and washed with 1N NaOH, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure to give the title compound (0.1 g; 100%), as colourless oil, which was used in the next step without further purification. 1 H-NMR (CDCl 3 ) 7.2 (d, 2H, J=8 Hz); 7.13 (d, 2H, J=8 Hz); 3.82 (s, 2H); 2.57 (t, 2H, J=7.9 Hz); 1.58 (m, 2H); 1.41 (s, 2H); 1.26 (m, 10H); 0.86 (t, 3H, J=7 Hz).
[0103] Step D: (2,2-Dimethyl-1,3-dioxan-5-yl)-N-(4-octylbenzyl)methylamine: When the product of Step C was substituted for 4-n-octylaniline in Example 5, Step A, the identical process afforded the title compound in 86% yield, as a colourless syrup. 1 H-NMR (CDCl 3 ) 7.23 (d, 2H, J=8 Hz); 7.11 (d, 2H, J=8 Hz); 3.96 (dd, 2H, J=5.57, 11.73 Hz); 11.73 Hz); 3.83 (s, 2H); 3.75 (dd, 2H, J=5.57, 2.69 (m, 1H); 2.56 (t, 2H, J=7.88 Hz); 1.81 (broad s, 1H+H 2 O); 1.4 (m, 5H); 1.25 (m, 13H); 0.86 (t, 3H, J=6.96 Hz).
[0104] Step E: 2-((4-n-Octylbenzylamino)methyl)propane-1,3-diol: A solution of the product of Step D (0.6 g; 0.13 mmol) in 60% trifluoroacetic acid (TFA) in CH 2 Cl 2 (2 ml) was stirred for 15 min at room temperature and the mixture was diluted to 5 ml with MeOH and evaporated to dryness under reduced pressure. The residue was dissolved in iso-propanol (iPrOH) (2 ml) and one drop of concentrated HCl was added. This was evaporated under reduced pressure and treated with anhydrous Et 2 O. The precipitate formed was filtered off, dried in vacuo for 1 h to give a hydrochloride salt of the title compound (0.04 g; 85%), as a colourless solid. 1 H-NMR (D 2 O) 7.32 (d, 2H, J=7.56 Hz); 7.21 (d, 2H, J=7.56 Hz); 4.2 (s, 2H); 4.66 (DHO); 3.69 (s, 4H); 3.36 (s, 2H); 2.52 (t, 2H, J=7.47 Hz); 1.49 (5, 2H); 1.16 (m, 10H); 0.74 (m, 3H).
Example 7
2-((Methyl(4-octylbenzyl)amino)methyl)propane-1,3-diol
[0105] Step A: (2,2-dimethyl-1,3-dioxan-5-yl)-N-methyl-N-(4-octylbenzyl)methyl amine: When the product of Example 6, Step D is substituted for 4-n-octylaniline and 30% aqueous HCHO is substituted for 2,2-dimethyl-1,3-dioxan-5-one in Example 3, Step A, the identical process afforded the title compound in 100% yield, as a colourless syrup. 1 H-NMR (CDCl 3 ) 7.2 (d, 2H, J=7.75 Hz); 7.11 (d, 2H, J=7.75 Hz); 3.83 (s, 2H); 3.94 (m, 4H); 3.64 (s, 2H); 2.83 (m, 1H); 2.56 (d, 2H, J=7.3 Hz); 2.29 (s, 3H); 1.58 (m, 2H+H 2 O); 1.25-1.42 (m, 18H); 0.86 (m, 3H).
[0106] Step B: 2-((Methyl(4-octylbenzyl)amino)methyl)propane-1,3-diol: When the product of Step A is substituted for (2,2-dimethyl-1,3-dioxan-5-yl)-N-(4-octylbenzyl)methylamine in Example 6, Step E, the identical process afforded the title compound in 79% yield, as a glassy solid. 1 H-NMR (D 2 O) 7.3 (d, 2H, J=7.8 Hz); 6.96 (d, 2H, J=7.8 Hz); 4.66 (DHO); 4.24 (s, 2H); 3.73 (m, 4H); 3.32 (m, 1H); 2.7 (s, 3H); 2.3 (t, 2H, J=7.63 Hz); 1.36 (m, 2H); 1.15 (s, 2H); 1.15 (m, 10H); 0.73 (t, 3H, J=6.73 Hz).
Example 8
4,4-Bis(hydroxymethyl)-1-(4-octylphenyl)imidazolidin-2-one
[0107] Step A: tert-Butyl 2,2-dimethyl-5-((4-octylphenylamino)methyl)-1,3-dioxan-5-ylcarbamate: To a mixture of 4-n-octylaniline (0.21 g; 1 mmol), tert-butyl 5-formyl-2,2-dimethyl-1,3-dioxan-5-ylcarbamate (Ooii et al, J. Org. Chem., 2004, 69, 7765; 0.26 g; 1 mmol) and NaBH(OAc) 3 (0.3 g; 1.4 mmol) in 1,2-dichloroethane (3.5 ml) AcOH (0.06 ml; 1 mmol) was added at room temperature with stirring under N 2 . After stirring for 2 h, the mixture was diluted to 20 ml with Et 2 O, washed with 1.M NaOH (2×5 ml), brine and dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure. The residue was dissolved in hexane (5 ml) and kept in the freezer (−18° C.) overnight. The crystals formed were filtered off, washed with small volume of hexane and dried to give the title compound (0.32 g; 71%), as colourless crystals. 1 H-NMR (CDCl 3 ) 6.96 (d, 2H, J=8.4 Hz); 6.58 (d, 2H, J=8.4 Hz); 4.84 (broad s, 1H); 4.01 (d, 2H, J=11.9); 3.85 (broad s, 1H); 3.8 (d, 2H, J=11.9 Hz); 3.44 (s, 2H); 2.46 (t, 2H, J=7.9 Hz); 1.5 (m, 2H); 1.45 (s, 3H); 1.43 (s, 9H); 1.42 (s, 3H); 1.26 (m, 10H); 0.86 (t, 2H, J=6.95 Hz).
[0108] Step B: 4,4-(2,2-Dimethyl-1,3-dioxanyl)-1-(4-octylphenyl)imidazolidin-2-one: A solution of the product of Step A (0.17 g; 0.38 mmol) and 60% NaH in mineral oil (0.043 g; 1.14 mmol) in anhydrous DMF (4 ml) was stirred overnight at ˜55° C. under N 2 . After removal of solvent in vacuo, the residue was diluted to 15 ml with Et 2 O, washed with 10% citric acid, H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc 8:2) to give the title compound (0.06 g; 42%) as a colourless solid and starting material (0.1 g; 58%). 1 H-NMR (CDCl 3 ) 7.41 (d, 2H, J=8.58 Hz); 7.12 (d, 2H, J=8.58 Hz); 5.27 (broad s, 1H); 3.84 (d, 2H, J=11.3 Hz); 3.78 (d, 2H, J=11.3 Hz); 3.68 (s, 2H); 2.55 (t, 2H, J=7.83 Hz); 1.56 (m, 2H); 1.28 (m, 10H); 0.84 (t, 3H, J=6.76 Hz).
[0109] Step C: 4,4-Bis(hydroxymethyl)-1-(4-octylphenyl)imidazolidin-2-one: When the product of Step B is substituted for (2,2-dimethyl-1,3-dioxan-5-yl)-N-(4-octylbenzyl)methylamine in Example 6, Step E, the identical process afforded the title compound in 74% yield, as a colourless solid, after purification by FCC (SiO 2 , CH 2 Cl 2 saturated with concentrated NH 4 OH/MeOH; 98:2). 1 H-NMR (CDCl 3 ) 7.30 (d, 2H, J=8.49 Hz); 7.02 (d, 2H, J=8.49 Hz); 6.53 (s, 1H); 4.65 (broad s, 2H); 3.48-3.62 (m, 6H); 2.47 (t, 2H, J=7.94 Hz); 1.51 (m, 2H); 1.25 (m, 10H); 0.87 (t, 3H, J=6.94 Hz).
Example 9
2-(4-(4-n-Octylphenyl)piperazin-1-yl)acetic acid
[0110] Step A: 4-n-Octyliodobenzene: To a suspension of n-octylbenzene (1 g; 5.2 mmol) and CF 3 SO 3 Ag (1.35 g; 5.2 mmol) in anhydrous CH 2 Cl 2 (15 ml) I 2 was added at 0° C. The resulting mixture was allowed to warm up to room temperature and stirred for additional 1 h, then filtered through a pad of Celite, washed with fresh CH 2 Cl 2 (2×15 ml) and combined filtrates washed with 5% Na 2 SO 3 , H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure to give the title product and 2-iodo isomer (1.64 g; 100%), as creamy oil, which was used in the next step without further purification. 1 H-NMR (CDCl 3 ) 7.7-7.8 (m, 0.3H); 7.56 (d, 1.7H, J=8.3 Hz); 7.29-7.16 (m, 0.6H); 6.9 (d, 1.4H, J=8.3 Hz); 6.85-6.82 (m, 0.3H); 2.68 (t, 0.6, J=8.01 Hz); 2.52 (t, 1.4H, J=7.89 Hz); 1.56 (m, 2H); 1.25 (m, 10H); 0.86 (m, 3H).
[0111] Step B: tert-Butyl 4-(benzoyloxy)piperazine-1-carboxylate: To a suspension of benzoyl peroxide+15% H 2 O (1.47 g; 4.55 mmol) and K 2 HPO 4 (1.19 g; 6.8 mmol) in DMF (11.36 ml) N-BOC piperazine (Sengmany et al, Tetrahedron, 2007, 63, 3672; 1 g; 5.4 mmol) was added and the mixture was stirred for 1 h at room temperature. To it, H 2 O (20 ml) was added and the resulting mixture was vigorously stirred until homogenous. This was extracted with EtOAc (15 ml). The organic phase was washed with H 2 O and combined aqueous phase was extracted with fresh EtOAc (3×10 ml). The combined organic phase was washed with H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure to give the title product (0.9 g; 65%), as a colourless solid. 1 H-NMR (CDCl 3 ) 8-7.96 (m, 2H); 7.59-7.53 (m, 1H); 7.45-7.38 (m, 2H); 4.01 (m, 2H); 3.41-3.2 (m, 4H); 2.9 (m, 2H); 1.46 (s, 9H).
[0112] Step C: tert-Butyl 4-(4-octylphenyl)piperazine-1-carboxylate: To a solution of the product of Step A (0.32 g; 1.01 mmol) in anhydrous THF (2 ml) 2 M iPrMgCl in THF (0.56 ml; 1.11 mmol) was added at −15° C. under N 2 , followed 1.27 M solution of anhydrous ZnCl 2 in THF (0.41 ml; 0.52 mmol), after stirring for 1 h at 0° C. The resulting mixture was stirred for 30 min on ice-bath under N 2 and the solution of the product of Step B (0.16 g; 0.51 mmol) and CuCl 2 (2.5 mol %) in anhydrous THF (10 ml) was added. The resulting mixture was allowed to warm up to room temperature and stirred for additional 10 min. This was diluted to 20 ml with Et 2 O and washed with 5% NaHCO 3 , H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc 9:1) to give the title compound (0.06 g; 31%), as a creamy syrup. 1 H-NMR (CDCl 3 ) 7.07 (d, 2H, J=8.6 Hz); 6.84 (d, 2H, J=8.6 Hz); 3.55 (t, 4H, J=5 Hz); 3.06 (t, 4H, J=5 Hz); 2.51 (t, 2H, J=7.94 Hz); 1.55-1.38 (m, 11H); 1.26 (m, 10H); 0.86 (t, 3H, J=6.93 Hz).
[0113] Step D: 1-(4-n-Octylphenyl)piperazine: A solution of the product of Step C (0.06 g; 0.16 mmol) in 60% TFA in CH 2 Cl 2 (2 ml) was stirred for 15 min at room temperature and the mixture was diluted to 5 ml with EtOH and evaporated to dryness under reduced pressure and kept in vacuo for 1 h, to give a TFA salt of the title compound (0.07 g; 100%). 1 H-NMR (CDCl 3 ) 9.5 (broad s, 2H); 7.29 (m, 4H); 3.8-3.16 (m, 8H); 2.6 (t, 2H, J=8 Hz); 1.58 (m, 2H); 1.26 (m, 10H); 0.86 (t, 3H, J=6.9 Hz).
[0114] Step E: tert-Butyl 2-(4-(4-octylphenyl)piperazin-1-yl)acetate: To a solution of the product of Step D (0.04 g, 0.146 mmol) and tert-butyl bromoacetate (0.026 ml; 0.16 mmol) in CH 2 Cl 2 (1 ml) DIPEA (0.052 ml; 0.32 mmol) was added at room temperature under N 2 . The mixture was stirred overnight at room temperature, diluted to 5 ml with Et 2 O and washed with 0.1 N HCl, H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc 7:3) to give the title compound (0.05 g; 88%), as a colourless heavy syrup. 1 H-NMR (CDCl 3 ) 7.05 (d, 2H, J=8.6 Hz); 6.83 (d, 2H, J=8.6 Hz); 3.32-3.15 (m, 6H); 2.73 (m, 4H); 2.5 (t, 2H, J=7.9 Hz); 1.55 (m, 2H); 1.46 (s, 9H); 1.26 (m, 10H); 0.86 (m, 3H).
[0115] Step F: 2-(4-(4-n-Octylphenyl)piperazin-1-yl)acetic acid: A solution of the product of Step E (0.05 g; 0.129 mmol) in 60% TFA in CH 2 Cl 2 (5 ml) was refluxed for 2 h, cooled to room temperature then diluted to 7 ml with EtOH. The resulting mixture was evaporated to dryness under reduced pressure kept in vacuo for 1 h. The residue was treated dissolved in EtOH (2 ml) and 3 drops of concentrated NH 4 OH was added. The resulting mixture was partially concentrated under reduced pressure and the precipitate, formed was filtered off, washed with Et 2 O and dried to give the titled compound (0.02 g; 47%) as colourless solid. 1 H-NMR (CD 3 OD+CDCl 3 ) 7.07 (d, 2H, J=8.6 Hz); 6.86 (d, 2H, J=8.6 Hz); 4.63 (s, CD 3 OH); 3.58 (s, 2H); 3.38 (m, 8H); 2.49 (t, 2H, J=7.8 Hz); 1.53 (m, 2H); 1.24 (m, 10H); 0.83 (m, 3H).
Example 10
2-(4-Octylphenethyl)propane-1,2,3-triol
[0116] Step A: 1-Ethynyl-4-octylbenzene: A mixture of Example 3, Step A (0.1 g; 0.46 mmol), dimethyl(1-diazo-2-oxoprpyl)phosphonate (0.11 g, 0.57 mmol) and anhydrous K 2 CO 3 (0.14 g, 1.01 mmol) in dry MeOH (5 ml) was stirred for 8 h under N 2 . After removing solvent under reduced pressure, the residue was diluted to 15 ml with Et 2 O and washed with H 2 O (2×10 ml) and dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was purified by FCC (SiO 2 , hexane) to give the title compound (0.05 g; 51%) as colourless oil. 1 H-NMR (CDCl 3 ) 7.38 (d, 2H, J=8.1 Hz); 7.11 (d, 2H, J=8.1 Hz); 3.0 (s, 1H); 2.58 (t, 2H, J=7.8 Hz); 1.58 (t, 3H, J=6.96 Hz); 1.27 (m, 10H); 0.86 (t, 3H, J=6.96 Hz).
[0117] Step B: 2,2-Dimethyl-5-((4-octylphenyl)ethynyl)-1,3-dioxan-5-ol: To a solution of the product of Step A (0.05 g; 0.233 mmol) in anhydrous THF (2 ml) 2 M n-butyllithium in cylohexane (0.13 ml; 0.26 mmol) was added drop wise at −15° C. under N 2 . After stirring for 15 min at −15° C., 2,2-dimethyl-1,3-dioxan-5-one (0.034 g; 0.26 mmol) was added and the resulting mixture was allowed to warm up to room temperature, diluted to 15 ml with Et 2 O and washed with H 2 O (2×10 ml), brine and dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc 95; 5) to give the title compound (0.03 g; 63%) as colourless oil. 1 H-NMR (CDCl 3 ) 7.33 (d, 2H, J=8.09 Hz); 7.09 (d, 2H, J=8.09 Hz); 4.11 (d, 2H, J=11.76 Hz); 3.83 (d, 2H, J=11.76 Hz); 3.99 (s, 1H); 2.57 (t, 2H, J=7.88 Hz); 1.56 (t, 3H, J=6.94 Hz); 1.49 (s, 3H); 1.46 (s, 3H); 1.26 (m, 10H); 0.86 (t, 3H, J=6.96 Hz).
[0118] Step C: 2-(4-Octylphenethyl)propane-1,2,3-triol: A mixture of the product of Step B (0.03 g; 0.087 mmol) and 10% Pd/C (0.05 g) in 5% TFA in EtOH (10 ml) was stirred for 1 h under H 2 (balloon) at room temperature, then filtered through a pad of Celite, washed with CH 2 Cl 2 (2×10 ml). To combined filtrates were evaporated to dryness under reduced pressure and dried in vacuo for 1 h to give title compound (0.027 g; 99%) as a colourless solid. 1 H-NMR (CDCl 3 ) 7.05 (s, 4H); 3.66 (broad m, 7H); 2.61 (m, 2H); 2.51 (t, 2H, J=7.92 Hz); 1.73 (m 2H); 1.55 (t, 3H, J=6.93 Hz); 1.26 (m, 10H); 0.87 (t, 3H, J=6.93 Hz).
Example 11
3-(3-(4-n-Octylphenyl)ureido)propanoic acid
[0119] Step A: Ethyl 3-(3-(4-octylphenyl)ureido)propanoate: To 4-n-octylaniline (0.1 g; 0.49 mmol) ethyl 3-isocyanatopropionate (0.08 g; 0.54 mmol) was added at room temperature. The resulting mixture was diluted to 1 ml with CH 2 Cl 2 , refluxed for 30 min and evaporated to dryness. The residue was treated with Et 2 O (5 ml) and the solid formed was filtered off and dried to give the title compound (0.15 g; 87%), as colourless crystals. 1 H-NMR (CDCl 3 ) 7.22-7.07 (m, 4H); 6.34 (broad s, 1H); 5.34 (m, 1H); 4.15-4.07 (m, 2H); 3.54-3.46 (m, 2H); 2.73 (m, 4H); 2.57-2.51 (m, 4H); 1.58 (m, 2H); 1.27-1.19 (m, 13H); 0.86 (m, 3H).
[0120] Step B: 3-(3-(4-n-Octylphenyl)ureido)propanoic acid: To a solution of the product of Step A (0.05 g; 0.143 mmol) in dioxane (1 ml) 2N KOH (0.36 ml; 0.72 mmol) was added and the mixture was refluxed for 15 min, cooled to room temperature and evaporated to dryness under reduced pressure. The residue was diluted to 2 ml with H 2 O and filtered. The filtrate was acidified to pH ˜4 with citric acid. The solid formed was filtered off, washed with H 2 O (3×2 ml), dried in vacuo to give the title compound (0.03 g; 65%), as a colourless solid. 1 H-NMR (CD 3 OD+CDCl 3 ) 7.16 (d, 2H, J=8.4 Hz); 7.0 (d, 2H, J=8.4 Hz); 4.21 (s, CD 3 OH); 3.4 (t, 2H, J=6.7 Hz); 2.73 (m, 4H); 2.5-2.44 (m, 4H); 1.5 (m, 2H); 1.2 (m, 10H); 0.81 (m, 3H).
Example 12
3-(3-Methyl-3-(4-octylphenyl)ureido)propanoic acid
[0121] Step A: tert-Butyl 4-n-octylphenyl(methyl)carbamate: A mixture of 4-noctylaniline (0.09 g; 0.44 mmol) and di-tert-butyl dicarbonate (0.1 g; 0.46 mmol) and a few drops of triethylamine was stirred at −50° C. for 1 h under N 2 , cooled to room temperature and kept in vacuo for 30 min. The residue was dissolved in anhydrous DMF (2 ml) and %60 NaH in mineral oil (0.02 g: 0.47 mmol) was added to it, followed by MeI (0.03 ml; 0.47 mmol), after stirring for 30 min under N 2 . The resulting mixture was stirred for 3 h at room temperature and solvent was removed in vacuo. The residue was diluted to 15 ml with Et 2 O and washed with 5% Na 2 SO 3 , H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure to give the title compound (0.14 g; 100%), as a creamy solid. 1 H-NMR (CDCl 3 ) 7.14-6.99 (m, 4H); 3.22 (s, 3H); 2.55 (m, 2H); 1.56 (m, 2H); 1.43 (s, 9H); 1.26 (m, 10H); 0.86 (m, 3H).
[0122] Step B: N-Methyl-4-n-octylaniline: A solution of the product of Step A (0.14 g; 0.44 mmol) in 60% TFA in CH 2 Cl 2 (5 ml) was stirred for 30 min at room temperature and the mixture was diluted to 5 ml with EtOH and a few drops of concentrated HCl was added. This was evaporated to dryness under reduced pressure, kept in vacuo for 1 h and the residue was partitioned between saturated NaHCO 3 (5 ml) and Et 2 O (15 ml). The organic phase was dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc 9:1) to give the title compound (0.055 g; 57%), as a creamy solid. 1 H-NMR (CDCl 3 ) 7.01 (d, 2H, J=8.2 Hz); 6.55 (d, 2H, J=8.2 Hz); 3.55 (broad s, 1H); 2.81 (s, 3H); 2.49 (t, 2H, J=7.9 Hz); 1.56 (m, 2H); 1.28 (m, 10H); 0.88 (t, 3H, J=6.8 Hz).
[0123] Step C: Ethyl 3-(3-methyl-3-(4-octylphenyl)ureido)propanoate: When the product of Step B is substituted for 4-n-octylaniline in Example 11, Step A, the identical process afforded the title compound in 99% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.15 (d, 2H, J=8.2 Hz); 7.05 (d, 2H, J=8.2 Hz); 4.77 (m, 1H); 4.03 (q, 2H, J=7.14 Hz); 3.54 (m, 2H); 3.37 (qr, 2H, J=6.1 Hz); 3.18 (s, 3H); 2.55 (t, 2H, J=7.5 Hz); 2.44 (t, 2H, J=6.1 Hz); 1.57 (m, 2H); 1.25 (m, 10H); 1.13 (t, 3H, J=7.14 Hz); 0.83 (t, 3H, J=6.9 Hz).
[0124] Step D: 3-(3-Methyl-3-(4-octylphenyl)ureido)propanoic acid: When the product of Step C is substituted for ethyl 3-(3-(4-octylphenyl)ureido)propanoate in Example 11, Step B, the identical process afforded the title compound in 84% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.19 (d, 2H, J=8.3 Hz); 7.09 (d, 2H, J=8.3 Hz); 4.83 (m, 1H); 3.54 (m, 2H); 3.4 (m, 2H); 3.22 (s, 3H); 2.6-2.5 (m, 4H); 1.59 (m, 2H); 1.27 (m, 10H); 0.86 (t, 3H, J=7 Hz).
Example 13
3-(3-(4-Octylphenyl)-2-oxoimidazolidin-1-yl)propanoic acid
[0125] Step A: Ethyl 3-(3-(4-octylphenyl)-2-oxoimidazolidin-1-yl)propanoate: To a solution of the product of Example 11, Step A (0.05 g; 0.143 mmol) in anhydrous DMF (2 ml) 60% NaH in mineral oil (0.014 g; 0.344 mmol) was added at room temperature. After stirring for 1 h, to it 1,2-dibromoethane (0.172 ml; 0.2 mmol) was added. This was stirred at −50° C. for 1 h under N 2 , cooled to room and solvents were removed in vacuo. The residue was diluted to 15 ml with Et 2 O, washed with H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc 9.5:0.5) to give the title compound (0.02 g; 37%) as a colourless solid. 1 H-NMR (CDCl 3 ) 7.4 (d, 2H, J=8.5 Hz); 7.1 (d, 2H, J=8.5 Hz); 4.13 (q, 2H, J=7.1 Hz); 3.76 (m, 2H); 3.57 (t, 2H, J=6.7 Hz); 3.5 (m, 2H); 2.6 (t, 2H, J=6.7 Hz); 2.53 (t, 2H, J=7.9 Hz); 1.55 (m, 2H); 1.24 (m, 13H); 0.85 (t, 3H, J=6.9 Hz).
[0126] Step B: 3-(3-(4-Octylphenyl)-2-oxoimidazolidin-1-yl)propanoic acid: When the product of Step A is substituted for ethyl 3-(3-(4-octylphenyl)ureido)propanoate in Example 11, Step B, the identical process afforded the title compound in 33% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.39 (d, 2H, J=8.4 Hz); 7.11 (d, 2H, J=8.4 Hz); 3.78 (t, 2H, J=7.3 Hz); 3.6-3.4 (m, 4H); 3.22 (s, 3H); 2.66 (t, 2H, J=6.5 Hz); 2.53 (t, 2H, J=7.7 Hz); 1.55 (m, 2H); 1.25 (m, 10H); 0.85 (t, 3H, J=6.9 Hz).
Example 14
2-(3-(4-Octylbenzyl)ureido)acetic acid
[0127] Step A: Ethyl 2-(3-(4-octylbenzyl)ureido)acetate: When the product of Example 6, Step C was substituted for 4-n-octylaniline and ethyl 2-isocyanatoacetate was substituted for ethyl 3-isocyanatopropionate in Example 11, Step A, the identical process afforded the title compound in 75% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.18 (d, 2H, J=8 Hz); 7.11 (d, 2H, J=8 Hz); 4.86 (m, 1H); 4.78 (m, 1H); 4.32 (d, 2H, J=5.6 Hz); 4.16 (q, 2H, J=7.1 Hz); 3.97 (d, 2H, J=5.3 Hz); 2.56 (t, 2H, J=8 Hz); 1.56 (m, 2H); 1.25 (m, 13H); 0.86 (t, 3H, J=6.9 Hz).
[0128] Step B: 2-(3-(4-Octylbenzyl)ureido)acetic acid: When the product of Step A was substituted for ethyl 3-(3-(4-octylphenyl)ureido)propanoate in Example 11, Step B, the identical process afforded the title compound in 87% yield, as a colourless solid. 1 H-NMR (CDCl 3 +CD 3 OD) 7.15 (d, 2H, J=8 Hz); 7.07 (d, 2H, J=8 Hz); 4.63 (CD 3 OH); 4.26 (s, 2H); 3.86 (s, 2H); 2.52 (t, 2H, J=7.8 Hz); 1.54 (m, 2H); 1.22 (m, 10H); 0.83 (t, 3H, J=7 Hz).
Example 15
2-(3-(4-Octylbenzyl)-2-oxoimidazolidin-1-yl)acetic acid
[0129] Step A: tert-Butyl 2-(2-oxoimidazolidin-1-yl)acetate: To a solution of imidazolidin-2-one (0.2 g; 2.3 mmol) in anhydrous DMF (5 ml) 60% NaH in mineral oil (0.18 g; 4.6 mmol) was added at room temperature, under N 2 . After stirring for 1 h, tert-butyl 2-bromoacetate (0.35 ml; 2.3 mmol) was added. The resulting mixture was stirred for additional 2 h and solvents were removed in vacuo. The residue was diluted to 15 ml with EtOAc, washed with H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , EtOAc) to give the title compound (0.12 g; 26%) as a colourless solid. 1 H-NMR (CDCl 3 ) 4.61 (broad s, 1H); 3.83 (s, 2H); 3.58-3.41 (m, 4H); 1.44 (s, 9H).
[0130] Step B: tert-Butyl 2-(3-(4-octylbenzyl)-2-oxoimidazolidin-1-yl)acetate: To a solution of the product of Step A (0.03 g; 0.15 mmol) in anhydrous DMF (5 ml) 60% NaH in mineral oil (0.006 g; 0.15 mmol) was added at room temperature, under N 2 . After stirring for 1 h, the product of Example 4, Step B (0.042 g; 0.15 mmol) was added. The resulting mixture was stirred for additional 4 h and solvents were removed in vacuo. The residue was diluted to 10 ml with EtOAc, washed with H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.01 g; 16%) as a colourless solid. 1 H-NMR (CDCl 3 ) 7.16 (d, 2H, J=8.1 Hz); 7.11 (d, 3H, J=8.1 Hz); 4.34 (s, 2H); 3.95 (s, 2H); 3.4 (m, 2H); 3.21 (m, 2H); 2.56 (t, 3H, J=7.9 Hz); 1.65 (m, 2H); 1.43 (s, 9H); 1.26 (m, 10H); 0.86 (t, 3H, J=7 Hz).
[0131] Step C: 2-(3-(4-Octylbenzyl)-2-oxoimidazolidin-1-yl)acetic acid: When the product of Step B was substituted for tert-butyl 2-(4-(4-octylphenyl)piperazin-1-yl)acetate in Example 9, Step F, the identical process afforded the title compound in 46% yield, as a colourless solid. 1 H-NMR (CDCl 3 +CD 3 OD) 7.0 (m, 4H); 4.42 (s, 2H); 3.72 (s, 2H); 3.31 (m, 2H); 3.11 (m, 2H); 2.44 (t, 2H, J=7.8 Hz); 1.43 (m, 2H); 1.13 (m, 10H); 0.73 (t, 3H, J=7 Hz).
Example 16
2-(1-(4-Octylbenzyl)hydrazine-carboxamido)acetic acid
[0132] Step A: tert-Butyl 2-(4-octylbenzylidene)hydrazinecarboxylate: To a mixture of Example 3, Step A (0.1 g; 0.46 mmol) and tert-butyl carbazate (0.06 g; 0.46 mmol) in anhydrous CH 2 Cl 2 (5 ml) anhydrous MgSO 4 was added and the resulting suspension was vigorously stirred for 2 h at room temperature and filtered. The filtrate was evaporated to dryness under reduced pressure to give the title compound (0.13 g; 87%) as yellowish solid, which was used in next step without further purification. 1 H-NMR (CDCl 3 ) 7.8 (broad s, 1H); 7.56 (d, 2H, J=8.1 Hz); 7.15 (d, 2H, J=8.1 Hz); 2.58 (t, 2H, J=7.9 Hz); 1.59 (m, 2H); 1.52 (s, 9H); 1.26 (m, 10H); 0.86 (t, 3H, J=7 Hz).
[0133] Step B: tert-Butyl 2-(4-octylbenzyl)hydrazinecarboxylate: To a solution of the product of Step A (0.13 g; 0.391 mmol) in anhydrous THF (1 ml) and glacial AcOH (0.6 ml) NaBH 3 CN (0.06 g; 0.95 mmol) was added at −0° C. (ice bath). The resulting mixture was stirred overnight at room temperature then diluted to 15 ml with Et 2 O. This was washed with 5% NaHCO 3 H 2 O, brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated under reduced pressure to give the title compound (0.01 g; 16%) as a colourless syrup, which was used in the next step without further purification. 1 H-NMR (CDCl 3 ) 7.23 (d, 2H, J=8 Hz); 7.12 (d, 3H, J=8 Hz); 6.0 (s, 1H); 4.1 (broad s, 2H); 3.94 (s, 2H); 2.57 (t, 3H, J=7.9 Hz); 1.56 (m, 2H); 1.45 (s, 9H); 1.26 (m, 10H); 0.86 (t, 3H, J=7 Hz).
[0134] Step C: tert-Butyl 2-(2-ethoxy-2-oxoethylcarbamoyl)-2-(4-octylbenzyl)-hydrazine-carboxylate: When the product of Step B was substituted for 4-n-octylbenzylamine in Example 14, Step A, the identical process afforded the title compound in 84% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.14 (m, 4H); 5.95 (s, 1H); 5.87 (t, 1H, J=5 Hz); 4.5 (broad s, 1H); 4.19 (q, 2H, J=7.1 Hz); 4.03 (d, 2H, J=5 Hz); 2.57 (t, 2H, J=7.9 Hz); 1.56 (m, 2H); 1.44 (s, 9H); 1.27 (m, 13H); 0.86 (t, 3H, J=7 Hz).
[0135] Step D: Ethyl 2-(1-(4-octylbenzyl)hydrazinecarboxamido)acetate: When the product of Step C was substituted for tert-butyl 4-n-octylphenyl(methyl)carbamate in Example 12, Step B, the identical process afforded the title compound in 89% yield, as a creamy solid, which was used in the next step without further purification. 1 H-NMR (CDCl 3 ) 7.15 (m, 4H); 6.84 (broad m, 1H); 4.66 (s, 2H); 4.2 (q, 2H, J=7.14 Hz); 4.02 (d, 2H, J=5.8 Hz); 3.42 (bs, 2H); 2.57 (t, 2H, J=7.9 Hz); 1.57 (m, 2H); 1.27 (m, 13H); 0.86 (t, 3H, J=6.9 Hz).
[0136] Step E: 2-(1-(4-Octylbenzyl)hydrazinecarboxamido)acetic acid: When the product of Step D is substituted for ethyl 3-(3-(4-octylphenyl)ureido)propanoate in Example 11, Step B, the identical process afforded the title compound in 78% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.15 (m, 4H); 6.91 (t, 1H, J=5.7 Hz); 4.66 (s, 2H); 4.02 (d, 2H, J=5.7 Hz); 3.56 (bs, 3H); 2.57 (t, 2H, J=7.9 Hz); 1.58 (m, 2H); 1.26 (m, 10H); 0.86 (t, 3H, J=7 Hz).
Example 17
3-(5-Octylindoline-1-carboxamido)propanoic acid
[0137] Step A: 5-iodoindoline: To a solution of 5-iodoindole (0.2 g; 0.82 mmol) in AcOH (5 ml) NaBH 3 CN (0.2 g; 3.8 mmol) was added at −10° C. under N 2 . After stirring for 1 h at room temperature the solvent was removed in vacuo and the residue was diluted to 30 ml with Et 2 O and washed with 1 N NaOH (5 ml), H 2 O (2×5 ml), brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure to give the title compound (0.2 g; 99%), which was used in next step without further purification. 1 H-NMR (CDCl 3 ) 7.35 (s, 1H); 7.25 (d, 1H, J=8.15 Hz); 6.43 (d, 1H, J=8.15 Hz); 5.21 (bs, 1H); 3.54 (t, 2H, J=8.36 Hz); 2.99 (t, 2H, J=8.36 Hz).
[0138] Step B: Ethyl 3-(5-iodoindoline-1-carboxamido)propanoate: When the product of Step A was substituted for 4-n-octylaniline in Example 11, Step A, the identical process afforded the title compound in 99% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.67 (d, 1H, J=8.3 Hz); 7.4 (m, 2H); 5.34 (m, 1H); 4.14 (q, 2H, J=7.1 Hz); 3.86 (t, 2H, J=8.8 Hz); 3.56 (q, 2H, J=5.9 Hz); 3.13 (t, 2H, J=8.6 Hz); 2.58 (t, 2H, J=5.7 Hz); 1.26 (t, 3H, J=7.1 Hz).
[0139] Step C: Ethyl 3-(5-(oct-1-ynyl)indoline-1-carboxamido)propanoate: A mixture of the product of Step B (0.16 g; 0.41 mmol), 1-octyne (0.073 ml; 0.49 mmol), Cl 2 Pd(PPh 3 ) 2 (0.02 g; 0.028 mmol) and CuI (0.005 g; 0.026 mmol) was degassed under reduced pressure and saturated with dry N 2 . After addition of DIPEA (0.5 ml), the resulting mixture was stirred for 2 h at room temperature under N 2 . The solvents were removed in vacuo and the residue was diluted to 15 ml with EtOAc and washed with 5% citric acid, 5% NaHCO 3 , H 2 O, brine and dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was purified by FCC (SiO 2 ; CH 2 Cl 2 ) to give the title compound (0.1 g; 65%) as a brownish solid. 1 H-NMR (CDCl 3 ) 7.75 (d, 1H, J=8.4 Hz); 7.16 (d, 1H, J=8.4 Hz); 7.1 (s, 1H); 5.34 (t, 1H, J=5.8 Hz); 4.11 (q, 2H, J=7.1 Hz); 3.82 (t, 2H, J=8.8 Hz); 3.52 (m, 2H); 3.06 (t, 2H, J=8.8 Hz); 2.56 (t, 2H, J=5.8 Hz); 2.33 (t, 2H, J=7.1 Hz); 1.53 (m, 2H); 1.52 (m, 2H); 1.26 (m, 6H); 1.23 (t, 2H, J=7.1 Hz); 0.86 (t, 3H, J=6.9 Hz).
[0140] Step D: Ethyl 3-(5-octylindoline-1-carboxamido)propanoate: A mixture of the product of Step C (0.1 g; 0.27 mmol) and 10% Pd/C (0.1 g) in EtOH (15 ml) was stirred at room temperature for 1 h under H 2 (balloon). The catalyst was removed by filtration through the Celite pad, washed with CH 2 Cl 2 (2×10 ml) and combined filtrates were evaporated to dryness under reduced pressure to give a title compound (0.09 g; 90%), as colourless solid. 1 H-NMR (CDCl 3 ) 7.71 (d, 1H, J=8.8 Hz); 6.94 (d, 1H, J=8.8 Hz); 6.93 (s, 1H); 5.29 (m, 1H); 4.14 (q, 2H, J=7 Hz); 3.82 (t, 2H, J=8.8 Hz); 3.57 (q, 2H, J=5.9 Hz); 3.11 (t, 2H, J=8.6 Hz); 2.59 (t, 2H, J=5.7 Hz); 2.51 (t, 2H, J=7.7 Hz); 1.57 (m, 2H); 1.26 (m, 13H); 0.86 (t, 3H, J=7 Hz).
[0141] Step E: 3-(5-Octylindoline-1-carboxamido)propanoic acid: When the product of Step D was substituted for ethyl 3-(3-(4-octylphenyl)ureido)propanoate in Example 11, Step B, the identical process afforded the title compound in 84% yield, as a colourless solid. 1 H-NMR (CDCl 3 ) 7.68 (d, 1H, J=8.7 Hz); 6.94 (m, 2H); 5.24 (t, 1H, J=5.9 Hz); 3.86 (t, 2H, J=8.7 Hz); 3.58 (q, 2H, J=5.9 Hz); 3.11 (t, 2H, J=8.5 Hz); 2.67 (t, 2H, J=5.8 Hz); 2.5 (t, 2H, J=8 Hz); 1.54 (m, 2H); 1.25 (m, 10H); 0.86 (t, 3H, J=6.8 Hz).
Example 18
4-(4-(N-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)sulfamoyl)phenyl)butyl-dihydrogen phosphate
[0142] Step A: 4-Bromo-N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)benzene sulfonamide: To a stirred solution of 4-bromo-benzenesulphonyl chloride (0.6 g, 2.34 mmol) in anhydrous CH 2 Cl 2 (5 ml) and Et 3 N (0.65 ml, excess) at 0° C. was added (−) cis-myrtanylamine (0.36 g, 2.34 mmol) and the stirring was continued overnight at room temperature. The reaction mixture was diluted with CH 2 Cl 2 (15 ml) and washed with H 2 O (2×100 ml). The organic layer was separated and dried over MgSO 4 and the solvent was distilled to afford the title compound (0.87 g, 100%), as pale paste, which was solidified on standing. 1 H-NMR (CDCl 3 ) 7.70 (d, 2H, J=6.78 Hz); 6.64 (d, 2H, J=6.90 Hz); 2.91 (t, 2H, J=7.59 Hz); 2.32-2.29 (m, 1H); 2.11-2.06 (m, 1H); 1.91-1.81 (m, 6H); 1.39-1.31 (m, 1H); 1.11 (s, 3H); 0.86 (s, 3H).
[0143] Step B: N-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxybut-1-ynyl)benzene sulfonamide: A solution of the product of Step A (0.37 g, 0.5 mmol) and but-3-yn-1-ol (0.12 ml, excess) in a mixture of DMF (5 ml) and DIPEA (0.5 ml) was degassed with N 2 and Cl 2 Pd(PPh 3 ) 2 (0.07 g) was added, followed by catalytic amount of CuI and the mixture was stirred for 16 h at room temperature. The reaction was quenched with saturated NH 4 Cl solution and diluted with H 2 O followed by the extraction with EtOAc (100 ml). The organic layer was separated, dried over MgSO 4 , filtered and the filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the product (0.11 g, 60%), as creamy paste. 1 H-NMR (CDCl 3 ) 7.66 (d, 2H, J=8.43 Hz); 7.51 (d, 2H, J=8.43 Hz); 3.81 (b, 2H); 3.01-2.86 (m, 2H); 2.71-2.67 (m, 4H); 2.50-2.10 (m, 2H); 1.94-1.82 (m, 5H); 1.52-1.48 (m, 1H); 1.18 (s, 3H); 1.02 (s, 3H).
[0144] Step C: N-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxybutyl)benzene sulfonamide: A mixture of the product of Step B (0.11 g, 0.3 mmol) and 10% Pd/C (0.06 g) in EtOH (10 ml) was stirred for 16 h under H 2 . The catalyst was filtered through Celite pad and the filtrate evaporated to dryness to give the title compound (0.11 g, 100%) as creamy gum. 1 H-NMR (CDCl 3 ) 7.74 (d, 2H, J=7.89 Hz); 7.29 (d, 2H, J=8.01 Hz); 4.9 (bs, 1H, NH); 3.71-3.65 (m, 2H); 2.92-2.87 (m, 2H); 2.70 (t, 2H, J=7.74 Hz); 2.45-2.30 (m, 1H); 2.25-2.10 (m, 1H); 1.86-1.58 (m, 9H); 1.3-1.1 (m, 2H); 1.08 (s, 3H); 0.83 (s, 3H).
[0145] Step D: 4-(4-(N-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)sulfamoyl)phenyl) butyl-dihydrogen phosphate: To a stirred solution of POCl 3 (0.006 ml, 0.66 mmol) in anhydrous CH 2 Cl 2 (3 ml) a solution of tert-butanol (0.062 ml, 0.65 mmol) and Et 3 N (0.09 ml, 0.65 mmol) was added drop wise at 0° C. under N 2 . The mixture was stirred for 0.5 h and to it a solution of the product of Step C (0.08 g, 0.22 mmol) in a mixture of anhydrous CH 2 Cl 2 (1 ml) and Et 3 N (0.03 ml) was added drop wise. The mixture was stirred for 1 h at room temperature. The solvent was evaporated under reduced pressure and the residue was treated dropwise with a solution of 10% NaOH until the mixture become homogenous. This was washed with CH 2 Cl 2 (2×10 ml), and the aqueous phase was acidified with 2M HCl. The product was extracted with CH 2 Cl 2 (20 ml) and dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give the title compound (0.065 g, 65%) as pale paste. 1 H-NMR (CDCl 3 ) 7.67 (d, 2H, J=7.13 Hz); 7.23 (d, 2H); 3.94 (bs, 1H, NH); 3.86 (d, 2H, J=7.67 Hz); 2.58 (b, 2H); 2.28 (b, 1H); 2.13 (b, 1H); 1.84-1.82 (b, 5H); 1.35 (b, 4H); 1.22-1.24 (b, 2H); 0.96 (s, 3H); 0.86 (s, 3H).
Example 19
4-(4-(3-(3-(2,2,2-trifluoroacetyl)-1H-indol-1-yl)propyl)phenyl)butyl-dihydrogen phosphate
[0146] Step A: 2,2,2-Trifluoro-1-(1H-indol-3-yl)ethenone: To a stirred solution of indole (0.5 g, 4.3 mmol) in anhydrous Et 2 O (10 ml) anhydrous pyridine (0.5 ml) was added at 0° C., followed by drop wise addition of (CF 3 CO) 2 O (0.87 ml, 5.16 mmol). The mixture was stirred for 15 min and the solvent was evaporated to dryness. The residue was diluted to 20 ml with EtOAc, washed with H 2 O, dried over MgSO 4 , filtered and the filtrate was evaporated to dryness. The residue was crystallized from CH 3 OH to give the title compound (0.56 g; 61%), as colourless solid. 1 H-NMR (CDCl 3 ) 9.04 (broad s, 1H); 8.40 (t, 1H, J=4.11 Hz); 8.06 (s, 1H); 7.48-7.45 (m, 1H); 7.40-7.35 (m, 2H).
[0147] Step B: 2,2,2-Trifluoro-1-(1-(prop-2-ynyl)-1H-indol-3-yl)ethanone: A mixture of product of Step A (0.55 g, 2.58 mmol), K 2 CO 3 (0.43 g, 3.11 mmol) and propyrgyl bromide (2 ml) in anhydrous DMF (8 ml). was stirred for 4 h. The mixture was quenched with NH 4 Cl solution and diluted to 50 ml with EtOAc. The organic layer separated and washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to give the title compound (0.57 g, 88%), as yellow crystalline material. 1 H-NMR (CDCl 3 ) 8.41-8.38 (b, 1H); 7.99 (s, 1H); 7.48-7.31 (m, 3H); 4.96 (d, 2H, J=2.55 Hz); 2.58 (t, 1H, J=2.55 Hz).
[0148] Step C: 2,2,2-Trifluoro-1-(1-(3-(4-iodophenyl)prop-2-ynyl)-1H-indol-3-yl)ethanone: A mixture of product of Step B (0.25 g, 1 mmol), 1,4 di-idobenzene (0.4 g, 1.2 mmol) Cl 2 Pd(PPh 3 ) 2 (0.06 g) and catalytic amount of CuI in a mixture of DMF:DIPEA (10 ml: 0.5 ml) at room temperature was degassed under reduced pressure and saturated with N 2 . This was stirred overnight at room temperature, quenched with NaHCO 3 solution and diluted to 50 ml with EtOAc. The organic layer was separated and washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.28 g, 51%), as light yellow solid. 1 H-NMR (CDCl 3 ) 8.43-8.40 (b, 1H); 8.12 (b, 1H); 7.66 (t, 2H, J=8.36 Hz); 7.55-7.51 (m, 1H); 7.44-7.38 (m, 2H); 7.14 (d, 2H, J=8.30 Hz); 5.16 (s, 2H).
[0149] Step D: 2,2,2-Trifluoro-1-(1-(3-(4-(4-hydroxybut-1-ynyl)phenyl)prop-2-ynyl)-1H-indol-3-yl)ethanone: When the product of Step C was substituted for 4-bromo-N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)benzene sulphonamide in Example 18, Step B, the identical process afforded the title compound in 84% yield, as creamy paste. 1 H-NMR (CDCl 3 ) 8.43-8.40 (m, 1H); 8.14 (s, 1H); 7.56-7.53 (m, 1H); 7.44-7.37 (m, 2H); 7.37 (s, 4H); 5.19 (s, 2H); 3.8 (t, 2H, J=6.24 Hz); 2.69 (t, 2H, J=6.24 Hz); 1.76 (bs, 1H).
[0150] Step E: 2,2,2-Trifluoro-1-(1-(3-(4-(4-hydroxybutyl)phenyl)propyl)-1H-indol-3-yl)ethanone: When the product of Step D was substituted for N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxybut-1-ynyl)benzene sulphonamide in Example 18, Step C, the identical process afforded the title compound in 92% yield, as pale paste. 1 H-NMR (CDCl 3 ) 8.40 (broad s, 1H); 7.86 (s, 1H); 7.37-7.32 (m, 3H); 7.11 (d, 2H, J=8.07 Hz); 7.05 (d, 2H, J=8.07 Hz); 4.19 (t, 2H, J=7.17 Hz); 3.72-3.63 (m, 4H); 2.66-2.59 (m, 4H); 1.68-1.60 (m, 4H).
[0151] Step F: 4-(4-(3-(3-(2,2,2-trifluoroacetyl)-1H-indol-1-yl)propyl)phenyl)butyl-dihydrogen phosphate: When the product of Step E was substituted for N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxy butyl)benzene sulphonamide in Example 18, Step D, the similar process afforded the title compound in 73% yield, as pale paste. 1 H-NMR (CDCl 3 ) 8.35 (broad s, 1H); 7.83 (s, 1H); 7.36-7.30 (m, 3H); 7.10-6.93 (m, 4H); 3.98 (m, 2H); 2.55-2.50 (m, 6H); 2.23-2.15 (m, 2H); 1.59 (b, 4H).
Example 20
4-(4-(2-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)phenyl)butyl-dihydrogen phosphate
[0152] Step A: 2-(2-(4-Iodophenoxy)ethyl)-6,6-dimethylbicyclo[3.1.1]heptane: To a stirred suspension of 4-iodophenol (0.5 g; 2.27 mmol) and 60% NaH (0.16 g, 2.3 mmol) in anhydrous DMF (5 ml) 2-(2-bromoethyl)-6,6-dimethylbicyclo[3.1.1]heptane (0.5 g, 2.2 mmol) was added the and mixture was stirred for 3 h at room temperature. After addition of more of 2-(2-bromoethyl)-6,6-dimethylbicyclo[3.1.1]heptane (0.2 g) the mixture was stirred for additional 2 h, quenched with NH 4 Cl solution and diluted to 20 ml with EtOAc. The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.61 g, 73%), as a colourless paste. 1 H-NMR (CDCl 3 ) 7.51 (d, 2H, J=8.91 Hz); 6.64 (d, 2H, J=8.88 Hz); 3.88 (t, 2H, J=3.21 Hz); 2.34-1.84 (m, 10H); 1.17 (s, 3H); 1.01 (s, 3H).
[0153] Step B: 4-(4-(2-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)phenyl)but-3-yn-1-ol: When the product of Step A was substituted for 4-bromo-N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)benzene sulphonamide in Example 18, Step B, the similar process afforded the title compound in 78% yield, as pale paste. 1 H-NMR (CDCl 3 ) 7.29 (d, 2H, J=8.76 Hz); 6.78 (d, 2H, J=8.82 Hz); 3.80-3.76 (m, 2H); 3.92 (t, 2H, J=1.89 Hz); 2.65 (t, 2H, J=6.21 Hz); 1.92-1.81 (m, 10H); 1.18 (5, 3H); 1.01 (s, 3H).
[0154] Step C: 4-(4-(2-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)phenyl) butan-1-ol: When the product of Step B was substituted for N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxybut-1-ynyl)benzene sulphonamide in Example 18, Step C, the similar process afforded the title compound in 99% yield, as a colourless paste. 1 H-NMR (CDCl 3 ) 7.05 (d, 2H, J=8.54 Hz); 6.78 (d, 2H, J=8.58 Hz); 3.91 (t, 2H, J=6.81 Hz); 3.64 (t, 2H, J=6.02 Hz); 2.57-2.53 (m, 2H); 1.90-1.57 (m, 14H); 1.18 (s, 3H); 1.01 (s, 3H).
[0155] Step D: 4-(4-(2-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)phenyl) butyl-di-hydrogen phosphate: When the product of Step C was substituted for N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxybutyl)benzene sulfonamide in Example 18, Step D, the similar process afforded the title compound in 60% yield, as pale paste. 1 H-NMR (CDCl 3 ) 7.05 (d, 2H, J=8.31 Hz); 6.74 (d, 2H, J=8.16 Hz); 3.93-3.84 (m, 4H); 2.53-2.15 (m, 16H); 1.15 (s, 3H); 0.99 (s, 3H).
Example 21
2-(4-(2-(6-Methoxy-2,3-dihydrobenzofuran-2-yl)ethyl)phenoxy)ethanol
[0156] Step A: 4-((6-Methoxybenzofuran-2-yl)ethynyl)phenyl acetate: When 4-iodophenyl acetate and 2-ethynyl-6-methoxybenzofuran were substituted for 4-bromo-N-(6,6-dimethylbicyclo [3.1.1]heptan-2-yl)benzene sulphonamide and but-3-yn-1-ol respectively in Example 18, Step B, the similar process afforded the title compound in 56% yield, as creamy paste. 1 H-NMR (CDCl 3 ) 7.56 (d, 2H, J=8.67 Hz); 7.41 (d, 1H, J=8.58 Hz); 7.10 (d, 2H, J=8.7 Hz); 6.97 (d, 1H, J=1.92 Hz); 6.9 (s, 1H); 6.88 (bd, 1H, J=8.61 Hz); 3.85 (5, 3H); 2.3 (s, 3H).
[0157] Step B: 4-(2-(6-Methoxy-2,3-dihydrobenzofuran-2-yl)ethyl)phenol: When the product of Step A was substituted for N-(6,6-dimethyl bicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxybut-1-ynyl)benzenesulphonamide in Example 18, Step C, the similar process (higher pressure of H 2 ) afforded the title compound in 96% yield, as creamy paste. 1 H-NMR (CDCl 3 ) 7.25-7.19 (m, 2H); 7.02-6.97 (m, 3H); 6.38-6.35 (m, 2H); 4.81-4.72 (m, 1H); 3.75 (s, 3H); 3.24-3.16 (m, 1H); 2.83-2.73 (m, 3H); 2.27 (s, 3H); 2.13-2.07 (m, 1H); 2.06-1.92 (m, 1H).
[0158] Step C: Ethyl 2-(4-(2-(6-methoxy-2,3-dihydrobenzofuran-2-yl)ethyl)phenoxy)acetate: To a stirred solution of the product of Step A (0.05 g, 0.19 mmol) and K 2 CO 3 (0.05 g, 0.36 mmol) in anhydrous DMF (5 ml) ethyl-bromo acetate (0.025 ml, 0.22 mmol) was added at room temperature. The mixture was stirred for 2 h and quenched with saturated NH 4 Cl solution, extracted in EtOAc (100 ml) and washed with H 2 O. The organic layer was separated and dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give the title compound (0.07 g; 100%), as pale oil. 1 H-NMR (CDCl 3 ) 7.10 (d, 2H, J=8.39 Hz); 6.97 (d, 1H, J=8.46 Hz); 6.80 (t, 2H, J=8.36 Hz); 6.35-6.33 (m, 2H); 4.75-4.71 (m, 1H); 4.56 (s, 2H); 4.22 (q, 2H, J=14.36, 7.17 Hz); 3.72 (s, 3H, OMe); 3.2-3.13 (m, 1H); 2.79-2.69 (m, 3H); 2.0-1.87 (m, 2H); 1.26 (t, 3H, J=7.12 Hz).
[0159] Step D: 2-(4-(2-(6-Methoxy-2,3-dihydrobenzofuran-2-yl)ethyl)phenoxy)ethanol: To the stirred slurry of LiAlH 4 (0.01 g, 0.026 mmol) in anhydrous Et 2 O (5 ml) the solution of the product of Step C (0.04 g, 0.11 mmol) in anhydrous Et 2 O (2 ml) was added drop wise and stirring was continued for 0.5 h at room temperature. The reaction mixture was quenched with EtOAc: H 2 O: MeOH mixture (7 ml: 3 ml: 1 ml), diluted to 20 ml with EtOAc and filtered through Celite. The filtrate was evaporated under reduced pressure and dried in vacuo to give the title compound (0.032 g, 94%), as colourless solid. 1 H-NMR (CDCl 3 ) 7.13 (d, 2H, J=8.54 Hz); 6.99 (d, 1H, J=8.56 Hz); 6.84 (d, 2H, J=8.58 Hz); 6.38-6.34 (m, 2H); 4.79-4.74 (m, 1H); 4.65 (t, 2H, J=4.14 Hz); 3.96-3.90 (m, 2H); 3.75 (s, 3H); 3.22-3.14 (m, 1H); 2.82-2.68 (m, 2H); 2.11-1.91 (m, 3H).
Example 22
2-((4-(5-(((4-Fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzyl) (methyl)amino)ethanol
[0160] Step A: 4-(5-(Hydroxymethyl)thiophen-2-yl)benzaldehyde: The thiphene-5-al-2-boronic acid (0.47 g, 2.97 mmol) was reduced with NaBH 4 (0.15 g, 3.95 mmol) in MeOH (3 ml) and solvent was evaporated to dryness. The residue was taken in 1,4-dioxane (12 ml) and 4-bromobenzaldehyde (0.65 g, 3.5 mmol) was added. To this Pd(PPh 3 ) 4 (0.05 g) was added with stirring at 80° C., followed by the addition of a solution of NaHCO 3 (0.6 g) in H 2 O (2 ml). The mixture was stirred at reflux for 1 h and the solvents were evaporated to dryness under reduced pressure. The residue was diluted to 100 ml with EtOAc and washed with H 2 O. The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.61 g, 80%), as creamy paste. 1 H-NMR (CDCl 3 ) 9.98 (s, 1H, CHO); 7.87 (d, 2H, J=8.3 Hz); 7.72 (d, 2H, J=8.31 Hz); 7.31 (d, 1H, J=3.74 Hz); 7.0 (d, 2H, J=3.7 Hz); 4.84 (s, 2H).
[0161] Step B: 4-(5-(((4-Fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde: To a stirred solution of the product of Step A (0.436 g, 2 mmol) in anhydrous CH 2 Cl 2 (10 ml) and Et 3 N (0.3 ml) mesyl chloride (0.4 ml) was added at 0° C. and stirring was continued for 1 h. The solvents were evaporated to dryness under reduced pressure and the residue was diluted to 50 ml with EtOAc and washed with H 2 O. The organic layer was separated and dried over MgSO 4 and filtered. The filtrate was evaporated to give the crude product (0.63 g) as pale paste, which was taken up in anhydrous toluene and 4-fluoro-N-isopropylaniline (0.5 ml) was added to it. The mixture was stirred overnight at reflux and the solvent was evaporated. The residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.14 g, 20%), as light creamy paste. 1 H-NMR (CDCl 3 ) 9.98 (s, 1H); 7.82 (d, 2H, J=8.31 Hz); 7.66 (d, 2H, J=8.31 Hz); 7.28 (d, 1H, J=3.69 Hz); 6.93-6.86 (m, 3H); 6.81-6.76 (m, 2H); 4.79 (s, 2H); 4.08-3.99 (m, 1H); 1.22 (d, 6H, J=6.6 Hz).
[0162] Step C: Methyl-2-((4-(5-(((4-fluorophenyl)(isopropyl)amino)methyl) thiophen-2-yl)benzyl)(methyl)amino) acetate: To a stirred solution of the product of Step B (0.09 g, 0.26 mmol) and sarcosine hydrochloride (0.07 g, 0.5 mmol) in 1,2-dichloroethane (5 ml) was added DIPEA (0.1 ml) and 10 drops of AcOH, followed by NaBH(OAc) 3 (0.11 g, 0.51 mmol). The mixture was stirred overnight at room temperature and diluted to 20 ml with CH 2 Cl 2 . The organic layer was washed with NaHCO 3 solution, H 2 O and dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.113 g, 100%) as creamy paste. 1 H-NMR (CDCl 3 ) 7.47 (d, 2H, J=8.19 Hz); 7.28 (d, 2H, J=8.18 Hz); 7.10 (d, 1H, J=3.62 Hz); 6.88-6.85 (m, 3H); 6.85-6.77 (m, 2H); 4.44 (s, 2H); 4.07-3.98 (m, 1H); 3.69 (s, 3H); 3.24 (s, 2H); 2.37 (s, 3H); 1.21 (d, 6H, J=6.6 Hz).
[0163] Step D: 2-((4-(5-(((4-Fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzyl)(methyl)amino)ethanol: When the product of Step C was substituted for ethyl-2-(4-(2-(6-methoxy-2,3-dihydrobenzofuran-2-yl)ethyl)phenoxy)acetate in Example 21, Step D, the similar process afforded the title compound in 28% yield, as light yellow paste. 1 H NMR (CDCl 3 ) 7.47 (d, 2H, J=8.05 Hz); 7.24 (d, 2H, J=8.04 Hz); 7.10 (d, 1H, J=3.60 Hz); 6.91-6.85 (m, 3H); 6.81-6.76 (m, 2H); 4.44 (s, 2H); 4.07-3.98 (m, 1H); 3.61 (t, 2H, J=5.31 Hz); 3.53 (s, 3H); 2.58 (t, 2H, J=5.31 Hz); 2.21 (s, 3H); 1.21 (d, 6H, J=6.56 Hz).
Example 23
2-(4-(5-(((4-Fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzylamino)propane-1,3-diol
[0164] Step A: N-(4-(5-(((4-Fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzyl)-2,2-dimethyl-1,3-dioxan-5-amine: When 2,2-dimethyl-1,3-dioxan-5-amine was substituted for sarcosine hydrochloride in Example 22, Step C, the similar process afforded the title compound in 90% yield, as creamy paste. 1 H NMR (CDCl 3 ) 7.47 (d, 2H, J=8.2 Hz); 7.29 (d, 2H, J=8.2 Hz); 7.0 (d, 1H, J=3.61 Hz); 6.9-6.85 (m, 3H); 6.82-6.76 (m, 2H); 4.38 (s, 2H); 4.07-4.0 (m, 1H); 3.96 (dd, 2H, J=11.7, 3.5 Hz); 3.81 (s, 2H); 3.72 (dd, 2H, J=11.8, 5.34 Hz); 2.68-2.63 (m, 1H); 1.41 (s, 3H); 1.4 (s, 3H); 1.21 (d, 6H, J=6.6 Hz).
[0165] Step B: 2-(4-(5-(((4-Fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzylamino)propane-1,3-diol: A solution of the product of Step A (0.025 g, 0.05 mmol) in a mixture of solvents (CH 3 OH, CH 2 Cl 2 , 30% HCl: 1 ml, 3 ml, 15 drops) was stirred for 3 h at room temperature. The solvents were evaporated and co-evaporated with iPrOH to give the title compound (0.012 g, 48%) as creamy paste. 1 H-NMR (CDCl 3 ) 7.45 (d, 2H, J=8.12 Hz); 7.23-7.33 (m, 4H); 7.16-7.09 (m, 3H); 6.88 (d, 2H, J=3.68 Hz); 4.95 (bs, 1H); 4.21 (s, 2H); 4.07-4.02 (m, 1H); 3.92-3.68 (m, 6H); 3.29-3.26 (m, 1H); 1.03 (d, 6H, J=6.6 Hz).
Example 24
2-(4-(3-((4-Fluorophenyl)(isopropyl)amino)propyl)benzylamino)propane-1,3-diol hydrochloride
[0166] Step A: N-(3-(4-(Diethoxymethyl)phenyl)prop-2-ynyl)-4-fluorobenzenamine: When 4-bromo-benzene-diethylacetal and 4-fluoro-N-propyrgylaniline was substituted for 4-bromo-N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)benzene sulphonamide and but-3-yn-1-ol, respectively, in Example 18, Step B, the similar process afforded the title compound in 36% yield, as pale paste. 1 H-NMR (CDCl 3 ) 7.38 (d, 2H, J=8.7 Hz); 6.84 (d, 2H, J=8.6 Hz); 6.92 (t, 2H, J=7.8 Hz); 6.68-6.64 (m, 2H); 5.46 (s, 1H); 4.10 (s, 3H); 3.62-3.44 (m, 4H); 1.21 (t, 6H, J=7.04 Hz).
[0167] Step B: N-(3-(4-(Diethoxymethyl)phenyl)propyl)-4-fluorobenzenamine: When the product of Step A was substituted for N-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)-4-(4-hydroxybut-1-ynyl)benzene sulphonamide in Example 18, Step C, the similar process afforded the title crude product (0.195 g; 96%) as creamy paste. 1 H-NMR (CDCl 3 ) 7.35 (d, 2H, J=8.01 Hz); 7.14 (d, 2H, J=8.1 Hz); 6.85 (t, 2H, J=7.54 Hz); 6.51-6.45 (m, 2H); 5.46 (s, 1H); 3.73-3.48 (m, 4H); 3.07 (t, 2H, J=6.97 Hz); 2.71 (t, 2H, 7.45 Hz); 1.96-1.85 (m, 2H); 1.22 (t, 6H, J=7.07 Hz).
[0168] Step C: 4-(3-((4-Fluorophenyl)(isopropyl)amino)propyl)benzaldehyde: A mixture of 4-(3-(4-fluorophenylamino)propyl)benzaldehyde (0.09 g, 0.35 mmol) [prepared form the product of Step B by stirring in acidifies CHCl 3 ] and 2-bromopropane (0.2 ml) and K 2 CO 3 (0.1 g; 0.73 mmol) was stirred at reflux in anhydrous DMF (5 ml) for 6 h. The solvent was evaporated under reduced pressure and the residue was diluted to 50 ml with EtOAc and washed with H 2 O. The organic layer separated and dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc), to give the title compound (0.078 g, 83%) as creamy paste. 1 H-NMR (CDCl 3 ) 10 (s, 1H); 7.78 (d, 2H, J=8.13 Hz); 7.32 (d, 2H, J=8.07 Hz); 6.93-6.86 (m, 2H); 6.82-6.66 (m, 2H); 3.07 (t, 2H, J=7.5 Hz); 2.71 (t, 2H, J=7.5 Hz); 2.71 (t, 2H, 7.62 Hz); 2.27-2.21 (m, 1H); 1.86-1.83 (m, 1H); 1.08 (d, 6H, J=6.6 Hz).
[0169] Step D: N-(4-(3-((4-Fluorophenyl)(isopropyl)amino)propyl)benzyl)-2,2-dimethyl-1,3-dioxan-5-amine: When the product of Step C and 2,2-dimethyl-1,3-dioxan-5-amine were substituted for 4-(5-(((4-fluorophenyl)(isopropyl)amino)methyl)-thiophen-2-yl)benzaldehyde and sarcosine hydrochloride in Example 22, Step C, the similar process afforded the title compound in 48% yield, as creamy paste. 1 H-NMR (CDCl 3 ) 7.24 (d, 2H, J=7.92 Hz), 7.11 (d, 2H, J=7.92 Hz), 6.87 (t, 2H, J=8.9 Hz), 6.69-6.62 (m, 2H), 3.95 (dd, 2H, J=11.7, 3.6 Hz), 3.83-3.69 (m, 4H), 3.06 (t, 2H, J=7.54 Hz), 2.66-2.58 (m, 3H), 1.83-1.76 (m, 3H), 1.41 (s, 3H), 1.4 (s, 3H), 1.08 (d, 2H, J=6.59 Hz).
[0170] Step E: 2-(4-(3-((4-Fluorophenyl)(isopropyl)amino)propyl)benzylamino) propane-1,3-diol hydrochloride salt: When the product of Step D was substituted for N-(4-(5-(((4-fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzyl)-2,2-dimethyl-1,3-dioxan-5-amine in Example 23, Step B, the identical process afforded the title compound in 67% yield, as a creamy paste. 1 H-NMR (CDCl 3 ) 7.39-7.19 (m, 6H); 7.11 (d, 2H, J=7.99 Hz); 4.21 (s, 2H); 3.94-3.67 (m, 5H); 3.4-3.7 (m, 2H); 3.3-3.26 (m, 1H); 2.56 (b, 2H); 1.68 (b, 1H); 1.22 (b, 1H); 1.04 (d, 6H, J=6.2 Hz).
Example 25
1-((4′-(N-(3-methoxyphenyl)-N-methylsulfamoyl)biphenyl-4-yl)methyl)azetidine-3-carboxylic acid
[0171] Step A: 4-Bromo-N-(3-methoxyphenyl)benzenesulfonamide: To a stirred solution of 3-methoxyaniline (0.48 g, 3.92 mmol) in anhydrous pyridine (5 ml) 4-bromobenzene-sulphonyl chloride (0.5 g, 1.96 mmol) was added and the mixture was stirred for 0.5 h. The solvent was removed in vacuo and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.51 g, 37%) as creamy paste. 1 H-NMR (CDCl 3 ) 7.65 (d, 2H, J=8.57 Hz); 7.52 (d, 2H, J=8.57 Hz); 7.10 (t, 1H, J=8.09 Hz); 6.69-6.61 (m, 2H); 4.37 (s, 2H); 3.71 (s, 3H, OMe).
[0172] Step B: 4-Bromo-N-(3-methoxyphenyl)-N-methylbenzenesulfonamide: To a stirred mixture of the product of Step A (0.5 g 1.46 mmol) and K 2 CO 3 (0.5 g) in anhydrous DMF (7 ml) was added CH 3 I (1 ml) and the stirring continued for 0.5 h at 50° C. The mixture was diluted to 50 ml with H 2 O and extracted with EtOAc (50 ml). The organic layer was washed with H 2 O and dried over MgSO 4 , passed through silica gel bead and the filtrate was evaporated to dryness to give the title compound (0.5 g, 96%) as pale solid. 1 H-NMR (CDCl 3 ) 7.58 (d, 2H, J=8.64 Hz); 7.40 (d, 2H, J=8.67 Hz); 7.18 (t, 1H, J=8.15 Hz); 6.80 (dd, 1H, J=8.34, 2.5 Hz); 6.69 (t, 1H, J=2.20 Hz); 6.58 (bd, 1H); 3.75 (s, 3H, OMe); 3.14 (s, 3H, N-Me).
[0173] Step C: 4′-Formyl-N-(3-methoxyphenyl)-N-methylbiphenyl-4-sulfonamide: When the product of Step B and 4-carbaldehyde-boronic acid were substituted for 4-bromobenzaldehyde and 5-(hydroxymethyl)thiophen-2-ylboronic acid, respectively, in Example 22, Step A, the similar process afforded the title compound in 73% yield, as pale solid. 1 H-NMR (CDCl 3 ) 10.07 (s, 1H); 7.98 (d, 2H, J=6.56 Hz); 7.75 (d, 2H, J=8.24 Hz); 7.7 (d, 2H, J=8.82 Hz); 7.66 (d, 2H, J=8.75 Hz); 7.19 (t, 1H, J=8.13 Hz); 6.81 (dd, 1H, J=8.30, 2.45 Hz); 6.74 (t, 1H, J=2.17 Hz); 6.65 (dd, 1H, J=7.96, 1.24 Hz); 3.76 (s, 3H); 3.20 (s, 3H).
[0174] Step D: Methyl-1-((4′-(N-(3-methoxyphenyl)-N-methylsulfamoyl)biphenyl-4-yl)methyl) azetidine-3-carboxylate: When the product of Step C and azatadine 3 methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl)(isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, in Example 22, Step C, the similar process the title compound in 69% yield, as pale paste. 1 H-NMR (CDCl 3 ) 7.64 (d, 2H, J=8.8 Hz); 7.58 (d, 2H, J=8 Hz); 7.54 (d, 2H, J=8.15 Hz); 7.36 (d, 2H, J=8.12 Hz); 7.17 (t, 1H, J=8.14 Hz); 6.80 (dd, 1H, J=8.07, 2.21 Hz); 6.72 (t, 1H, J=2.10 Hz); 6.64 (dd, 1H, J=7.80, 1.67 Hz); 3.74 (s, 3H); 3.71 (s, 2H); 3.69 (s, 3H); 3.64-3.58 (m, 2H); 3.42-3.36 (m, 4H); 3.18 (s, 3H).
[0175] Step E: 1-((4′-(N-(3-methoxyphenyl)-N-methylsulfamoyl)biphenyl-4-yl)methyl)azetidine-3-carboxylic acid: To a stirred solution of the product of Step D (0.06 g, 0.13 mmol) in THF (3 ml) a solution of LiOH (0.006 g, 0.25 mmol) in H 2 O (1 ml) was added at 80° C. The mixture was stirred for 0.5 h and solvents were evaporated to dryness. The residue was purified by FCC (SiO 2 ) to give the title compound (0.0026 g, 43%) as creamy solid. 1 H-NMR (CDCl 3 :CD 3 OD) 7.58 (s, 4H); 7.58 (d, 2H, J=8 Hz); 7.56 (d, 2H, J=7.23 Hz); 7.49 (d, 2H, J=8.25 Hz); 7.13 (t, 1H, J=8.14 Hz); 6.76 (dd, 1H, J=8.33, 2.05 Hz); 6.68 (t, 1H, J=2.15 Hz); 6.58 (dd, 1H, J=7.94, 1.32 Hz); 4.25 (s, 2H); 4.21-4.02 (m, 4H); 3.70 (s, 3H); 3.38-3.32 (m, 3H); 3.13 (s, 3H).
Example 26
2-(((4′-(((4-Fluorophenyl)(isopropyl)amino)methyl)biphenyl-4-yl)methyl)(methyl)amino)acetic acid
[0176] Step A: 4-Fluoro-N-isopropylaniline: A mixture of 4-fluoro-aniline (1.12 g; 10 mmol), 2-bromopropane (1.13 ml) and K 2 CO 3 (1.38 g, 10 mmol) in anhydrous DMF (6 ml) was stirred for 5 h at reflux. The mixture was cooled to room temperature, diluted to 100 ml with H 2 O and extracted with EtOAc (50 ml). The organic layer was washed with H 2 O (2×20 ml) and dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.65 g; 43%), as light yellow oil. 1 H-NMR (CDCl 3 ) 6.89-6.82 (m, 2H); 6.53-6.47 (m, 2H); 3.58-3.49 (m, 1H); 1.18 (d, 6H, J=6.25 Hz).
[0177] Step B: N-(4-Bromobenzyl)-4-fluoro-N-isopropylbenzenamine: When the product of Step A and 4-bromobenzaldehyde were substituted for sarcosine hydrochloride salt and 4-(5-(((4-fluorophenyl)) isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde, respectively, in Example 22, Step C, the similar process afforded the title compound in 93% yield, as a pale paste. 1 H-NMR (CDCl 3 ) 7.39 (d, 2H, J=8.18 Hz); 7.14 (d, 2H, J=8.08 Hz); 6.91-6.81 (m, 2H); 6.62-6.57 (m, 2H); 4.26 (s, 2H); 4.11-4.04 (m, 1H); 1.18 (d, 2H, J=5.34 Hz).
[0178] Step C: 4′-(((4-Fluorophenyl)(isopropyl)amino)methyl)biphenyl-4-carbaldehyde: When the product of Step B and 4-carbaldehyde-boronic acid were substituted for 4-bromobenzaldehyde and 5-(hydroxymethyl) thiophen-2-ylboronic acid, respectively, in Example 22, Step A, the similar process afforded the title compound in 65% yield, as creamy gum. 1 H-NMR (CDCl 3 ) 10.03 (s, 1H); 7.92 (d, 2H, J=7.97 Hz); 7.56 (d, 2H, J=7.95 Hz); 7.38 (d, 2H, J=8.29 Hz); 6.86 (t, 2H, J=8.46 Hz); 6.67-6.62 (m, 2H); 4.38 (s, 2H); 4.17-4.12 (m, 1H); 1.2 (d, 6H, J=6.96 Hz).
[0179] Step D: Methyl-2-(((4′-(((4-fluorophenyl)isopropyl)amino)methyl)biphenyl-4-yl)methylymethyl)amino)acetate: When the product of Step C was substituted for 4-(5-(((4-fluorophenyl))isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde in Example 22, Step C, the similar process afforded the title compound in 96% yield, as a creamy paste. 1 H-NMR (CDCl 3 ) 7.54-7.49 (m, 4H); 7.38-7.31 (m, 4H); 6.86 (t, 2H, J=8.45 Hz); 6.83-6.64 (m, 2H); 4.37 (s, 2H); 4.19-4.09 (m, 1H); 3.70 (5, 3H); 3.69 (s, 2H); 3.28 (s, 2H); 2.4 (s, 3H); 1.17 (d, 6H, J=7.71 Hz).
[0180] Step E: 2-(((4′-(((4-Fluorophenyl)(isopropyl)amino)methyl)biphenyl-4-yl)methyl)(methyl)amino)acetic acid: When the product of Step D was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl) azetidine-3-carboxylate in Example 25, Step E, the similar process afforded the title compound in 87% yield, as creamy solid. 1 H-NMR (CDCl 3 +CD 3 OD) 7.40-7.18 (m, 8H); 6.76 (t, 2H, J=8.82 Hz); 6.61-6.56 (m, 2H); 4.25 (s, 2H); 4.16 (s, 2H); 4.07-4.01 (m, 1H); 2.59 (s, 3H); 1.11 (d, 6H, J=6.48 Hz).
Example 27
1-((4′-(((4-Fluorophenyl)(isopropyl)amino)methyl)biphenyl-4-yl)methyl)azetidine-3-carboxylic acid
[0181] Step A: Methyl-1-((4′-(((4-fluorophenyl)(isopropyl)amino)methyl)biphenyl-4-yl)methyl)azetidine-3-carboxylate: When 4′-(((4-Fluorophenyl)(isopropyl)amino)methyl)biphenyl-4-carbaldehyde and azatadine 3-methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl))isopropyl)amino)-methyl)thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, in Example 22, Step C, the similar process afforded the title compound in 65% yield, as creamy paste. 1 H-NMR (CDCl 3 ) 7.53 (d, 2H, J=8.12 Hz); 7.48 (d, 2H, J=8.2 Hz); 6.85 (t, 2H, J=9.09 Hz); 6.67-6.62 (m, 2H); 4.37 (s, 2H); 4.16-4.11 (m, 1H); 3.86 (bs, 4H); 3.69 (s, 3H); 3.58-3.51 (m, 1H); 1.19 (d, 6H, J=6.63 Hz).
[0182] Step B: 1-((4′-(((4-Fluorophenyl)(isopropyl)amino)methyl)biphenyl-4-yl)methyl)azetidine-3-carboxylic acid: When the product of Step A was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar process afforded the title compound in 60% yield, as creamy solid. 1 H-NMR (CDCl 3 +CD 3 OD) 7.66 (d, 2H, J=8.13 Hz); 7.62-7.57 (m, 4H); 7.41 (d, 2H, J=8.07 Hz); 6.95-6.85 (m, 2H); 6.85-6.75 (m, 2H); 4.44 (s, 2H); 4.39 (s, 2H); 4.39-4.2 (m, 2H); 3.5-3.45 (m, 1H); 1.26 (d, 6H, J=6.54 Hz).
Example 28
1-(4-(4-oxo-4-(3,4,5-trimethoxyphenyl)but-2-en-2-yl)benzyl)azetidine-3-carboxylic acid
[0183] Step A: 3-Bromo-1-(3,4,5-trimethoxyphenyl)but-2-en-1-one: 1-(3,4,5-trimethoxyphenyl) but-2-yn-1-one (0.5 g, 2.58 mmol) was dissolved in AcOH (5 ml) and 48% HBr (5 drops) was added to it. The mixture was stirred for 2 h at 50° C. This was evaporated to dryness and the residue was diluted to 50 ml with EtOAc, washed with NaHCO 3 solution and H 2 O. The organic layer was dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and dried in vacuo to give the title compound (0.53 g, 65%), as a pale solid. 1 H-NMR (CDCl 3 ) 7.30 (s, 1H); 7.03 (s, 2H); 3.91 (s, 9H); 2.79 (s, 3H).
[0184] Step B: 4-(4-oxo-4-(3,4,5-trimethoxyphenyl)but-2-en-2-yl)benzaldehyde: When the product of Step A and 4-carbaldehyde-boronic acid were substituted for 5-(hydroxymethyl)thiophen-2-ylboronic acid and 4-bromobenzaldehyde, respectively, in Example 22, Step A, the similar process afforded the title compound in 81% yield, as creamy gum. 1 H-NMR (CDCl 3 ) 10.05 (s, 1H); 7.92 (d, 2H, J=8.25 Hz); 7.68 (d, 2H, J=8.28 Hz); 7.23 (s, 2H); 7.10 (s, 1H); 3.91 (s, 9H); 2.55 (s, 3H).
[0185] Step C: Methyl-1-(4-(4-oxo-4-(3,4,5-trimethoxyphenyl)but-2-en-2-yl)benzyl) azetidine-3-carboxylate: When the product of Step B and azatadine 3 methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl)) isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, in Example 22, Step-C, the similar process afforded the title compound in 66% yield, as pale paste. 1 H-NMR (CDCl 3 ) 7.49 (d, 2H, J=8.28 Hz); 7.30 (d, 2H, J=8.29 Hz); 7.22 (s, 2H), 7.06 (s, 1H); 3.90 (s, 9H); 3.68 (s, 3H); 3.64 (s, 2H); 3.56-3.52 (m, 2H); 3.37-3.32 (m, 3H).
[0186] Step D: 1-(4-(4-oxo-4-(3,4,5-trimethoxyphenyl)but-2-en-2-yl)benzyl)azetidine-3-carboxylic acid: When the product of Step C was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar process afforded the title compound in 53% yield, as light yellow solid. 1 H-NMR(CDCl 3 +CD 3 OD) 7.31 (d, 2H, J=8.18 Hz); 7.28 (d, 2H, J=8.28 Hz); 6.71 (s, 2H); 6.62 (s, 1H); 4.24 (s, 2H); 4.17-4.04 (m, 4H); 3.55-3.38 (s, 1H); 2.15 (s, 3H).
Example 29
1-((4′-(3-(3-(Trifluoromethyl)phenyl)but-2-enoyl)biphenyl-4-yl)methyl)azetidine-3-carboxylic acid
[0187] Step A: 1-(4-Bromophenyl)but-2-yn-1-one: To an ice cold solution of 4-bromobenzaldehyde (1.3 g, 7 mmol) 0.5 M solution of propynyl magnesium bromide in THF (15 ml, 7.5 mmol) was added under N 2 . The mixture was stirred for 10 min, quenched with saturated NH 4 Cl solution and diluted to 50 ml with EtOAc. The organic layer was washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was dissolved in 1,4-dioxane (25 ml). To it MnO 2 (2 g) was added and the resulting suspension was stirred for 4 h at reflux. The mixture was filtered through Celite pad and the filtrate was evaporated to dryness and dried in vacuo to give the title compound (1.29 g, 83%) as a pale solid. 1 H-NMR (CDCl 3 ) 7.97 (d, 2H, J=9 Hz); 7.61 (d, 2H, J=9 Hz); 2.14 (s, 3H).
[0188] Step B: 4′-But-2-ynoylbiphenyl-4-carbaldehyde: When the product of Step A and 4-carbaldehyde-boronic acid were substituted for 4-bromobenzaldehyde and 5-(hydroxymethyl)thiophen-2-ylboronic acid, respectively, in Example 22, Step A, the similar procedure afforded the title compound in 58% yield, as a creamy gum. 1 H-NMR (CDCl 3 ) 10.07 (s, 1H); 8.23 (d, 2H, J=8.4 Hz); 7.98 (d, 2H, J=8.4 Hz); 7.78 (d, 2H, J=8.24 Hz); 7.72 (d, 2H, J=8.54 Hz); 2.18 (s, 3H).
[0189] Step C: 4′-(3-Bromobut-2-enoyl)biphenyl-4-carbaldehyde: When the product of Step B was substituted for 1-(3,4,5-trimethoxyphenyl)but-2-yn-1-one in Example 28, Step A, the similar process afforded the title compound in 56% yield, as pale solid. 1 H-NMR (CDCl 3 ) 10.07 (s, 1H); 8.03-7.96 (m, 4H); 7.79-7.71 (m, 4H); 7.41 (s, 1H); 2.84 (s, 3H).
[0190] Step D: 4′-(3-(3-(Trifluoromethyl)phenyl)but-2-enoyl)biphenyl-4-carbaldehyde: When the product of Step C and 3-trifluoromethyl-boronic acid were substituted for 4-bromo benzaldehyde and 5-(hydroxymethyl)thiophen-2-ylboronic acid, respectively, in Example 22, Step A, the similar procedure afforded the title compound in 73% yield, as creamy gum. 1 H-NMR (CDCl 3 ) 10.07 (s, 1H); 8.1 (d, 2H, J=8.5 Hz); 7.99-7.93 (m, 3H); 7.8-7.57 (m, 5H); 7.18 (s, 1H); 2.61 (s, 3H).
[0191] Step E: Methyl-1-((4′-(3-(3-(trifluoromethyl)phenyl)but-2-enoyl)biphenyl-4-yl)methyl)azetidine-3-carboxylate: When the product of Step D and azatadine 3 methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl)) isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, in Example 22, Step C, the similar procedure afforded the title compound in 58% yield, as a pale paste. 1 H-NMR (CDCl 3 ) 8.04 (d, 2H, J=8.4 Hz); 7.78-7.51 (m, 8H); 7.4 (d, 2H, J=8.2 Hz); 7.16 (d, 1H, J=1.21 Hz); 3.76 (s, 2H); 3.7 (s, 3H); 3.73-3.62 (m, 4H); 3.47-3.41 (m, 3H); 2.58 (bs, 3H).
[0192] Step F: 1-((4′-(3-(3-(Trifluoromethyl)phenyl)but-2-enoyl)biphenyl-4-yl)methyl)azetidine-3-carboxylic acid: When the product of Step E was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar process afforded the title compound in 62% yield, as a light yellow solid. 1 H-NMR (CDCl 3 +CD 3 OD) 7.84 (d, 2H, J=8.34 Hz); 7.59-7.33 (m, 6H); 4.7 (d, 2H); 3.96-3.92 (m, 4H); 3.19-3.14 (m, 1H); 2.36 (s, 3H).
Example 30
1-(4-(4-oxo-2-phenyl-4H-chromen-6-yl)benzyl)azetidine-3-carboxylic acid
[0193] Step A: 5-Bromo-2-isopropoxybenzaldehyde: To a stirred solution of 2-isopropoxybenzaldehyde (0.51 g, 3.1 mmol), in DMF (10 ml) NBS (0.55 g, 3.1 mmol) was added and the reaction mixture was stirred overnight at room temperature. The reaction was quenched with NaHCO 3 solution and extracted in EtOAc (50 ml). The organic layer was washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give the title compound (0.62 g, 82%) as light yellow oil. 1 H-NMR (CDCl 3 ) 10.37 (s, 1H); 7.89 (d, 1H, J=2.52 Hz); 7.55 (dd, 1H, J=8.85, 2.58 Hz); 6.87 (d, 1H, J=8.88 Hz); 4.67-4.58 (m, 1H); 1.35 (d, 6H, J=6.03 Hz).
[0194] Step B: 1-(5-Bromo-2-isopropoxyphenyl)-3-phenylprop-2-yn-1-one: To a stirred solution of phenyl-acetylene (0.27 ml, 2.46 mmol) in anhydrous THF (3 ml) 2M iPrMgC1 in THF (1.25 ml) was added drop wise at 0° C. under N 2 . After stirring for 15 min, the solution of product of Step A (0.5 g, 2.06 mmol) in anhydrous THF (2 ml) was added drop wise and the mixture was stirred for 1 h at room temperature. The mixture was quenched with saturated NH 4 Cl and extracted with EtOAc (50 ml). The organic layer was washed with H 2 O, dried over MgSO 4 . and filtered. The filtrate was evaporated to dryness to give a creamy paste (0.59 g; 83%). [ 1 H-NMR (CDCl 3 ) 7.68 (d, 1H, J=2.49 Hz); 7.46-7.43 (m, 2H); 7.36 (dd, 1H, J=8.75, 2.54 Hz); 7.32-7.28 (m, 3H); 6.79 (d, 1H, J=6.77 Hz); 5.79 (d, 1H, J=5.23 Hz); 4.64-4.58 (m, 1H); 3.13 (d, 1H, J=5.91 Hz); 1.37 (d, 6H)]. This was dissolved in dioxane (10 ml) and MnO 2 (1 g) was added to it. The resulting suspension was stirred for 6 h at reflux, then filtered through Celite and the solvent was evaporated to dryness to give the title compound (0.54 g, 76.5%), as light yellow paste. 1 H-NMR (CDCl 3 ) 8.00 (d, 1H, J=2.61 Hz); 7.61-7.52 (m, 3H); 7.44-7.35 (m, 3H); 6.88 (d, 1H, J=8.91 Hz); 4.68-4.60 (m, 1H); 1.36 (d, 6H).
[0195] Step C: 4-(4-Oxo-2-phenyl-4H-chromen-6-yl)benzaldehyde: A solution of the product of Step B (0.3 g, 0.88 mmol), was treated with HBr/AcOH, as described in Example 28, Step A, to give a light creamy solid (0.18 g, 68%). 1 H-NMR (CDCl 3 ) 8.36 (d, 1H, J=2.43 Hz); 7.92-7.88 (m, 2H); 7.77 (dd, 1H, J=8.88, 2.46 Hz); 7.58-7.50 (m, 3H); 7.47 (d, 1H, J=8.86 Hz); 6.83 (s, 1H)], which was reacted with 4-carbaldehyde-boronic acid in Example 22, Step A, to give the title compound (0.078 g, 48%), as creamy solid. 1 H-NMR (CDCl 3 ) 10.07 (s, 1H); 8.5 (d, 1H, J=2.31 Hz); 8.00-7.93 (m, 2H); 7.84 (d, 2H, J=8.22 Hz); 7.71-7.63 (m, 3H); 7.56-7.48 (m, 3H); 6.87 (s, 1H).
[0196] Step D: Methyl 1-(4-(4-oxo-2-phenyl-4H-chromen-6-yl)benzyl)azetidine-3-carboxylate: When the product of Step C and azatadine 3 methylcarboxylate hydrochloride were substituted for -(5-(((4-fluorophenyl))isopropyl)amino)methyl) thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, as in Example 22, Step C, the similar procedure afforded the title compound in 31% yield, as light green paste. 1 H-NMR (CDCl 3 ) 8.43 (d, 1H, J=2.29 Hz); 7.96-7.91 (m, 3H); 7.63 (d, 3H); 7.54-7.39 (m, 3H); 7.38 (d, 2H, J=8.18 Hz); 6.85 (s, 1H); 3.73 (s, 3H); 3.71 (s, 2H); 3.71-3.62 (broad, 2H); 3.42-3.35 (b, 3H).
[0197] Step E: 1-(4-(4-oxo-2-phenyl-4H-chromen-6-yl)benzyl)azetidin e-3-carboxylic acid: When the product of Step D was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar process afforded the title compound in 36% yield, as creamy solid. 1 H-NMR (CDCl 3 +CD 3 OD) 8.31 (broad s, 1H); 7.86 (broad s, 3H); 7.77-7.52 (m, 7H); 6.69 (s, 1H); 4.21 (broad s, 2H); 4.18-4.02 (m, 4H); 3.3 (s, 1H).
Example 31
3′-(1-Admantanyl)-4′methoxybiphenyl-4-yl)methyl)azetidine-3-carboxylic acid
[0198] Step A: 2-(1-Admantanyl)-4-bromophenol: To a stirred solution of 4-bromophenol (1 g; 5.8 mmol) and admant-1-ol (0.88 g; 5.8 mmol) in AcOH (5 ml) concentrated H 2 SO 4 (1 ml) was added drop wise and stirring was continued for 50 h. The solvent was distilled to half of the volume and the mixture was poured onto ice cold H 2 O (100 ml) and extracted with EtOAc (150 ml). The organic layer was washed with NaHCO 3 solution, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.976 g, 55%), as a colourless solid. 1 H-NMR (CDCl 3 ) 7.27 (d, 1H, J=2.43 Hz); 7.13 (dd, 1H, J=8.4-2.43 Hz); 6.51 (d, 1H, J=8.37 Hz); 4.76 (s, 1H, OH); 2.07 (s, 10H); 1.75 (b, 5H).
[0199] Step B: 2-(1-Admantanyl)-4-bromomethoxybenzene: To a stirred mixture of the product of Step A (0.5 g; 1.62 mmol) and K 2 CO 3 (0.335 g; 2.42 mmol) in danhydrous DMF (5 ml) CH 3 I (1 ml) was added. The reaction mixture was stirred for 2 h and then diluted to 100 ml with H 2 O and extracted with EtOAc (100 ml). The organic layer was dried over MgSO 4 and filtered. The filtrate was passed through silica gel bead. The filtrate was evaporated to dryness to give the title compound (0.49 g, 94%), as light yellow green solid. 1 H-NMR (CDCl 3 ) 7.27-7.22 (m, 2H); 6.31 (d, 1H, J=6.5 Hz); 3.78 (s, 3H); 2.04 (s, 10H); 1.74 (b, 5H).
[0200] Step C: 3′-(1-Admantanyl)4′methoxy-4-carbaldehyde: When the product of Step B and 4-carbaldehyde-boronic acid were substituted for 4-bromobenzaldehyde and 5-(hydroxymethyl)thiophen-2-ylboronic acid, respectively, in Example 22, Step A, the similar process afforded the title compound in 42% yield, as pale solid. 1 H-NMR (CDCl 3 ) 10.02 (s, 1H); 7.90 (d, 2H, J=8.22 Hz); 7.70 (d, 2H, J=8.22 Hz); 7.51 (d, 1H, J=2.31 Hz); 7.46 (dd, 1H, J=8.4-2.3 Hz); 6.95 (d, 1H, J=8.4 Hz); 3.88 (s, 3H); 2.14 (b, 6H); 2.07 (b, 3H); 1.8 (b, 6H).
[0201] Step D: Methyl-1-3′-(1-admantanyl)4′methoxybiphenyl-4-yl)methyl)azetidine-3-carboxylate: When the product of Step C and azatadine 3 methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl)) isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively in Example 22, Step C, the similar procedure afforded the title compound in 82% yield, as pale paste. 1 H-NMR (CDCl 3 ) 7.48 (d, 2H, J=8.16 Hz); 7.42 (d, 1H, J=2.3 Hz); 7.37 (dd, 1H, J=8.4-2.3 Hz); 7.28 (d, 2H, J=8.15 Hz); 6.91 (d, 1H, J=8.4 Hz); 3.85 (s, 3H); 3.7 (s, 3H); 3.62 (s, 2H); 3.56-3.52 (m, 2H); 3.35-3.31 (m, 3H); 2.13 (b, 5H); 2.06 (b, 3H); 1.77 (b, 5H); 1.65 (b, 2H).
[0202] Step E: 3′-(1-Admantanyl)-4-methoxybiphenyl-4-yl)methyl)azetidine-3-carboxylic acid: When the product of Step D was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar procedure afforded title compound in 37% yield, as creamy solid. 1 H-NMR (CDCl 3 +CD 3 OD) 7.53 (broad s, 4H); 7.36 (d, 1H, J=2.1 Hz); 7.31 (broad d, 1H, J=8.35 Hz); 6.87 (d, 2H, J=8.47 Hz); 4.3 (s, 2H); 4.19-4.15 (m, 4H); 3.81 (s, 3H); 3.54-3.51 (m, 1H); 2.07-2.00 (m, 9H); 1.73-1.71 (m, 6H).
Example 32
1-(4-(3-(1-Admantnyl)-4-methoxybenzyloxy)benzyl)azetidine-3-carboxylic acid
[0203] Step A: 3-(1-Admantanyl)-4-methoxybenzaldehyde: When 4-hydroxybenzaldehyde was substituted for 4-bromophenol in Example 31, Step A, the similar procedure afforded 3-(1-admantanyl)-4-hydroxybenzaldehyde in 56% yield, as a pale white solid. 1 H-NMR (CDCl 3 ) 9.84 (s, 1H); 7.78 (d, 1H, J=2.07 Hz); 7.61 (dd, 1H, J=8.13, 2.01 Hz); 6.77 (d, 1H, J=8.16 Hz); 5.88 (bs, 1H); 2.12 (s, 6H); 2.09 (s, 3H); 1.78 (s, 6H). This was methylated by similar procedure as described in Example 31, Step B, to give the title compound in 64% yield, as light yellow solid. 1 H-NMR (CDCl 3 ) 9.86 (s, 1H); 7.76 (d, 1H, J=2.07 Hz); 7.7 (dd, 1H, J=8.4, 2.1 Hz); 6.95 (d, 1H, J=8.4 Hz); 3.91 (s, 3H); 2.09 (s, 9H); 1.76 (s, 6H).
[0204] Step B: 4-(3-(1-Admantnyl)-4-methoxybenzyloxy)benzaldehyde: To a stirred suspension of product of Step A (0.09 g, 0.32 mmol) in MeOH (5 ml) NaBH 4 (0.018 g, 0.47 mmol) was added and the mixture was stirred for 0.5 h. The solvent was evaporated to dryness and the residue was taken in NaHCO 3 solution and extracted with EtOAc (25 ml). The organic layer was separated, dried over MgSO 4 , and filtered. The filtrate was evaporated and the residue was dried in vacuo to give a relevant benzyl alcohol (0.095 g; 100%), as a creamy gum. 1 H-NMR (CDCl 3 ) 7.21 (d, 1H, J=2.17 Hz); 7.16 (dd, 1H, J=8.21, 2.17 Hz); 6.83 (d, 1H, J=8.21 Hz); 4.59 (bd, 2H, J=4.24 Hz); 3.82 (s, 3H, OMe); 2.08 (s, 6H); 2.05 (s, 3H); 1.76 (s, 6H). To a stirred solution of above product in anhydrous CH 2 Cl 2 (5 ml) CBr 4 (0.14 g, 0.42 mmol) was added, followed by PPh 3 (0.11 g, 0.42 mmol). The mixture was stirred for 1 h at room temperature and the solvent was distilled off. The residue was taken in EtOAc (10 ml) and the insoluble material was filtered off. The filtrate was evaporated to give the relevant benzyl bromide (0.14 g), which was added as a solution in DMF (2 ml) to a stirred suspension of 4-hydroxybenzaldehyde (0.069 g, 0.57 mmol) and K 2 CO 3 (0.080 g, 0.58 mmol) in anhydrous DMF (3 ml) and this was stirred for 2 h at 70° C. The mixture was quenched with saturated NR 4 Cl solution and extracted with EtOAc (50 ml). The organic layer was dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.05 g, 31.4%), as colourless solid. 1 H-NMR (CDCl 3 ) 9.88 (5, 1H); 7.82 (d, 2H, J=8.78 Hz); 7.26-7.21 (m, 3H); 7.01 (d, 2H, J=8.7 Hz); 6.87 (d, 1H, J=8.2 Hz); 5.04 (s, 2H); 3.83 (s, 3H); 2.08 (s, 6H); 2.05 (s, 3H); 1.76 (s, 6H).
[0205] Step C: Methyl 1-(4-(3-(1-admantanyl)-4-methoxybenzyloxy)benzyl)azetidine-3-carboxylate: When the product of Step B and azatadine 3 methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl))-isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, in Example 22, Step C, the similar procedure afforded the title compound in 69% yield, as a pale paste. 1 H-NMR (CDCl 3 ) 7.24-7.20 (m, 2H); 7.16 (d, 2H, J=8.55 Hz); 6.91 (d, 2H, J=8.62 Hz); 6.85 (d, 1H, J=8.17 Hz); 4.92 (s, 2H); 3.82 (s, 3H); 3.69 (s, 3H); 3.52 (s, 2H); 3.49 (s, 1H); 3.47 (s, 2H); 3.31-3.24 (m, 3H); 2.08 (s, 6H); 2.04 (s, 3H); 1.75 (s, 6H).
[0206] Step D: 1-(4-(3-(1-Admantnyl)-4-methoxybenzyloxy)benzyl)azetidine-3-carboxylic acid: When the product of Step C was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar procedure afforded the title compound in 61% yield, as creamy solid. 1 H-NMR (CDCl 3 :CD 3 OD) 7.33 (d, 2H, J=8.59 Hz); 7.17-7.12 (m, 2H); 6.92 (d, 2H, J=8.64 Hz); 6.79 (d, 1H, J=8.21 Hz); 4.87 (s, 2H); 4.13 (s, 2H); 4.08-4.02 (m, 4H); 2.0 (s, 6H); 1.97 (s, 3H); 1.68 (s, 6H).
Example 33
1-(4-(2-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)benzyl)azetidine-3-carboxylic acid
[0207] Step A: 4-(2-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)benzaldehyde: (6,6-Dimethylbicyclo[3.1.1]hept-2-en-2-yl)ethanol was brominated as described in Example 32, Step B and the bromination product was used in next step without further purification, where it was treated with 4-hydroxybenzaldehyde as described in Example 32, Step B to afford the title compound in 91% yield, as creamy paste.
[0208] Step B: Methyl-1-(4-(2-(6,6-dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)benzyl)azetidine-3-carboxylate: When the product of Step A and azatadine 3 methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl))-isopropyl)amino)methyl)thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, in Example 22, Step C, the similar procedure afforded the title compound in 76% yield, as light yellow paste. 1 H-NMR (CDCl 3 ) 7.17 (d, 2H, J=8.56 Hz); 6.81 (d, 2H, J=8.61 Hz); 3.91 (t, 2H, J=1.98 Hz); 3.71-3.65 (m, 7H); 3.44-3.41 (m, 3H); 2.03-1.17 (m, 10H); 1.17 (s, 3H); 1.01 (s, 3H).
[0209] Step C: 1-(4-(2-(6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)ethoxy)benzyl) azetidine-3-carboxylic acid: When the product of Step B was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar procedure afforded the title compound in 87% yield, as creamy paste. 1 H-NMR (CDCl 3 +CD 3 OD) 7.21 (d, 2H, J=7.98 Hz); 6.79 (d, 2H, J=7.99 Hz); 3.94-3.71 (m, 8H); 3.27-3.25 (m, 1H); 2.36-1.20 (m, 10H); 1.14 (s, 3H); 0.97 (s, 3H).
Example 34
1-(4-(12-Oxo-12H-chromeno[2,3-b]quinolin-2-yl)benzyl)azetidine-3-carboxylic acid
[0210] Step A: 6-Bromo-4-oxo-2-(phenylamino)-4H-chromene-3-carbaldehyde: To a stirred solution of 6-bromo-4-oxo-4H-chromene-3-carbaldehyde (2 g, 7.93 mmol) in anhydrous benzene (15 ml) phenyl-hydroxylamine (0.95 g, 8.71 mmol) was added. The solution was kept for 1 h at room temperature when the crystalline solid appeared. To this glacial AcOH (0.5 ml) was added and the mixture was stirred for 5 h at reflux. The solvent was distilled off and the residue was crystallized from MeOH to give the title compound (2.1 g, 78%), as yellow crystalline solid. 1 H-NMR (CDCl 3 ) 12.43 (broad s, 1H); 10.28 (s, 1H); 8.34 (d, 1H, J=2.46 Hz); 7.69 (dd, 1H, J=8.76, 2.49 Hz); 7.46-7.29 (m, 6H).
[0211] Step B: 2-Bromo-12H-chromeno[2,3-b]quinolin-12-one: To the product of Step A (1 g; 2.92 mmol) concentrated H 2 SO 4 (1 ml) was gently added with stirring. The mixture was kept in sealed vial for 24 h, at room temperature, than poured onto ice water and extracted with CH 2 Cl 2 (50 ml). The organic layer was washed with NaHCO 3 solution, H 2 O, dried over MgSO 4 and filtered. The filtrate was distilled off and the residue was crystallized from CH 3 CN to give the title compound (0.73 g, 77%), as green yellow solid. 1 H-NMR (CDCl 3 ) 9.28 (s, 1H); 8.44 (d, 1H, J=2.1 Hz); 8.1-8.06 (m, 2H); 7.94-7.84 (m, 2H); 7.63 (t, 1H, J=7.88 Hz); 7.51 (d, 1H, J=8.83 Hz).
[0212] Step C: 4-(12-Oxo-12H-chromeno[2,3-b]quinolin-2-yl)benzaldehyde: When the product of Step B and 4-carbaldehyde-boronic were substituted for 4-bromobenzaldehyde and 5-(hydroxymethyl)thiophen-2-ylboronic acid, respectively, in Example 22, Step A, the similar procedure afforded the title compound in 52% yield, as off white solid. 1 H-NMR (CDCl 3 ) 10.08 (s, 1H); 9.33 (s, 1H); 8.6 (d, 1H, J=2.34 Hz); 8.14-8.05 (m, 3H); 8.00 (d, 2H, J=8.25 Hz); 7.96-7.89 (m, 1H); 7.85 (d, 2H, J=8.22 Hz); 7.74 (d, 1H, J=8.7 Hz); 7.64 (t, 1H, J=7.8 Hz).
[0213] Step D: Methyl-1-(4-(12-oxo-12H-chromeno[2,3-b]quinolin-2-yl)benzyl) azetidine-3-carboxylate: When the product of Step C and azatadine 3 methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl))isopropyl)amino)methyl) thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectively, in Example 22, Step C, the similar procedure affored the title compound in 48% yield, as pale paste. 1 H-NMR (CDCl 3 ) 9.32 (s, 1H); 8.53 (s, 1H); 8.12-8.07 (m, 2H); 8.00 (dd, 1H, J=8.7, 2.4 Hz); 7.91 (t, 1H, J=5.55 Hz); 7.7-7.6 (m, 4H); 7.38 (d, 2H, J=8.22 Hz); 3.71 (s, 3H); 3.67 (s, 2H); 3.57-3.53 (m, 2H); 3.39-3.35 (m, 3H).
[0214] Step E: 1-(4-(12-Oxo-12H-chromeno[2,3-b]quinolin-2-yl)benzyl)azetidine-3-carboxylic acid: When the product of Step D was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar procedure afforded the title compound in 50% yield, as yellow solid. 1 H-NMR (CDCl+CD 3 OD) 9.25 (broad s, 1H); 8.44 (m, 2H); 7.76-7.54 (m, 5H); 4.31-4.07 (m, 4H); 4.27-3.95 (m, 2H).
Example 35
1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylic acid
[0215] Step A: (5-Chlorobenzofuran-3-yl)methanol: To a mixture of 4-chloro-2-iodophenol (1 g, 3.92 mmol), tert-butyl(3-(tert-butyldimethylsilyl)prop-2-ynyloxy)-dimethylsilane (1.93 g, 6.8 mmol), LiCl (0.15 g; 3.5 mmol) and Na 2 CO 3 (0.636 g; 6 mmol) in anhydrous DMF (10 ml) Pd(OAc) 2 (0.3 g) was added at 100° C. under N 2 and heating was continued for 1.5 h. The solvent was removed in vacuo and the residue was diluted to 100 ml with EtOAc, washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the coupling product (0.64 g; 26%). This was dissolved in THF (5 ml) and 1M TBAF in THF (2 ml) was added to it and the mixture was stirred for 4 h at reflux. The solvent was distilled off and the residue was dilute to 50 ml with EtOAc, washed with 1M HCl, H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.33 g; 99%), as creamy paste. 1 H-NMR (CDCl 3 ) 7.63 (d, 1H, J=2.11 Hz); 6.60 (b, 1H); 7.37 (d, 1H, J=8.72 Hz); 7.25 (dd, 1H, J=8.71, 2.13 Hz); 4.79 (s, 2H).
[0216] Step B: 4-((5-Chlorobenzofuran-3-yl)methoxy)benzaldehyde: When the product of Step A was substituted for 3-(1-admantanyl)-4-methoxy benzaldehyde in Example 32, Step B, the similar procedure afforded the title compound in 9% yield, as pale paste. 1 H-NMR (CDCl 3 ) 9.89 (s, 1H); 7.84 (d, 2H, J=8.74 Hz); 7.72 (s, 1H); 7.60 (d, 1H, J=2.07 Hz); 7.41 (d, 1H, J=8.76 Hz); 7.28 (dd, 1H, J=8.75, 2.09 Hz); 7.09 (d, 2H, J=8.73 Hz); 5.23 (s, 2H).
[0217] Step C: Methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate: When the product of Step B and azatadine 3-methylcarboxylate hydrochloride were substituted for 4-(5-(((4-fluorophenyl)(isopropyl)amino)methyl)-thiophen-2-yl)benzaldehyde and sarcosine hydrochloride, respectfully, in Example 22, Step C, the similar procedure afforded the title compound in 45% yield, as off white solid. 1 H-NMR (CDCl 3 ) 7.68 (s, 1H); 7.60 (bs, 1H); 7.39 (d, 2H, J=8.77 Hz); 7.28-7.18 (m, 3H); 6.93 (d, 2H, J=6.62 Hz); 5.12 (s, 2H); 3.69 (s, 3H); 3.54-3.47 (m, 5H); 3.36-3.28 (m, 4H).
[0218] Step D: 1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylic acid: When the product of Step C was substituted for methyl-1-(4-((5-chlorobenzofuran-3-yl)methoxy)benzyl)azetidine-3-carboxylate in Example 25, Step E, the similar procedure afforded the title compound in 57% yield, as creamy solid. 1 H-NMR (CDCl 3 +CD 3 OD) 7.78 (s, 1H); 7.57 (d, 2H, J=2.06 Hz); 7.53 (s, 1H); 7.39 (d, 1H, J=8.8 Hz); 7.36 (d, 2H, J=8.66 Hz); 7.24 (dd, 1H, J=8.75, 2.12 Hz); 7.04 (d, 2H, J=8.67 Hz); 5.18 (s, 2H); 4.20-4.06 (m, 6H); 3.36-3.27 (m, 1H).
Example 36
2-Amino-2-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0219] Step A: N-Hydroxy-3-iodo-4-isopropoxybenzimidamide: A suspension of 3-iodo-4-isopropoxybenzonitrile (0.576 g; 2 mmol), HCl×NH 2 OH (0.276 g; 4 mmol) and DIPEA (0.69 ml; 4 mmol) in EtOH (50 ml) was stirred for 18 h at 50° C. The solvent was distilled off and the residue was diluted to 50 ml with EtOAc and washed with H 2 O. The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was distilled off to give the title product (0.61 g; 95%), as colourless solid. 1 H-NMR (CDCl 3 ) 8.0 (d, 1H, J=2.22 Hz); 7.55 (dd, 1H, J=9.54, 2.28 Hz); 6.77 (d, 1H, J=8.7 Hz); 4.95 (b, 2H); 4.69-4.63 (m, 1H); 1.42 (d, 6H).
[0220] Step B: 5-(3-Chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole: A mixture of 3-chloro-4-propoxybenzoic acid (0.298 g, 0.93 mmol), the product of Step A (0.2 g, 0.93 mmol) and EDC (0.214 g, 1.1 mmol) in anhydrous DMF (3 ml) was stirred overnight at 45° C. 1 M TBAF in THF (0.3 ml) was added and this was stirred for 2.5 h at 110° C. The reaction mixture was diluted to 20 ml with H 2 O and extracted with EtOAc (2×15 ml). The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was distilled off and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.22 g, 47.4%), as a colourless solid. 1 H-NMR (CDCl 3 ) 8.56 (d, 1H, J=2.04 Hz); 8.21 (d, 1H, J=2.37 Hz); 8.07-8.02 (m, 2H); 7.00 (d, 1H, J=8.73 Hz); 6.87 (d, 1H, J=8.67 Hz); 4.68-4.63 (m, 1H); 4.08 (t, 2H, J=6.45 Hz); 1.93-1.87 (m, 2H); 1.36 (d, 6H, J=6.06 Hz); 1.09 (t, 3H, J=7.44 Hz).
[0221] Step C: 4-(5-(3-Chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol: To a solution of the product of Step B (0.2 g, 0.4 mmol) in anhydrous CH 2 Cl 2 (2 ml) 1 M BCl 3 in CH 2 Cl 2 (3 ml) was added drop wise at rt. After 1 h, more of 1M BCl 3 in CH 2 Cl 2 (1 ml) was added and this was stirred for 1 h. The reaction mixture was quenched with saturated NH 4 Cl solution and extracted with CH 2 Cl 2 (20 ml). The organic layer was separated, dried over MgSO 4 and filtered. The filtrates was evaporated to dryness and the residue was crystallized from MeOH to give the title compound (0.145 g, 79%), as colourless solid. 1 H-NMR (CDCl 3 ) 8.47 (d, 1H, J=1.95 Hz); 8.21 (d, 1H, J=2.1 Hz); 8.06-8.04 (m, 1H); 8.03-8.02 (m, 1H); 7.07 (d, 1H, J=8.49 Hz); 7.00 (d, 1H, J=8.7 Hz); 4.08 (t, 2H, J=6.45 Hz); 1.94-1.87 (m, 2H); 1.09 (t, 3H, J=7.44 Hz).
[0222] Step D: tert-Butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: A solution of the product of Step C (0.1 g; 0.22 mmol) and tert-butyl 5-ethynyl-2,2-dimethyl-1,3-dioxan-5-ylcarbamate (0.056 g; 0.22 mmol) in a mixture of DMF and DIPEA (3 ml: 0.3 ml) was degassed with N 2 and Cl 2 Pd(PPh 3 ) 4 (0.025 g) was added, followed by catalytic amount of CuI. The mixture was stirred overnight at 45° C. under N 2 , diluted to 20 ml with saturated NH 4 Cl and extracted with EtOAc (40 ml). The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was distilled off and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.11 g, 78%), as pale paste. 1 H-NMR (CDCl 3 ) 8.34 (d, 1H, J=1.29 Hz); 8.24 (d, 1H, J=2.13 Hz); 8.08 (t, 1H, J=1.56 Hz); 8.05 (t, 1H, J=1.56 Hz); 7.53 (d, 1H, J=8.67 Hz); 7.03 (d, 1H, J=8.67 Hz); 6.75 (s, 1H); 4.26-4.19 (m, 4H); 4.06 (t, 2H, J=5.49 Hz); 1.94-1.87 (m, 2H); 1.41 (s, 9H); 1.36 (s, 6H); 1.1 (t, 3H, J=7.44 Hz).
[0223] Step E: 2-Amino-2-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: To a stirred solution of product of Step D (0.1 g, 0.17 mmol) in CH 2 Cl 2 (0.5 ml) TFA (1 ml) was added. After stirring for 1 h at room temperature, EtOH (2 ml) was added and stirring was continued for additional 1 h. The mixture was evaporated to dryness and the residue was purified by FCC (SiO 2 , CH 2 Cl 2 saturated with concentrated NH 4 OH/MeOH; 98:2) to give the title product (0.035 g, 46%) as colourless solid. 1 H-NMR (DMSO-d 6 ) 8.3 (d, 1H, J=1.11 Hz); 8.15 (d, 1H, J=2.01 Hz); 8.09 (dd, 1H, J=8.67, 2.04 Hz); 7.94 (dd, 1H, J=8.58, 1.53 Hz); 7.68 (d, 1H, J=8.61 Hz); 7.37 (d, 1H, J=8.76 Hz); 6.92 (s, 1H); 4.91 (b, 2H); 4.14 (t, 2H, J=6.36 Hz); 3.69 (d, 2H, J=10.6 Hz); 3.59 (d, 2H, J=10.6 Hz); 1.83-1.72 (m, 2H); 0.97 (t, 3H, J=7.41 Hz).
Example 37
(E)-2-Amino-2-(5-(5-(4-methylstyryl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0224] Step A: (E)-3-(3-Iodo-4-isopropoxyphenyl)-5-(4-methylstyryl)-1,2,4-oxadiazole: When (E)-3-p-tolylacrylic acid was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar process afforded the title compound in 52% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.53 (d, 1H, J=2.07 Hz); 8.01 (dd, 1H, J=8.58, 2.1 Hz); 7.82 (d, 1H, J=16.35 Hz); 7.49 (d, 1H, J=8.1 Hz); 6.97 (d, 1H, J=16.38 Hz); 6.87 (d, 1H, J=8.76 Hz); 4.69-4.6 (m, 1H); 1.4 (d, 6H, J=5.85 Hz).
[0225] Step B. (E)-2-Iodo-4-(5-(4-methylstyryl)-1,2,4-oxadiazol-3-yl)phenol: When the product of Step A was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 53% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.44 (d, 1H, J=1.95 Hz); 8.0 (dd, 1H, J=8.49, 2.01 Hz); 7.84 (d, 1H, J=16.35 Hz); 7.49 (d, 1H, J=8.16 Hz); 7.07 (d, 1H, J=8.49 Hz); 6.98 (d, 1H, J=16.83 Hz); 5.61 (s, 1H).
[0226] Step C: (E)-tert-Butyl 2,2-dimethyl-5-(5-(5-(4-methylstyryl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-1,3-dioxan-5-ylcarbamate: When the product of Step B was substituted for 4-(5-(3-chloro-4-propoxy phenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar process afforded the title compound in 68% yield, as pale paste. 1 H-NMR (CDCl 3 ) 8.30 (d, 1H, J=1.32 Hz); 8.03 (dd, 1H, J=8.61, 1.68 Hz); 7.84 (d, 1H, J=16.38 Hz); 7.53-7.49 (m, 3H); 7.21 (d, 2H, J=5.34 Hz); 7.0 (d, 1H, J=15.15 Hz); 5.28 (s, 1H); 4.24 (b, 4H); 2.39 (s, 3H); 1.46-1.39 (m, 15H).
[0227] Step D: (E)-2-Amino-2-(5-(5-(4-methylstyryl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step C was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-yl carbamate in Example 36, Step E, the similar procedure afforded the title compound in 48% yield, as colourless solid. 1 H-NMR (DMSO-d 6 ) 8.23 (b, 1H); 7.9-7.85 (m, 2H); 7.72-7.64 (m, 3H); 7.33 (d, 1H, J=16.2 Hz); 7.25 (d, 2H, J=6.3 Hz); 6.87 (s, 1H); 4.77 (b, 2H); 3.63 (b, 2H); 3.56 (b, 2H); 2.32 (s, 3H); 1.95 (b, 2H).
Example 38
2-Amino-2-(5-(5-(4-bromo-3-chlorophenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0228] Step A: 5-(4-Bromo-3-chlorophenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole: When 4-bromo-3-chlorobenzoic acid was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 72% yield, as creamy solid. 1 H-NMR (CDCl 3 ) 8.55 (d, 1H, J=2.07 Hz); 8.27 (d, 1H, J=1.89 Hz); 8.04 (dd, 1H, J=8.61, 2.04 Hz); 7.91 (dd, 1H, J=8.34, 1.95 Hz); 7.79 (d, 1H, J=8.37 Hz); 6.87 (d, 1H, J=8.67 Hz); 4.7-4.6 (m, 1H); 1.4 (d, 6H, J=5.94 Hz).
[0229] Step B: 4-(5-(4-Bromo-3-chlorophenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol: When the product of Step A was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 86% yield, as creamy solid. 1 H-NMR (CDCl 3 ) 8.47 (d, 1H, J=1.98 Hz); 8.28 (d, 1H, J=1.95 Hz); 8.03 (dd, 1H, J=8.49, 1.98 Hz); 7.92 (dd, 1H, J=8.37, 1.98 Hz); 7.84 (d, 1H, J=8.37 Hz); 7.08 (d, 1H, J=8.52 Hz); 5.65 (b, 1H).
[0230] Step C: tert-Butyl 5-(5-(5-(4-bromo-3-chlorophenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: When the product of Step B was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 58% yield, as pale paste. 1 H-NMR (CDCl 3 ) 8.34 (d, 1H, J=1.53 Hz); 8.31 (d, 1H, J=1.95 Hz); 8.06 (dd, 1H, J=8.61, 1.68 Hz); 7.94 (dd, 1H, J=8.37, 1.98 Hz); 7.8 (d, 1H, J=8.37 Hz); 7.54 (d, 1H, J=8.61 Hz); 6.76 (s, 1H); 5.34 (bs, 1H); 4.3-4.24 (m, 4H); 1.55 (s, 9H); 1.47 (s, 6H).
[0231] Step D: 2-Amino-2-(5-(5-(4-bromo-3-chlorophenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step C was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 39% yield, as creamy solid. 1 H-NMR (DMSO-d 6 ) 8.31 (b, 2H); 8.05 (d, 1H, J=8.52 Hz); 8.00 (d, 1H, J=8.49 Hz); 7.94 (d, 1H, J=8.58 Hz); 7.68 (d, 1H, J=8.46 Hz); 6.91 (s, 1H); 4.88 (bs, 1H); 3.66 (bs, 2H); 3.58 (bs, 2H).
Example 39
2-Amino-2-(5-(5-(3-chloro-4-(thiophen-3-yl)phenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0232] Step A: tert-Butyl 5-(5-(5-(3-chloro-4-(thiophen-3-yl)phenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: To a stirred mixture of the product of Example 38, Step C (0.09 g, 0.15 mmol) and 3-thiophene-boronic acid (0.028 g, 0.22 mmol) in a mixture of dioxane and H 2 O (5 ml:1 ml), Pd(PPh 3 ) 4 (0.03 g) was added at 80° C., followed by the NaHCO 3 solution (0.065 g in 1 ml H2O) and this was stirred for 2 h. The solvent was distilled off and the residue was diluted to 20 ml with EtOAc, washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated and the residue was purified by FCC (SiO 2 , hexane/EtOAc), to give the title compound (0.065 g, 71%), as pale paste. 1 H-NMR (CDCl 3 ) 8.45 (d, 1H, J=1.53 Hz); 8.25-8.22 (m, 2H); 7.94 (dd, 1H, J=8.7, 1.8 Hz); 7.55-7.42 (m, 3H); 7.38-7.37 (m, 2H); 6.78 (s, 1H); 5.43 (bs, 1H); 4.29-4.13 (m, 4H); 1.46 (s, 9H); 1.27 (b, 6H).
[0233] Step B: 2-Amino-2-(5-(5-(3-chloro-4-(thiophen-3-yl)phenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step A was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 48% yield, as colourless solid. 1 H-NMR (DMSO-d 6 ) 8.42 (s, 1H); 8.28 (s, 1H); 8.2 (d, 1H, J=8.41 Hz); 8.11 (d, 1H, J=8.1 Hz); 7.82 (s, 1H); 7.64-7.61 (m, 3H); 7.4 (b, 1H); 6.92 (s, 1H); 4.9 (bs, 2H); 3.66 (b, 2H); 3.59 (b, 2H).
Example 40
2-Amino-2-(5-(5-(3,4-diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0234] Step A: 5-(3,4-Diethoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole: When 3,4-diethoxy benzoic acid was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 60% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.57 (d, 1H, J=2.05 Hz); 8.05 (dd, 1H, J=8.58, 2.03 Hz); 8.02 (d, 1H, J=2.07 Hz); 7.76 (dd, 1H, J=8.41, 1.94 Hz); 7.66 (d, 1H, J=1.93 Hz); 6.96 (d, 1H, J=8.5 Hz); 6.87 (d, 1H, J=8.69 Hz); 4.67-4.63 (m, 1H); 4.24-4.14 (m, 4H); 1.53-1.4 (m, 6H); 1.38 (d, 6H, J=6.64 Hz).
[0235] Step B: 4-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol: When the product of Step A was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 84% yield, as a creamy solid. 1 H-NMR (CDCl 3 ) 8.48 (d, 1H, J=2.05 Hz); 8.04 (dd, 1H, J=8.46, 1.98 Hz); 7.76 (dd, 1H, J=8.43, 2.0 Hz); 7.65 (d, 1H, J=1.98 Hz); 7.07 (d, 1H, J=8.5 Hz); 6.96 (d, 1H, J=8.46 Hz); 5.63 (bs, 1H); 4.24-4.09 (m, 4H); 1.56-1.42 (m, 6H).
[0236] Step C: tert-Butyl 5-(5-(5-(3,4-diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: When the product of Step B was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 66% yield, as creamy paste. 1 H-NMR (CDCl 3 ) 8.35 (d, 1H, J=1.57 Hz); 8.08 (dd, 1H, J=8.62, 1.68 Hz); 7.79 (dd, 1H, J=8.44, 1.94 Hz); 7.69 (d, 1H, J=1.93 Hz); 7.52 (d, 1H, J=8.54 Hz); 6.96 (d, 1H, J=8.5 Hz); 6.75 (s, 1H); 5.32 (b, 1H); 4.36-4.15 (m, 8H); 3.95 (s, 2H); 1.54-1.47 (m, 21H).
[0237] Step D: 2-Amino-2-(5-(5-(3,4-diethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step C was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-yl carbamate in Example 36, Step E, the similar procedure afforded the title compound in 61% yield, as creamy solid. 1 H-NMR (DMSO-d 6 ) 8.27 (s, 1H); 7.92 (d, 1H, J=8.23 Hz); 7.75-7.61 (m, 3H); 7.17 (d, 1H, J=8.34 Hz); 6.88 (s, 1H); 4.78 (b, 2H); 4.15-4.00 (b, 4H); 3.65-3.64 (b, 2H); 3.57-3.55 (b, 2H); 1.35 (b, 6H).
Example 41
2-Amino-2-(5-(5-(4-propoxy-3-methoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0238] Step A: 5-(4-Propoxy-3-methoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole: When 4-propoxy-3-methoxybenzoic acid was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 58% yield, as creamy solid. 1 H-NMR (CDCl 3 ) 8.58 (d, 1H, J=2.01 Hz); 8.06 (dd, 1H, J=8.61, 2.07 Hz); 7.77 (dd, 1H, J=8.43, 1.98 Hz); 7.66 (d, 1H, J=1.92 Hz); 6.97 (d, 1H, J=8.46 Hz); 6.88 (d, 1H, J=8.7 Hz); 4.69-4.61 (m, 1H); 4.06 (t, 2H, J=6.81 Hz); 3.98 (s, 3H); 1.93-1.88 (m, 2H); 1.06 (t, 3H, J=7.38 Hz).
[0239] Step B: 4-(5-(4-Propoxy-3-methoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol: When the product of Step A was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 80% yield, as creamy solid. 1 H-NMR (CDCl 3 ) 8.48 (d, 1H, J=1.98 Hz); 8.04 (dd, 1H, J=8.46, 1.98 Hz); 7.7 (dd, 1H, J=8.43, 2.01 Hz); 7.65 (d, 1H, J=1.95 Hz); 7.07 (d, 1H, J=8.49 Hz); 6.97 (d, 1H), J=8.46 Hz); 5.63 (s, 1H); 4.06 (t, 2H, J=6.8 Hz); 4.02 (s, 3H); 1.94-1.87 (m, 2H); 1.06 (t, 3H, J=7.41 Hz).
[0240] Step C: tert-Butyl 5-(5-(5-(4-propoxy-3-methoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: When the product of Step B was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 68% yield, as pale paste. 1 H-NMR (CDCl 3 ) 8.35 (d, 1H, J=1.23 Hz); 8.08 (dd, 1H, J=8.61, 1.68 Hz); 7.8 (dd, 1H, J=8.41, 1.98 Hz); 7.68 (d, 1H, J=1.92 Hz); 7.52 (d, 1H, J=8.64 Hz); 6.98 (d, 1H, J=8.49 Hz); 6.75 (s, 1H); 5.32 (bs, 1H); 4.26 (b, 4H); 4.06 (t, 2H, J=6.81 Hz); 3.98 (s, 3H); 1.93-1.88 (m, 2H); 1.49 (s, 9H); 1.44 (s, 6H); 1.06 (t, 3H, J=7.38 Hz).
[0241] Step D: 2-Amino-2-(5-(5-(4-Propoxy-3-methoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step C was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 57% yield, as colourless solid. 1 H-NMR (DMSO-d 6 ) 8.28 (s, 1H); 7.92 (d, 1H, J=2.82 Hz); 7.61 (m, 3H); 7.16 (d, 1H, J=8.53 Hz); 6.88 (s, 1H); 4.78 (b, 2H); 4.01 (t, 2H, J=6.03 Hz); 3.99 (s, 3H); 3.77-3.57 (m, 4H); 1.78-1.71 (m, 2H); 0.96 (t, 3H, J=7.29 Hz).
Example 42
5-(3,4-Diethoxyphenyl)-3-(2-methylbenzofuran-5-yl)-1,2,4-oxadiazole
[0242] Step A: 2-Methylbenzofuran-5-carbonitrile: 2-Iodo-4-cynophenol (0.25 g, 1 mmol) and saccharin (0.1 g) in HMDSA (2 ml) was refluxed for 2 h under N 2 , until the solution became clear. The solvent was distilled off under reduced pressure and the residue was dissolved in anhydrous THF (2 ml). This was added to a solution made by mixing anhydrous ZnCl 2 (0.3 g; 2.2 mmol) with 0.5 M 1-propynyl magnesium bromide in THF (7.8 ml) in anhydrous THF (5 ml) at room temperature under N 2 . To it, Pd (PPh 3 ) 4 (0.15 g) was added at room temperature under N 2 followed by catalytic amount of CuI. The mixture was stirred at room temperature for 3 h and quenched with saturated NH 4 Cl solution. The mixture was diluted to 50 ml with EtOAc and washed with H 2 O. The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was evaporated and the residue was dissolved in 1,4-dioxane (4 ml) and 1 M TBAF in THF (0.3 ml) was added and this was stirred for 4 h at reflux. The solvent was distilled off and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.145 g, 91%), as colourless solid. 1 H-NMR (CDCl 3 ) 7.78 (s, 1H); 7.46-7.44 (m, 2H); 6.41 (bs, 1H); 2.47 (s, 3H).
[0243] Step B: 5-(3,4-Diethoxyphenyl)-3-(2-methylbenzofuran-5-yl)-1,2,4-oxadiazole: The product Step A was converted to N-hydroxy-2-methylbenzofuran-5-carboximidamide by method described for Example 36, Step A. When N-hydroxy-2-methylbenzofuran-5-carboximidamide and 3,4-diethoxybenzoic acid were substituted for N-hydroxy-3-iodo-4-isopropoxybenzimidamide and 3-chloro-4-propoxybenzoic acid, respectively, in Example 36, Step B, the similar procedure afforded the title compound in 6% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.28 (bs, 1H); 8.00 (dd, 1H, J=8.55, 1.68 Hz); 7.8 (dd, 1H, J=8.4, 1.98 Hz); 7.68 (d, 1H, J=1.92 Hz); 7.47 (d, 1H, J=8.58 Hz); 6.97 (d, 1H, J=8.46 Hz); 6.45 (s, 1H); 4.23-4.16 (m, 4H); 2.48 (3H); 1.52-1.47 (m, 6H).
Example 43
2-Amino-2-(5-(5-(6-methoxybenzofuran-2-yl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0244] Step A: Ethyl 2-(2-formyl-5-methoxyphenoxy)acetate: A mixture of 2-hydroxy-4-methoxybenzaldehyde (1 g; 6.58 mmol), BrCH 2 CO 2 Et (0.806 ml; 7.24 mmol) and K 2 CO 3 (1 g, 7.24 mmol) in anhydrous DMF (5 ml) was stirred overnight at room temperature. The mixture was diluted with EtOAc (100 ml) and H 2 O (100 ml). The organic layer was separated and dried over MgSO 4 , and filtrate evaporated, to give the product (1.29 g; 97%), as colourless solid. 1 H-NMR (CDCl 3 ) 1.28 (tr, 3H, J=7.11 Hz); 3.84 (s, 3H); 4.25 (q, 2H, J=7.14, 14.28 Hz); 4.69 (s, 2H); 6.30 (d, 1H, J=2.16 Hz); 6.58 (dd, 1H, J=1.77, 8.73 Hz); 7.83 (d, 1H, J=8.7 Hz); 10.36 (s, 1H).
[0245] Step B: Ethyl 6-methoxybenzofuran-2-carboxylate: A mixture of the product of Step A (1.28 g, 5.37 mmol) and DBU (0.3 ml) was heated for 3 h at 160° C. with stirring, cooled to room temperature and dissolved in EtOAc: MeOH mixture (99:1). The mixture was filtered through the silica bead and the filtrate was evaporated to give the title compound (1.11 g; 77%), as colourless solid. 1 H-NMR (CDCl 3 ) 1.40 (tr, 3H, J=7.13 Hz); 3.85 (s, 3H); 4.40 (q, 2H, J=7.13, 14.25 Hz); 4.45 (s, 1H); 6.91 (dd, 1H, J=2.25, 8.68 Hz); 7.04 (d, 1H, J=1.87 Hz); 7.51 (d, 1H, J=5.17 Hz),
[0246] Step C: 6-Methoxybenzofuran-2-carboxylic acid: To a stirred solution of Product of Step B (0.25 g, 1.21 mmol) in a mixture of THF, MeOH and H 2 O (5 ml:2 ml:1 ml), LiOH (0.145 g, 6 mmol) in H 2 O (0.5 ml) was added and the mixture was stirred for 3 h at room temp. The solvents were distilled off and the residue was portioned between EtOAc (20 ml) and 1M HCl (2 ml). The organic layer was washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give the title compound (0.21 g, 91%), as a colourless solid. 1 H-NMR (DMSO-d 6 ) 7.61 (d, 1H, J=8.67 Hz); 7.54 (s, 1H); 7.24 (d, 1H, J=1.59 Hz); 6.93 (dd, 1H, J=8.67, 2.4 Hz); 3.8 (s, 3H).
[0247] Step D: 3-(3-Iodo-4-isopropoxyphenyl)-5-(6-methoxybenzofuran-2-yl)-1,2,4-oxadiazole: When the product of Step C was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 67% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.6 (d, 1H, J=2.04 Hz); 8.08 (dd, 1H, J=8.58, 2.1 Hz); 7.63 (b, 1H); 7.57 (d, 1H, J=8.7 Hz); 7.13 (d, 1H, J=1.8 Hz); 6.97 (dd, 1H, J=8.7, 2.19 Hz); 6.87 (d, 1H, J=8.73 Hz); 4.69-4.59 (m, 1H); 3.88 (s, 3H); 1.4 (d, 6H, J=6.33 Hz).
[0248] Step E: 2-Iodo-4-(5-(6-methoxybenzofuran-2-yl)-1,2,4-oxadiazol-3-yl)phenol: When the product of Step D was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 65% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.53 (d, 1H, J=2.01 Hz); 8.06 (dd, 1H, J=8.49, 2.01 Hz); 7.64 (b, 1H); 7.6 (d, 1H, J=8.7 Hz); 7.13 (b, 1H); 7.08 (d, 1H, J=8.46 Hz); 6.98 (dd, 1H, J=8.7, 2.22 Hz); 3.89 (s, 3H).
[0249] Step F: tert-Butyl 5-(5-(5-(6-methoxybenzofuran-2-yl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: When the product of Step E was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 64% yield, as pale paste.
[0250] Step G: 2-Amino-2-(5-(5-(6-methoxybenzofuran-2-yl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step F was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 26% yield, as creamy green solid. 1 H-NMR (CD 3 OD) 8.39 (d, 1H, J=1.74 Hz); 8.08 (dd, 1H, J=8.73, 1.89 Hz); 7.68 (b, 1H); 7.63 (d, 1H, J=8.73 Hz); 7.58 (d, 1H, J=8.7 Hz); 7.14 (d, 1H, J=1.8 Hz); 7.03 (s, 1H); 6.92 (dd, 1H, J=8.7, 2.22 Hz); 3.98 (d, 2H, J=11.00 Hz); 3.88 (d, 2H, J=11.01 Hz); 3.85 (s, 3H).
Example 44
2-Amino-2-(5-(5-(4-propylphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0251] Step A: 3-(3-Iodo-4-isopropoxyphenyl)-5-(4-propylphenyl)-1,2,4-oxadiazole: When 4-propylbenzoic acid was substituted for 3-chloro-4-propoxy benzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 82% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.58 (d, 1H, J=2.04 Hz); 8.11-8.05 (m, 3H); 7.34 (d, 2H, J=8.25 Hz); 6.88 (d, 1H, J=8.73 Hz); 4.7-4.59 (m, 1H); 2.67 (t, 2H, J=7.83 Hz); 1.72-1.41 (m, 2H); 0.95 (t, 3H, J=7.29 Hz).
[0252] Step B: 2-Iodo-4-(5-(4-propylphenyl)-1,2,4-oxadiazol-3-yl)phenol: When the product of Step A was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 82% yield, as colourless solid. 1 H-NMR (CDCl 3 ) 8.48 (d, 1H, J=1.98 Hz); 8.08 (d, 2H, J=8.25 Hz); 8.03 (dd, 1H, J=8.49, 2.01 Hz); 7.33 (d, 2H, J=8.25 Hz); 7.07 (d, 1H, J=8.49 Hz); 2.66 (t, 2H, J=7.5 Hz); 1.71-1.61 (m, 2H); 0.95 (t, 3H, J=7.29 Hz).
[0253] Step C: tert-Butyl 2,2-dimethyl-5-(5-(5-(4-propylphenyl)-1,2,4-oxadiazol-3-yl)benzo-furan-2-yl)-1,3-dioxan-5-ylcarbamate: When the product of Step B was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 35% yield, as pale paste. 1 H-NMR (CDCl 3 ) 8.35 (s, 1H); 8.13-8.06 (m, 3H); 7.52 (d, 1H, J=8.64 Hz); 7.34 (d, 2H, J=8.22 Hz); 6.75 (s, 1H); 5.35 (s, 1H); 4.26 (b, 4H); 2.67 (t, 2H, J=7.41 Hz); 1.74-1.67 (m, 2H); 1.64 (s, 6H); 1.5 (s, 9H); 0.96 (t, 2H, J=7.29 Hz).
[0254] Step D: 2-Amino-2-(5-(5-(4-propylphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step C was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 28% yield, as creamy solid. 1 H-NMR (DMSO-d 6 ) 8.30 (s, 1H); 8.08 (d, 2H, J=6.6 Hz); 7.94 (d, 1H, J=7.5 Hz); 7.68 (d, 1H, J=7.5 Hz); 7.46 (d, 2H, J=7.5 Hz); 6.92 (s, 1H); 3.67 (b, 2H); 3.59 (b, 2H); 2.65 (b, 2H); 1.63-1.6 (m, 2H); 0.88 (t, 2H, J=6.3 Hz).
Example 45
2-Amino-2-(5-(5-(4-ethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0255] Step A: 5-(4-Ethoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole: When 4-ethoxybenzoic acid was substituted for 3-chloro-4-propoxy benzoic acid in Example 36, Step B, the similar procedure affored the title compound in 53% yield, as white solid. 1 H-NMR (CDCl 3 ) 8.57 (d, 1H, J=2.04 Hz); 8.11 (d, 2H, J=8.88 Hz); 8.05 (dd, 1H, J=8.58, 2.04 Hz); 6.99 (d, 2H, J=8.88 Hz); 6.87 (d, 1H, J=8.67 Hz); 4.69-4.61 (m, 1H); 4.11 (q, 2H, J=6.99, 13.98 Hz); 1.45 (t, 3H, J=6.99 Hz).
[0256] Step B: 4-(5-(4-Ethoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol: When the product of Step A was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 87% yield, as white solid. 1 H-NMR (CDCl 3 ) 8.47 (d, 1H, J=1.95 Hz); 8.11 (d, 2H, J=8.94 Hz); 8.03 (dd, 1H, J=8.46, 2.01 Hz); 7.07 (d, 2H, J=8.49 Hz); 4.11 (q, 2H, J=6.96, 13.98 Hz); 1.45 (t, 3H, J=6.96 Hz).
[0257] Step C: tert-Butyl 5-(5-(5-(4-ethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: When the product of Step B was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 60% yield, as pale paste. 1 H-NMR (CDCl 3 ) 8.34 (s, 1H); 8.14 (d, 2H, J=8.88 Hz); 8.07 (dd, 1H, J=8.61, 1.68 Hz); 7.51 (d, 1H, J=8.52 Hz); 7.00 (d, 2H, J=8.94 Hz); 6.75 (s, 1H); 5.34 (s, 1H); 4.3-4.14 (b, 4H); 4.1 (t, 2H, J=7.02 Hz); 1.44-1.39 (b, 18H).
[0258] Step D: 2-Amino-2-(5-(5-(4-ethoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step C was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 32% yield, as light yellow solid. 1 H-NMR (DMSO-d 6 ) 8.09 (s, 1H); 7.96 (d, 2H, J=8.4 Hz); 7.7 (d, 1H, J=8.4 Hz); 7.15 (d, 2H, J=9 Hz); 6.98 (s, 1H); 5.1 (b, 2H); 4.13 (q, 2H, J=6.9, 13.8 Hz); 3.73 (d, 2H, J=8.1 Hz); 3.64 (d, 2H, J=8.1 Hz); 1.34 (t, 3H, J=6.9 Hz).
Example 46
2-Amino-2-(6-chloro-5-(5-(4-propyl phenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0259] Step A: 2-Chloro-N-hydroxy-5-iodo-4-isopropoxybenzimidamide: To a stirred solution of 2-chloro-4-isopropoxybenzonitrile (0.8 g, 4.1 mmol) and CF 3 CO 2 Ag (1.3 g, 5.1 mmol) in CH 2 Cl 2 (50 ml) I 2 (1 g, 4 mmol) was added and the mixture was stirred for 6 h at reflux. This was filtered through the Celite bead and the washed with CH 2 Cl 2 . The combined filtrates were evaporated to dryness and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give 2-chloro-5-iodo-4-isopropoxybenzonitrile (0.335 g, 26%), as white solid. 1 H NMR (CDCl 3 ) 7.99 (s, 1H); 6.82 (s, 1H); 4.66-4.58 (m, 1H); 1.41 (d, 6H, J=6.03 Hz. This (0.32 g, 1 mmol) was converted to the title compound (0.335 g; 95%) according to the procedure of Example 36 Step A. 1 H NMR (CDCl 3 ) 7.89 (s, 1H); 6.79 (s, 1H); 4.86-4.49 (m, 1H); 1.4 (d, 6H)
[0260] Step B: 3-(2-Chloro-5-iodo-4-isopropoxyphenyl)-5-(4-propylphenyl)-1,2,4-oxadiazole: When the product of Step A and 4-propylbenzoic acid were substituted for N-hydroxy-3-iodo-4-isopropoxybenzimidamide and 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 20% yield, as white solid. 1 H NMR (CDCl 3 ) 8.46 (s, 1H); 8.10 (d, 2H, J=8.25 Hz); 7.34 (d, 2H, J=8.28 Hz); 6.92 (s, 1H); 7.67-7.59 (m, 1H); 2.67 (t, 2H, J=7.35 Hz); 1.72-1.65 (m, 2H); 1.43 (d, 6H, J=6.06 Hz); 0.96 (t, 3H, J=7.32 Hz).
[0261] Step C: 5-Chloro-2-iodo-4-(5-(4-propylphenyl)-1,2,4-oxadiazol-3-yl)phenol: When the product of Step B was substituted for 5-(3-chloro-4-propoxy phenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 55% yield, as creamy solid. 1 H NMR (CDCl 3 ) 8.37 (s, 1H); 8.10 (d, 2H, J=8.25 Hz); 7.33 (d, 2H, J=8.25 Hz); 7.16 (s, 1H); 5.78 (b, 1H); 2.67 (t, 2H, J=7.38 Hz); 1.74-1.56 (m, 2H); 0.96 (t, 3H, J=7.32 Hz).
[0262] Step D: 2-Amino-2-(6-chloro-5-(5-(4-propylphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate was replaced with the tert-butyl 5-(6-chloro-5-(5-(4-propylphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate (obtained as crude via a process as described in Example 36, Step D) the similar procedure as in Example 36, Step E gave the title compound (0.006 g, 40%) as white solid. 1 H NMR (CD 3 OD) 8.12 (d, 2H, J=8.28 Hz); 8.12 (s, 1H); 7.75 (s, 1H); 7.43 (d, 2H, J=8.31 Hz); 6.9 (s, 1H); 3.88 (d, 2H, J=10.9 Hz); 3.78 (d, 1H, J=10.9 Hz); 2.7 (t, 2H, J=7.41 Hz); 1.76-1.64 (m, 2H); 0.97 (t, 3H, J=7.32 Hz).
Example 47
2-Amino-2-(5-(5-(1-butyl-1H-pyrazol-4-yl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0263] Step A: 1-Butyl-1H-pyrazole-4-carboxylic acid: To a stirred suspension of 4-iodopyrazole (0.3 g, 1.55 mmol) and 60% NaH (0.08 g, 2 mmol) in anhydrous THF (1 ml) butyl bromide (0.5 ml) was added and the mixture was stirred overnight at 70° C. The mixture was quenched with saturated NH 4 Cl and extracted with EtOAc (50 ml). The organic layer was washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was distilled off and the residue was dried in vacuo to give 1-butyl-4-iodo-1H-pyrazole (0.39 g, 100%), as colourless oil. 1 H NMR (CDCl 3 ) 7.47 (s, 1H); 7.39 (s, 1H); 4.09 (t, 2H, J=7.14 Hz); 1.85-1.75 (m, 2H); 1.35-1.23 (m, 2H); 0.91 (t, 3H, J=7.32 Hz). To a stirred solution of the above product (0.36 g, 1.44 mmol) in anhydrous THF (0.5 ml) 2M iPrMgCl in THF (2 ml) was added at 0° C. and after warming up to room temperature anhydrous DMF (1 ml) was added to it. This was stirred for 1 h at room temperature, than quenched with saturated NH 4 Cl and extracted with EtOAc (30 ml). The organic layer was washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give 1-butyl-1H-pyrazole-4-carbaldehyde (0.27 g; 100%), as pale oil. 1 H NMR (CDCl 3 ) 9.82 (s, 1H); 7.93 (s, 1H); 7.89 (s, 1H); 4.13 (t, 2H, J=7.11 Hz); 1.9-1.8 (m, 2H); 1.4-1.22 (m, 2H); 0.92 (t, 3H, J=7.29 Hz). To a stirred solution of above aldehyde (0.22 g, 1.44 mmol) in the mixture of dioxane and H 2 O (15 ml: 3 ml) KMnO 4 (0.25 g; 1.58 mmol) was added over a period of 30 min. The mixture was evaporated to dryness and the residue was treated in the mixture of EtOAc and MeOH (20 ml: 5 ml) and filtered through Celite pad. The filtrate was evaporated to dryness to give the title compound (0.24 g; 100%), as creamy crystalline solid. 1 H NMR (CDCl 3 ) 7.8 (s, 1H); 7.56 (b, 1H); 4.05 (b, 2H); 1.7 (b, 2H); 1.18 (b, 2H); 0.83 (b, 3H).
[0264] Step B: 5-(1-Butyl-1H-pyrazol-4-yl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole: When the product of Step A was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B the similar procedure afforded the title compound in 17% yield, as creamy gum. 1 H NMR (CDCl 3 ) 8.53 (d, 1H, J=2.07 Hz); 8.1 (s, 1H); 8.08 (s, 1H); 8.00 (dd, 1H, J=8.61, 2.16 Hz); 8.87 (d, 1H, J=8.73 Hz); 4.68-4.6 (m, 2H); 4.2 (t, 2H, J=7.11 Hz); 2.02-1.85 (m, 2H); 1.42-1.32 (m, 2H); 0.95 (t, 3H, J=7.32 Hz).
[0265] Step C: 4-(5-(1-Butyl-1H-pyrazol-4-yl)-1,2,4-oxadiazol-3-yl)-2-iodophenol: When the product of Step B was substituted for 5-(3-chloro-4-propoxy phenyl)-3-(3-iodo-4-isopropoxy phenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 72% yield, as creamy solid. 1 H NMR (CDCl 3 ) 8.45 (d, 1H, J=1.98 Hz); 8.12 (s, 1H); 8.09 (s, 1H); 7.99 (dd, 1H, J=8.49, 2.01 Hz); 7.06 (d, 1H, J=8.49 Hz); 4.2 (t, 2H, J=7.08 Hz); 2.02-1.85 (m, 2H); 1.42-1.26 (m, 2H); 0.95 (t, 3H, J=7.29 Hz).
[0266] Step D: tert-Butyl 5-(5-(5-(1-butyl-1H-pyrazol-4-yl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: When the product of Step C was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 68% yield, as pale paste. 1 H NMR (CDCl 3 ) 8.3 (s, 1H); 8.13 (s, 1H); 8.01 (s, 1H); 7.51 (d, 1H, J=8.7 Hz); 6.74 (s, 1H); 5.32 (s, 1H); 4.29-4.18 (m, 6H); 2.02-1.91 (m, 2H); 1.54-1.34 (b, 17H); 0.96 (t, 3H, J=7.35 Hz).
[0267] Step E: 2-Amino-2-(5-(5-(1-butyl-1H-pyrazol-4-yl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step D was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 46% yield, as light creamy solid. 1 H NMR (CD 3 OD) 8.46 (broad s, 1H); 8.32 (broad s, 1H); 8.13 (broad s, 1H); 8.02 (d, 1H, J=7.98 Hz); 7.62 (d, 1H, J=8.31 Hz); 6.97 (s, 1H); 4.25 (t, 2H, J=6.21 Hz); 3.93 (b, 4H); 1.91-1.86 (m, 2H); 1.36-1.31 (m, 2H); 0.95 (t, 3H, J=7.02 Hz).
Example 48
2-Amino-2-(5-(5-(3-nitro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0268] Step A: 3-Nitro-4-propoxybenzoic acid: To a stirred solution of 3-nitro-4-propoxymethylbenzoate (0.35 g, 1.46 mmol) in a mixture of THF and EtOH (3 ml:1 ml) the solution of LiOH (0.345 g; 15 mmol) in H 2 O (1 ml) was added and the mixture was stirred for 4 h at room temperature. The solvent was distilled off and the residue was treated with 1 M HCl and extracted with EtOAc (50 ml). The organic layer was washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give the title compound (0.32 g, 97%), as creamy solid. 1 H NMR (CDCl 3 ) 8.53 (d, 1H, J=1.65 Hz); 8.21 (dd, 1H, J=8.79, 1.62 Hz); 7.12 (d, 1H, J=8.82 Hz); 4.14 (t, 2H, J=6.39 Hz); 1.94-1.82 (m, 2H); 1.07 (t, 3H, J=7.35 Hz).
[0269] Step B: 3-(3-Iodo-4-isopropoxyphenyl)-5-(3-nitro-4-propoxyphenyl)-1,2,4-oxadiazole: When the product of Step A was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 66% yield, as creamy solid. 1 H NMR (CDCl 3 ) 8.64 (d, 1H, J=2.13 Hz); 8.55 (d, 1H, J=2.1 Hz); 8.3 (dd, 1H, J=8.82, 2.16 Hz); 8.2 (dd, 1H, J=8.58, 2.01 Hz); 7.2 (d, 1H, J=8.88 Hz); 6.96 (d, 1H, J=8.85 Hz); 4.7-4.62 (m, 1H); 4.16 (t, 2H, J=6.39 Hz); 1.94-1.84 (m, 2H); 1.42 (d, 6H, J=6.03 Hz); 1.08 (t, 3H, J=7.35 Hz).
[0270] Step C: 2-Iodo-4-(5-(3-nitro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)phenol: When the product of Step B was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 77% yield, as creamy solid. 1 H NMR (CDCl 3 ) 8.65 (d, 1H, J=2.16 Hz); 8.47 (d, 1H, J=1.95 Hz); 8.3 (dd, 1H, J=8.82, 2.19 Hz); 8.03 (dd, 1H, J=8.49, 2.01 Hz); 7.21 (d, 1H, J=8.88 Hz); 7.08 (d, 1H, J=8.49 Hz); 4.17 (t, 2H, J=6.39 Hz); 1.96-1.84 (m, 2H); 1.09 (t, 3H, J=7.38 Hz).
[0271] Step D: tert-Butyl 2,2-dimethyl-5-(5-(5-(3-nitro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-1,3-dioxan-5-ylcarbamate: When the product of Step C was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 54% yield, as pale solid. 1 H NMR (CDCl 3 ) 8.68 (d, 1H, J=2.16 Hz); 8.35-8.31 (m, 2H); 8.06 (dd, 1H, J=8.64, 1.71 Hz); 7.54 (d, 1H, J=8.64 Hz); 7.21 (d, 1H, J=8.97 Hz); 6.76 (s, 1H); 5.33 (s, 1H); 4.3-3.95 (m, 6H); 2.41-1.87 (m, 2H); 1.58-1.21 (m, 15H); 1.09 (t, 3H, J=7.44 Hz).
[0272] Step E: 2-Amino-2-(5-(5-(3-nitro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step D was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxy phenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 49% yield, as creamy solid. 1 H NMR (DMSO-d 6 ) 8.6 (s, 1H); 8.37 (d, 1H, J=8.37 Hz); 8.31 (s, 1H); 7.94 (d, 1H, J=8.52 Hz); 7.68 (d, 1H, J=8.52 Hz); 7.59 (d, 1H, J=8.82 Hz); 6.91 (s, 1H); 4.87 (b, 2H); 4.23 (t, 2H, J=5.82 Hz); 3.67 (d, 2H, J=10.05 Hz); 3.58 (d, 2H, J=9.96 Hz); 1.78-1.71 (m, 2H); 0.97 (t, 3H, J=7.26 Hz).
Example 49
5-(3-(2-(2-Amino-1,3-dihydroxypropan-2-yl)benzofuran-5-yl)-1,2,4-oxadiazol-5-yl)-2-propoxybenzonitrile
[0273] Step A: 3-Cyano-4-propoxybenzoic acid: To a stirred solution of 3-bromo-4-propoxybenzaldehyde (0.6 g, 2.47 mmol) in anhydrous DMF (5 ml) CuCN (0.67 g; 7.4 mmol) was added and the mixture was stirred for 4 h at reflux. After cooling to room temperature, the mixture was treated with EtOAc (50 ml) and 1M HCl (10 ml) and stirred for 15 min. The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give 5-formyl-2-propoxybenzonitrile (0.41 g; 88%), as yellow oil 1 H NMR (CDCl 3 ) 9.87 (s, 1H); 8.07 (d, 1H, J=1.95 Hz); 8.03 (dd, 1H, J=8.67, 2.1 Hz); 7.06 (d, 1H, J=8.7 Hz); 4.13 (t, 2H, J=6.45 Hz); 1.97-1.85 (m, 2H); 1.1 (t, 3H, J=7.35 Hz). The above benzaldehyde was oxidised via a similar procedure as described in Example 47 Step A, to give the title compound (0.29 g; 68%), as white solid. 1 H NMR (CDCl 3 ) 8.3 (d, 1H, J=1.71 Hz); 8.23 (dd, 1H, J=8.88, 2.1 Hz); 7.00 (d, 1H, J=7.62 Hz); 4.12 (t, 2H, J=6.48 Hz); 1.97-1.85 (m, 2H); 1.09 (t, 3H, J=7.38 Hz).
[0274] Step B: 5-(3-(3-Iodo-4-isopropoxyphenyl)-1,2,4-oxadiazol-5-yl)-2-propoxy benzonitrile: When the product of Step A was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 57% yield, as creamy solid. 1 H NMR (CDCl 3 ) 8.55 (d, 1H, J=2.1 Hz); 8.4 (d, 1H, J=2.1 Hz); 8.31 (dd, 1H, J=8.85, 2.16 Hz); 8.04 (dd, 1H, J=8.61, 2.1 Hz); 7.09 (d, 1H, J=8.94 Hz); 6.88 (d, 1H, J=8.7 Hz); 4.7-4.6 (m, 1H); 4.14 (t, 2H, J=6.48 Hz); 1.98-1.87 (m, 2H); 1.42 (d, 6H, J=6.06 Hz); 1.18 (t, 3H, J=7.38 Hz).
[0275] Step C: 5-(3-(4-Hydroxy-3-iodophenyl)-1,2,4-oxadiazol-5-yl)-2-propoxy benzonitrile: When the product of Step B was substituted for 5-(3-chloro-4-propoxyphenyl)-3-(3-iodo-4-isopropoxyphenyl)-1,2,4-oxadiazole in Example 36, Step C, the similar procedure afforded the title compound in 74% yield, as creamy solid. 1 H NMR (CDCl 3 ) 8.46 (d, 1H, J=1.95 Hz); 8.4 (d, 1H, J=2.13 Hz); 8.31 (dd, 1H, J=8.88, 2.19 Hz); 8.02 (dd, 1H, J=8.49, 1.68 Hz); 7.1 (d, 1H, J=8.94 Hz); 7.09 (d, 1H, J=8.49 Hz); 5.64 (bs, 1H); 4.12 (t, 2H, J=6.48 Hz); 2.02-1.86 (m, 2H); 1.1 (t, 3H, J=7.38 Hz).
[0276] Step D: tert-Butyl 5-(5-(5-(3-cyano-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate: When the product of Step C was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 44% yield, as pale paste. 1 H NMR (CDCl 3 ) 8.42 (d, 1H, J=2.16 Hz); 8.34 (dd, 1H, J=6.63, 2.19 Hz); 8.06 (dd, 1H, J=8.61, 1.71 Hz); 7.99 (b, 1H); 7.52 (d, 1H, J=8.58 Hz); 7.1 (d, 1H, J=8.94 Hz); 6.76 (s, 1H); 5.33 (s, 1H); 4.26 (t, 4H, J=11.4 Hz); 4.15 (t, 2H, J=11.4 Hz); 4.15 (t, 2H, J=6.48 Hz); 2.02-1.87 (m, 2H); 1.56-1.38 (m, 15H); 1.1 (t, 3H, J=7.38 Hz).
[0277] Step E: 5-(3-(2-(2-Amino-1,3-dihydroxypropan-2-yl)benzofuran-5-yl)-1,2,4-oxadiazol-5-yl)-2-propoxy benzonitrile: When product of Step D was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate (obtained as crude via a process as described in Example 36, Step D) in Example 36, Step E, the similar procedure afforded the title compound in 29% yield, as off white solid. 1 H NMR (DMSO-d 6 ) 8.49 (d, 1H, J=2.22 Hz); 8.39 (dd, 1H, J=8.91, 2.22 Hz); 8.28 (d, 1H, J=1.41 Hz); 7.93 (dd, 1H, J=8.55, 1.71 Hz); 7.68 (d, 1H, J=8.58 Hz); 7.48 (d, 1H, J=9.06 Hz); 6.89 (s, 1H); 4.78 (b, 2H); 4.22 (t, 2H, J=6.42 Hz); 3.68-3.52 (m, 4H); 1.84-1.73 (m, 2H); 1.0 (t, 3H, J=7.41 Hz).
Example 50
2-Amino-2-(5-(5-(3-bromo-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol
[0278] Step A: 3-Bromo-4-propoxybenzoic acid: 3-Bromo-4-propoxybenzaldehyde was oxidized by KMnO 4 , according to the procedure as described in Example 47, Step A, to give the title compound in 96%, as white solid. 1 H-NMR (DMSO-d 6 ) 0.98 (t, 3H, J=7.32 Hz); 1.68-1.79 (m, 2H); 4.06 (t, 2H, J=6.39 Hz); 7.14 (d, 1H, J=8.7 Hz); 7.87 (dd, 1H, J=2.07, 8.61 Hz); 8.01 (d, 1H, J=2.04 Hz); 11.2 (broad s, 1H).
[0279] Step B: 4-(5-(3-Bromo-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol: When the product of Step A was substituted for 3-chloro-4-propoxybenzoic acid in Example 36, Step B, the similar procedure afforded the title compound in 70% yield, as white solid. 1 H NMR (CDCl 3 ) 8.47 (s, 1H); 8.38 (s, 1H); 8.08 (d, 1H, J=9.09 Hz); 8.03 (d, 1H, J=8.79 Hz); 7.7 (d, 1H, J=8.55 Hz); 6.98 (d, 1H, J=8.67 Hz); 4.08 (t, 2H, J=6.39 Hz); 1.96-1.84 (m, 2H); 1.1 (t, 3H, J=7.35 Hz).
[0280] Step C: tert-Butyl 5-(5-(5-(3-bromo-4-propoxy-phenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-yl-carbamate: When with the product of Step C was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 98% yield, as pale paste.
[0281] Step D: 2-Amino-2-(5-(5-(3-bromo-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)propane-1,3-diol: When the product of Step C is substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate in Example 36, Step E, the similar procedure afforded the title compound in 10% yield, as light yellow solid. 1 H NMR (CD 3 OD) 8.32 (b, 2H); 8.1 (d, 1H, J=8.46 Hz); 8.00 (d, 1H, J=8.52 Hz); 7.59 (d, 1H, J=8.61 Hz); 7.18 (d, 1H, J=8.58 Hz); 6.91 (s, 1H); 4.1 (t, 2H, J=6.06 Hz); 3.91 (d, 2H, J=10.98 Hz); 3.03 (d, 2H, J=10.95 Hz); 3.32 (b, 2H); 1.9-1.8 (m, 2H); 1.1 (t, 3H, J=7.35 Hz).
Example 51
2-Amino-2-(5-octylbenzo[b]thiophen-2-yl)propane-1,3-diol
[0282] Step A: 2-Iodo-4-octylaniline: To a stirred mixture of 4-octyl aniline (0.33 g, 1.6 mmol) and H 2 O 2 (30%, 0.5 ml) in CH 3 OH (1.5 ml) was added I 2 (0.2 g, 0.8 mmol) and the mixture was stirred overnight at room temperature. The solvent was distilled off and the residue was diluted to 10 ml with CH 2 Cl 2 , washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated to dryness to give the title compound (0.46 g, 86%) as yellow paste. 1 H NMR (CDCl 3 ) 7.44 (d, 1H, J=1.83 Hz); 6.93 (dd, 1H, J=8.07, 1.86 Hz); 6.65 (d, 1H, J=8.1 Hz); 4.1 (b, 2H); 2.43 (t, 2H, J=7.5 Hz); 1.54-1.49 (m, 2H); 1.26 (b, 10H); 0.87 (t, 3H, J=6.39 Hz).
[0283] Step B: 2-Iodo-4-octylbenzenethiol: To a stirred mixture of the product of Step A (0.4 g; 1.21 mmol) in 35% HCl (0.2 ml) an ice cold solution of NaNO 2 (0.1 g, 1.3 mmol) in H 2 O (1 ml) was added at 0° C., followed by a solution of K-ethylxhanthate, freshly prepared by rapid stirring of a mixture of KOH (0.085 g, 1.5 mmol) and CS 2 (0.173 g, 1.5 mmol) in a mixture of EtOH and H 2 O (1 ml: 1.5 ml) for 2.5 h at room temperature. The resulting mixture was stirred for 5 h at 55° C., than cooled to room temperature and extracted with EtOAc (50 ml). The organic layer was separated, washed with H 2 O, dried over MgSO 4 and filtered. The filtrate was evaporated and the residue was diluted to 20 ml with EtOH and KOH (0.5 g, 3.62 mmol) was added. This was stirred for 5 h at reflux and the mixture was evaporated to dryness and the residue was treated with 1M HCl and extracted with EtOAc (20 ml). The organic layer was separated, dried over MgSO 4 and filtered. The filtrate was evaporated and the residue was purified by FCC (SiO 2 , hexane/EtOAc) to give the title compound (0.1 g, 24%), as a yellow paste, which was used as such in next step. 1 H NMR (CDCl 3 ) 7.75 (b, 1H); 7.28 (d, 1H, J=7.95 Hz); 7.00 (dd, 1H, J=7.95, 2.0 Hz); 7.02 (s, 1H); 2.51-2.45 (m, 2H); 1.53 (b, 2H); 1.25 (b, 10H); 0.86 (t, 3H, J=6.42 Hz).
[0284] Step C: tert-Butyl 2,2-dimethyl-5-(5-octylbenzo[b]thiophen-2-yl)-1,3-dioxan-5-ylcarbamate When with the product of Step B was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 24% yield, as white solid. 1 H NMR (CDCl 3 ) 7.65 (d, 1H, J=8.16 Hz); 7.47 (s, 1H); 7.1 (d, 1H, J=6.18 Hz); 7.1 (s, 1H); 5.44 (b, 1H); 4.16 (b, 4H); 2.66 (t, 2H, J=7.5 Hz); 1.6-1.1 (m, 27H); 0.86 (t, 3H, J=6.18 Hz).
[0285] Step D: 2-Amino-2-(5-octylbenzo[b]thiophen-2-yl)propane-1,3-diol: When tert-butyl 5-(5-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-ylcarbamate was replaced with the product of Step C the similar procedure as described in Example 36, Step E gave the title compound (0.008 g, 38%) as light yellow solid. 1 H NMR (CD 3 OD) 7.74 (d, 1H, J=8.28 Hz); 7.6 (s, 1H); 7.4 (s, 1H); 7.2 (dd, 2H, J=8.34, 1.59 Hz); 4.0 (d, 2H, J=11.46 Hz); 3.94 (d, 2H, J=11.46 Hz); 2.7 (t, 2H, J=7.53 Hz); 1.64 (b, 2H); 1.34-1.26 (b, 10H); 0.85 (t, 3H, J=4.8 Hz).
Example 52
2-Amino-2-(5-octylbenzofuran-2-yl)propane-1,3-diol
[0286] Step A: 2-Iodo-4-octylphenol: A mixture of 4-octyl phenol (0.15 g, 0.73 mmol), CF 3 CO 2 Ag (0.25 g, 1 mmol) and I 2 (0.185 g, 0.73 mmol) in CH 2 Cl 2 (10 ml) was stirred for 0.5 h at 0° C., then for 0.5 h at room temperature. The solution was filtered through Celite bead and washed with CH 2 Cl 2 (30 ml). The filtrates were evaporated to dryness to give the title compound (0.21 g, 87%) as fawn oil. 1 H NMR (CDCl 3 ) 7.32 (d, 1H, J=8.34 Hz); 7.28 (d, 1H, J=1.26 Hz); 6.98 (dd, 1H, 8.37, 1.71 Hz); 6.62 (s, 1H); 4.69 (t, 2H, J=5.88 Hz); 3.62-3.38 (m, 4H); 2.59 (t, 2H, J=7.29 Hz); 1.56-1.51 (m, 2H); 1.34-1.2 (m, 10H); 0.81 (t, 3H, J=6.48 Hz).
[0287] Step B: tert-Butyl 2,2-dimethyl-5-(5-octylbenzofuran-2-yl)-1,3-dioxan-5-ylcarbamate: When with the product of Step A was substituted for 4-(5-(3-chloro-4-propoxyphenyl)-1,2,4-oxadiazol-3-yl)-2-iodophenol in Example 36, Step D, the similar procedure afforded the title compound in 53% yield, as a light yellow paste. 1 H NMR (CDCl 3 ) 7.33 (d, 1H, J=6.27 Hz); 7.32 (s, 1H); 7.01 (dd, 1H, J=8.4, 1.71 Hz); 6.59 (s, 1H); 5.3 (s, 1H); 4.17 (s, 4H); 2.64 (t, 2H, J=7.77 Hz); 1.62-1.24 (m, 27H); 0.86 (t, 3H, J=6.42 Hz).
[0288] Step C: 2-Amino-2-(5-octylbenzofuran-2-yl)propane-1,3-diol: When the product of Step B was substituted for tert-butyl 5-(5-(5-(3-chloro-4-propoxy phenyl)-1,2,4-oxadiazol-3-yl)benzofuran-2-yl)-2,2-dimethyl-1,3-dioxan-5-yl-carbamate in Example 36, Step E, the similar procedure afforded the title compound in 51% yield, as off white solid. 1 H NMR (DMSO-d 6 ) 7.44 (d, 1H, J=1.98 Hz); 7.0 (dd, 1H, J=8.28, 1.98 Hz); 6.87 (d, 1H, J=8.22 Hz); 5.11 (s, 1H); 2.47 (t, 2H, J=7.5 Hz); 1.56-1.51 (m, 2H); 1.27-1.26 (m, 10H); 0.87 (t, 3H, J=6.45 Hz).
Example 53
2-(4-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)indoline-1-carboxamido)acetic acid
[0289] Step A: N-Hydroxy-1H-indole-4-carboximidamide: A mixture of 4-cyanoindole (0.64 g; 4.5 mmol), HCl×H 2 NOH (1.1 g; 15.8 mmol), and Na 2 CO 3 (0.79 g; 7.43 mmol) in H 2 O (8 ml) and EtOH (2 ml) was gently stirred for 15 min, then refluxed for 6 h under N 2 . After cooling most of the EtOH was removed under reduced pressure and the product was extracted with EtOAc (3×10 ml). The organic phase was separated, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure to give the title compound (0.74 g; 94%), as a creamy foam. 1 H-NMR (DMSO-d 6 +CDCl 3 +CD 3 OD) 7.4-7.3 (m, 1H); 7.2-7.12 (m, 2H); 7.01 (t, 1H, J=7.8 Hz); 6.74 (d, 1H, J=3.1 Hz); 3.68 (HDO); 1.71 (broad s, H 2 O).
[0290] Step B: 5-(3,4-Diethoxyphenyl)-3-(1H-indol-4-yl)-1,2,4-oxadiazole To a solution of 3,4-diethoxybenzoic acid (0.11 g; 0.52 mmol), and the product of Step A (0.09 g; 0.51 mmol) in anhydrous THF (2 ml), PyBroP (0.25 g; 0.54 mmol) was added followed by DIPEA (0.21 ml; 1.22 mmol), with stirring, at room temperature under N 2 . After 2 h of stirring, the mixture was diluted to 15 ml with EtOAc, washed with saturated NH 4 Cl (2×5 ml), brine, dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure and the residue was suspended in anhydrous toluene (10 ml). To it 1M TBAF in THF (0.5 ml) was added and the reaction mixture was refluxed for 3 h under N 2 , cooled to room temperature and solvents were removed under reduced pressure. The residue was washed with H 2 O (5 ml) and the solid was purified by FCC (SiO 2 ; CH 2 Cl 2 ) to give the title compound (0.06 g; 34%) as colourless solid. 1 H-NMR (CDCl 3 ) 8.42 (s, 1H); 8.06 (dd, 1H, J=2, 8.4 Hz); 7.83 (d, 1H, J=8.4 Hz); 7.74 (d, 1H, J=2 Hz); 7.54 (d, 1H, J=8.1 Hz); 7.37-7.31 (m, 3H); 6.98 (d, 1H, J=8.5 Hz); 4.26-4.16 (m, 4H); 1.5 (m, 6H).
[0291] Step C: 5-(3,4-Diethoxyphenyl)-3-(indolin-4-yl)-1,2,4-oxadiazole: To a solution of the product of Step B (0.06 g; 0.172 mmol) in 1M BH 3 in THF (0.35 ml; 0.35 mmol) TFA (0.4 ml) was added drop wise at 0° C. with stirring. After the addition was completed (˜5 min), the reaction was quenched with H 2 O (0.5 ml) and solvents were removed under reduced pressure. The residue was diluted to 10 ml with EtOAc and was washed with 10% NaOH (2×2 ml), brine and dried over anhydrous MgSO 4 and filtered. The filtrate was evaporated to dryness under reduced pressure to give the title compound (0.026 g; 43%) as a creamy foam, which was used in the next step without further purification. 1 H-NMR (CDCl 3 ) 7.78 (dd, 1H, J=1.9, 7.2 Hz); 7.68 (d, 1H, J=1.9 Hz); 7.52 (d, 1H, J=7.2 Hz); 7.17 (t, 1H, J=7.7); 6.97 (d, 1H, J=8.5 Hz); 6.75 (d, 1H, J=7.7 Hz); 4.19 (m, 4H); 3.65 (t, 2H, J=8.9 Hz); 3.45 (tr, 2H, J=8.9 Hz); 1.7 (broad s, 1H+H 2 O); 1.49 (m, 6H).
[0292] Step D: Ethyl 2-(4-(5-(3,4-diethoxyphenyl)-1,2,4-oxadiazol-3-yl)indoline-1-carboxamido)acetate: When the product of Step E was substituted for n-octylaniline and ethyl isocyanatoacetate was substituted for ethyl 3-isocyanatopropionate in Example 11, Step A the similar process afforded the title compound in 61%, as colourless solid. 1 H-NMR (CDCl 3 ) 8.11 (d, 1H, J=7.4 Hz); 7.78 (dd, 2H, J=2, 7.1 Hz); 7.67 (d, 1H, J=2 Hz); 7.31 (t, 1H, J=8 Hz); 6.97 (d, 1H, J=8.5 Hz); 5.13 (t, 1H, J=5.1 Hz); 4.28-4.04 (m, 10H); 3.61 (t, 1H, J-8.6 Hz); 1.52-1.47 (m, 6H); 1.32 (t, 3H, J=7.1 Hz);
[0293] Step E: 2-(4-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)indoline-1-carboxamido)acetic acid: When the product of Step D was substituted for ethyl 3-(3-(4-octylphenyl)ureido)propanoate in Example 11, Step B the identical process afforded the title compound in 75% yield. 1 H-NMR (DMSO-d 6 ) 8.03 (d, 1H, J=9 Hz); 7.73 (dd, 1H, J=2, 8 Hz); 7.61-7.59 (m, 2H); 7.29 (t, 1H, J=7.9 Hz); 7.17 (d, 1H, J=8.6 Hz); 7.09 (broad m, 1H); 4.17-4.0 (m, 4H); 3.98 (t, 2H, J=5.8 Hz); 3.74 (d, 2H, J=5.2 Hz); 3.47 (t, 2H, J=9 Hz); 1.38-1.32 (m, 6H).
Example 54
3-(4-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)indoline-1-carboxamido)propanoic acid
[0294] Step A: Ethyl 3-(4-(5-(3,4-diethoxyphenyl)-1,2,4-oxadiazol-3-yl)indoline-1-carboxamido)propanoate: When the product of Example 16 Step C was substituted for n-octylaniline in Example 11, Step A the identical process afforded the title compound in 52% yield. 1 H-NMR (CDCl 3 ) 8.1 (d, 1H, J=9 Hz); 7.79-7.75 (m, 2H); 7.67 (d, 1H, J=2 Hz); 7.31 (t, 1H, J=8 Hz); 6.97 (d, 1H, J=8.5 Hz); 5.38 (tr, 1H, J=5.7 Hz); 4.24-4.12 (m, 6H); 3.98 (t, 2H, J=8.6 Hz); 3.63-3.55 (m, 4H); 2.61 (t, 2H, J=5.9 Hz); 1.27 (t, 3H, J=9 Hz);
[0295] Step B: 3-(4-(5-(3,4-Diethoxyphenyl)-1,2,4-oxadiazol-3-yl)indoline-1-carboxamido)propanoic acid: When the product of Step A was substituted for ethyl 3-(3-(4-octylphenyl)ureido)propanoate in Example 11, Step B the identical process afforded the title compound in 61% yield. 1 H-NMR (CDCl 3 ) 8.03 (d, 1H, J=9 Hz); 7.72 (dd, 1H, J=1.9, 8.4 Hz): 7.59-7.56 (m, 2H); 7.27 (t, 1H, J=7.9 Hz); 7.16 (d, 1H, J=8.6 Hz); 6.76 (t, 1H, J=5.3 Hz); 4.04-4.16 (m, 4H); 3.92 (t, 2H, J=8.6 Hz); 3.43 (tr, 2H, J=8.4 Hz); 3.36-3.28 (m, 2H+H 2 O); 2.48-2.42 (m, 2H); 1.37-1.32 (m, 6H).
Example 55
S1P Receptors Activity Evaluation
[0296] Selected Compounds of the Examples were evaluated at Millipore Corporation, USA, using S1P1 receptor; [ 35 S]-GTPgamaS binding assay. A [ 35 S]-GTPgamaS binding assay at Millipore was conducted by GPCR Profiler™ Custom Service Laboratory, Temecula, Calif., Millipore, Inc. to monitor dose-dependent agonist selectivity for selected Examples against the S1P1 receptors. The assay was completed with sample compounds subjected to an eight-point, four-fold dose response curve with starting concentration of 10 μM. Selectivity was determined upon initial addition of compounds followed by a 30 minute incubation at 30° C. Following compound incubation, bounded [35S]-GTPgamaS was determined by filtration and scintillation counting. Percentage activation and inhibition values were determined relative to the reference agonist at S1P1 and are shown in Table 10.
[0297] Independently, selected compounds were evaluated for S1P1 and S1P3 agonistic activity. The S1P1 assay system was GTPgama-S35 binding in membranes from CHO K1 cells, expressing S1P1 human receptor. The S1P3 assay system was calcium mobilization in CHO K1 cells expressing S1P3 human receptor. There was no significant background response to S1P in the CHO K1 cells with either assay. Compounds were tested initially at a concentration of 10 μM. Those compounds with significant efficacy (Emax >0.15 relative to S1P) at either receptor type were used to generate concentration-effect (dose response) curves at that receptor. These analyses provided efficacy (Emax) and potency (EC 50 ) of the compounds relative to S1P, shown in Table 10.
[0000]
TABLE 10
S1P1 and S1P3 agonistic activity of selected compounds of Formula (I):
Efficacy
Entry
EC 50 (μM)
EC 50 S 1 P 1 /
(% of
EC 50 (μM)
Number
Example
S1P1
EC 50 S 1 P
maximum)
S 1 P 3
1
3
0.29
135.5
102.5
ND
2
9
1.63
761.7
88
ND
3
11
0.46
215
96
ND
4
13
3.21
1500
58
ND
5
17
1.76
542
97
ND
6
19
5.99
2799
130
ND
7
27
0.6
280.4
127
ND
8
29
0.2
93.46
102
ND
9
32
0.06
28
107
ND
10
33
0.14
65.42
97
ND
11
36
0.047
4.18
101
NA
12
37
1.82
160.8
40
NA
13
38
0.26
28.17
74
NA
14
39
3.46
305
16
NA
15
40
0.057
4.75
106
0.38
NA = no activity;
ND = not determined.
Example 56
Lymphopenia Assay
[0298] The study was performed at vivoPharm Pty Ltd, Adelaide, Australia, to determine the ability of the compounds of invention to induce lymphopenia in female BALB/c mice. On day 0, 27 female BALB/c mice were randomised based on body weight into nine groups of three mice each. Animals received a single i.p. administration of Test compounds and blood was collected by cardiac puncture either 6 or 24 h after administration. Treatment with 3 mg/kg of Example 40 was shown to decrease lymphocyte counts at both 6 and 24 h, compared to untreated animals ( FIG. 1 ). Changes to other haematological parameters were not observed.
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The invention relates to novel compounds that have S1P receptor modulating activity. Further, the invention relates to a pharmaceutical comprising at least one compound of the invention for the treatment of diseases and/or conditions caused by or associated with inappropriate S1P receptor modulating activity or expression, for example, autoimmune response. A further aspect of the invention relates to the use of a pharmaceutical comprising at least one compound of the invention for the manufacture of a medicament for the treatment of diseases and/or conditions caused by or associated with inappropriate S1P receptor modulating activity or expression such as autoimmune response.
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RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 61/416,808, filed on Nov. 24, 2010. The entire teachings of the above application are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Development of fluorescent molecules and their application are indispensable techniques for the analysis of a variety of biological phenomena. During the past few decades, a number of fluorescent small molecules have been developed as reporters and chemosensors for use in biological analyses, which typically are elaborately designed to selectively detect a target substance or conjugated to biomolecules 1 . These fluorescent molecules employ an increase or decrease in their emission intensity in response to the surrounding medium or through specific molecular recognition events. Due to their simplicity and high sensitivity, fluorescent sensors have been widely utilized as popular tools for chemical, biological and medical applications. The most general strategy for fluorescent sensor design is to combine fluorescence dye molecules with designed receptors for specific analytes, expecting that the recognition event between receptor and analyte will lead to a fluorescence property change of the dye moiety. Although many fluorescent sensors have been successfully developed through this approach, each individual development requires a major effort in both the design and synthesis of the sensors. Also, the sensor's scope of application is limited to the selected specific analytes that the sensor was rationally designed for, so-called Analyte Directed Sensors. Combinatorial dye library synthesis offers one of the most promising alternatives as Diversity Directed Sensors, once an efficient synthetic route can be developed for a diverse set of dyes.
[0003] Neural stem cells (NSC) generate the nervous system, promote neuronal plasticity and repair damage throughout life by self-renewing and differentiating into neurons and glia 2,3 . Beneficial effects of NSC engraftment into the affected brain areas in several brain diseases have been demonstrated by animal experiments 4,5 . NSC also has great potential for drug screening and efficacy testing significantly reducing the time and efforts needed in drug discovery. The conventional methods for the isolation and characterization of NSC depend on their behavior in a defined culture medium such as neurosphere formation and immunodetection of marker molecules. These methods, however, are time-dependent and involve the use of antibodies which may render the cells unsuitable for further experimental and therapeutic applications. Therefore, a need exists to develop novel chemical compounds that are useful for detection of neural stem cells.
SUMMARY OF THE INVENTION
[0004] A novel chemical structure with fluorescence emission and specificity to neural stem cells is described. This scaffold is compatible with a range of chemical functional groups, and can be bioconjugated to proteins as well as other macromolecules of interest, such as carbohydrates and lipids. One of the compounds, named as compound of designation (CDr3), selectively stains both human and mouse neural stem cells (NSC) by binding to a NSC marker protein fatty acid binding protein 7 (FABP7).
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] The foregoing will be apparent from the following more particular description of example embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating embodiments of the present invention.
[0006] FIG. 1A shows the selective staining of NS5 by CDr3. Nuclei of all E14, NS5, D-NS5 and MEF were visualized by Hoechst 33342 (DAPI); but only NS5 was selectively stained by CDr3 (TxRd). Top panel, bright field (BF) images; middle and bottom panels, fluorescent images obtained with DAPI and Texas Red filter set. Scale bar, 50 μm.
[0007] FIG. 1B shows the chemical structure of CDr3.
[0008] FIG. 1C shows the flow cytometry dot plot images of E14, NS5, D-NS5 and MEF incubated with CDr3. DMSO was added for unstained control cells. The images of each type of cells were overlaid. Segregated NS5 cells by CDr3 are marked.
[0009] FIG. 1D shows selective staining of NS5 by CDr3. Mixed primary mouse brain cells (PC) cultured for 2 weeks in vitro were incubated with CDr3 and Hoechst 33342. The images of living cells are shown in bright field (BF) and fluorescence (DAPI and Texas Red) panels. The primary brain cells with various morphologies were not stained by CDr3, while NS5 treated in parallel was stained. The images of the same cells were acquired after immunocytochemical staining (ICC) with antibodies to neuron-specific class III β-tubulin (Tuj1; TxRd channel) and astrocyte-specific glial fibrillary acidic protein (GFAP; FITC channel). Scale bar, 100 μm.
[0010] FIG. 2A shows the identification of CDr3 binding protein. A protein lysate of CDr3-stained NS5 was separated by 2DE. The major fluorescent spot was marked with a circle (left panel). Many silver-stained protein spots were detected in a duplicate gel (right panel).
[0011] FIG. 2B shows the MS/MS fragment ion analysis of tryptic peptide (MVVTLTFGDIVAVR) SEQ ID No.: 1, indicated FABP7 as a binding target of CDr3. Only the main y-series of ion fragmentation was labeled in the spectrum. M* indicates oxidation at methionine residue.
[0012] FIG. 2C shows the fluorescence signals from EGFP and CDr3 overlap only in the cells expressing either mouse FABP7 or human FABP7 fused to EGFP. The fluorescence images were acquired on a Nikon Ti microscope using DAPI (Hoechst), FITC (EGFP) and Texas Red (Cdr3) filter sets. Scale bar, 50 μm.
[0013] FIG. 3A shows real-time RT-PCR analysis data of FABP7 expression in H1, ReNcell VM and ReNcell VM-differentiated neurons. Relative expression level of FABP7 to GAPDH is depicted.
[0014] FIG. 3B shows that the strong signal of FABP7 protein (14 kDa) was detected by Western blotting in ReNcell VM (lane 3) lysate, while it was not detectable in the lysates of H1 (lane 1) and ReNcell VM-differentiated neurons (lane 2). β-Actin (42 kDa) staining demonstrates consistent loading across sample lanes. Fluorescence scan showed CDr3-labelled FABP7 only in the lysate of ReNcell VM (lane 3) incubated with CDr3.
[0015] FIG. 3C shows the immunocytochemistry of FABP7 in H1, ReNcell VM and ReNcell VM-differentiated neurons (D-ReNcell VM). Only ReNcell VM was brightly stained by FABP7 antibody. Scale bar, 50 μm. Upper panel, nuclei staining with DAPI; lower panel, FABP7 staining with antibody.
[0016] FIG. 3D shows H1, ReNcell VM and ReNcell VM-differentiated neurons incubated with CDr3. Fluorescence signal was detected only in ReNcell VM. Upper panel, bright field image; lower panel, fluorescence image. Scale bar, 50 μm.
[0017] FIG. 4A shows differentiated E14 cell distribution in FACS after staining with CDr3. The CDr3-stained embryoid body cells were separated into CDr3 bright and CDr3 dim populations.
[0018] FIG. 4B shows the higher expression of FABP7 in CDr3 bright than in CDr3 dim cells, which was determined by immunocytochemistry followed by flow cytometry. The primary FABP7 antibody was detected by an Alexa Fluor 488-conjugated secondary antibody.
[0019] FIG. 5 shows the higher expression of FABP7, Hes1, Musashi, Nestin and Pax6 in CDr3 bright cells than in CDr3 dim cells. The CDr3 bright and CDr3 dim cells were collected separately by FACS for gene expression analysis by real time RT-PCR and neurosphere assay.
[0020] FIG. 6A shows the flow cytometry dot plot images showing shift of stained
[0021] E14.5 fetal mouse brain cells to bright fluorescence (+) compared to control group (−).
[0022] FIG. 6B shows the numbers (left panel) and the sizes (right panel) of neurospheres for the cells sorted by CDr3, CD133 antibody, SSEA-1 antibody and Aldefluor compared to unsorted cells.
[0023] FIG. 7 shows the numbers (upper panel) and sizes (lower panel) of neurospheres cultured in the presence of CDr3 and DMSO used as a vehicle.
[0024] FIG. 8 shows number of NS5 cells (left panel) and percentage of BrdU-positive cells (right panel) cultured in the presence of CDr3 and DMSO used as a vehicle.
[0025] FIG. 9 shows the spectroscopic information of CDr3.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The teachings of all patents, published applications and references cited herein are incorporated by reference in their entirety.
[0027] The invention pertains to a novel chemical structure with fluorescence emission and specificity to neural stem cells. This scaffold is compatible with a range of chemical functional groups, and can be bioconjugated to proteins as well as other macromolecules of interest, such as carbohydrates and lipids. One of the compounds, named as compound of designation (CDr3), selectively stains both human and mouse neural stem cells (NSC) by binding to a NSC marker protein fatty acid binding protein 7 (FABP7).
[0028] One embodiment of the invention is a compound represented by structural
[0029] Formula (I) or pharmaceutically acceptable salts thereof:
[0000]
[0000] wherein:
[0030] R is (C 6 -C 10 )aryl, (C 5 -C 10 )heteroaryl, (C 6 -C 10 )aryl(C 2 -C 6 )alkenyl or 2-4 member polycyclyl, wherein each 2-4 member polycyclyl optionally and independently contains 1-2 ring heteroatoms selected from oxygen, nitrogen and sulfur;
and wherein R is optionally substituted with 1-4 substituents independently selected from (C 1 -C 6 )alkyl, halo(C 1 -C 6 )alkyl, hydroxy(C 0 -C 6 )alkyl, (C 6 -C 10 )aryl, halo (C 6 -C 10 )aryl, hydroxy(C 6 -C 10 )aryl, (C 1 -C 6 )alkoxy, halo(C 1 -C 6 )alkoxy, (C 3 -C 8 )cycloalkyl, halo(C 6 -C 10 )aryl(C 1 -C 6 )alkoxy, halogen, amino, (C 1 -C 6 )alkoxy(C 6 -C 10 )aryl(C 1 -C 6 )alkoxy, nitro, (3 to 9 membered)heterocyclyl, (C 0 -C 6 )alkyl(C 6 -C 10 )aryl(C 0 -C 6 )alkoxy, (C 5 -C 10 )heterocycle, —OCF 3 , —B(OH) 2 , cyano(C 1 -C 6 )alkylene amino, (C 1 -C 6 )alkoxyamino, (C 6 -C 10 )aryl(C 2 -C 6 )alkenyl, (C 2 -C 6 )alkenyl(C 1 -C 6 )alkoxy, (C 1 -C 6 )sulfoxy or —N(CH 3 )(C 1 -C 6 )OH.
[0032] Another embodiment of the invention is a method for detection of a neural stem cell (NSC) comprising:
a) staining said neural stem cell with a compound, forming a dye-stained neural stem cell by binding said compound to a marker protein of said neural stem cell, wherein said compound is of structural Formula (I) or pharmaceutically acceptable salts thereof: b) optionally incubating product of step a) to form a said incubated dye-stained stem (intensity of fluorescence can be increased by incubation for the period of time sufficient for achieving desired intensity, e.g., from about 1 hour to about 24 hours, but less or more time may be acceptable.); c) analyzing said incubated dye-stained stem cell by a flow cytometry and FACS; and d) subjecting said dye-stained neural stem cell to two-dimensional SDS-PAGE (2DE) fluorescence scanning to detect fluorescence signal, wherein the presence of a signal is indicative of the presence of said neural stem cell.
[0037] In one embodiment of the invention said method is applied in neural stem cell biology and regenerative medicine.
[0000]
[0038] (a) pyridine, piperidine, 50° C., 48 h, then 80° C., 24 h, (b)H 2 , Pd/C, MeOH, RT, 6 h, (c) K 2 CO 3 , H 2 O/EtOH, reflux, overnight, (d) 2,2,2-trichloroethanol, pyridine, DCC, EA, RT, overnight, (e) 3,5-dimethyl-1H-pyrrole-2-carbaldehyde, POCl 3 , DCM, RT, 4 h, (f) DIEA, BF 3 OEt 2 , DCM, RT, overnight, (g) R—CHO, pyrrolidine, acetic acid, ACN, 85° C., 15 min.
[0000]
CHART 1
Building block acid chlorides employed in the synthesis
(R-CHO in Scheme 1).
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Definitions
[0039] “Alkyl” means a saturated aliphatic branched or straight-chain monovalent hydrocarbon radical having the specified number of carbon atoms. Thus, “(C 1 -C 6 ) alkyl” means a radical having from 1-6 carbon atoms in a linear or branched arrangement. “(C 1 -C 6 )alkyl” includes methyl, ethyl, propyl, butyl, pentyl and hexyl.
[0040] “Alkylene” means a saturated aliphatic straight-chain divalent hydrocarbon radical having the specified number of carbon atoms. Thus, “(C 1 -C 6 )alkylene” means a divalent saturated aliphatic radical having from 1-6 carbon atoms in a linear arrangement. “(C 1 -C 6 )alkylene” includes methylene, ethylene, propylene, butylene, pentylene and hexylene.
[0041] “Heterocycle” means a saturated or partially unsaturated (4-7 membered) monocyclic heterocyclic ring containing one nitrogen atom and optionally 1 additional heteroatom independently selected from N, O or S. When one heteroatom is S, it can be optionally mono- or di-oxygenated (i.e., —S(O)— or -S(O) 2 —). Examples of monocyclic heterocycle include, but not limited to, azetidine, pyrrolidine, piperidine, piperazine, hexahydropyrimidine, tetrahydropyran, tetrahydropyran, morpholine, thiomorpholine, thiomorpholine 1,1-dioxide, tetrahydro-2H-1, 2-thiazine, tetrahydro-2H-1,2-thiazine 1,1-dioxide, isothiazolidine, or isothiazolidine 1,1-dioxide.
[0042] “Cycloalkyl” means saturated aliphatic cyclic hydrocarbon ring. Thus, “C 3 -C 7 cycloalkyl” means (3-7 membered) saturated aliphatic cyclic hydrocarbon ring. C 3 -C 7 cycloalkyl includes, but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
[0043] The term “alkoxy” means —O-alkyl; “hydroxyalkyl” means alkyl substituted with hydroxy; “aralkyl” means alkyl substituted with an aryl group; “alkoxyalkyl” mean alkyl substituted with an alkoxy group; “alkylamine” means amine substituted with an alkyl group; “cycloalkylalkyl” means alkyl substituted with cycloalkyl; “dialkylamine” means amine substituted with two alkyl groups; “alkylcarbonyl” means —C(O)-A*, wherein A* is alkyl; “alkoxycarbonyl” means —C(O)—OA*, wherein A* is alkyl; and where alkyl is as defined above and includes methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy.
[0044] “Cycloalkoxy” means an cycloalkyl-O— group wherein the cycloalkyl is as defined above. Exemplary (C 3 -C 7 )cycloalkyloxy groups include cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexoxy and cycloheptoxy.
[0045] Haloalkyl and halocycloalkyl include mono, poly, and perhaloalkyl groups where each halogen is independently selected from fluorine, chlorine, and bromine.
[0046] “Hetero” refers to the replacement of at least one carbon atom member in a ring system with at least one heteroatom selected from N, S, and O. A hetero ring system may have 1 or 2 carbon atom members replaced by a heteroatom.
[0047] “Halogen” and “halo” are interchangeably used herein and each refers to fluorine, chlorine, bromine, or iodine.
[0048] “Cyano” means —C≡N.
[0049] “Nitro” means —NO 2 .
[0050] As used herein, an amino group may be a primary (-NH 2 ), secondary (—NHR x ), or tertiary (—NR x R y ), wherein R x and R y may be any of the optionally substituted alkyls described above.
[0051] The terms “haloalkyl” and “haloalkoxy” mean alkyl or alkoxy, as the case may be, substituted with one or more halogen atoms. The term “halogen” means F, Cl, Br or I. Preferably the halogen in a haloalkyl or haloalkoxy is F.
[0052] The term “acyl group” means —C(O)B*, wherein B* is an optionally substituted alkyl group or aryl group (e.g., optionally substituted phenyl).
[0053] An “alkylene group” is represented by —[CH 2 ] z —, wherein z is a positive integer, preferably from one to eight, more preferably from one to four.
[0054] An “alkenylene group” is an alkylene in which at least a pair of adjacent methylenes are replaced with —CH═CH—.
[0055] The term “(C6-C10)aryl” used alone or as part of a larger moiety as in “arylalkyl”, “arylalkoxy”, or “aryloxyalkyl”, means carbocyclic aromatic rings. The term “carbocyclic aromatic group” may be used interchangeably with the terms “aryl”, “aryl ring” “carbocyclic aromatic ring”, “aryl group” and “carbocyclic aromatic group”. An aryl group typically has 6-14 ring atoms. A “substituted aryl group” is substituted at any one or more substitutable ring atom. The term “C 6-14 aryl” as used herein means a monocyclic, bicyclic or tricyclic carbocyclic ring system containing from 6 to 14 carbon atoms and includes phenyl, naphthyl, anthracenyl, 1,2-dihydronaphthyl, 1,2,3,4-tetrahydronaphthyl, fluorenyl, indanyl, indenyl and the like.
[0056] The term “heteroaryl”, “heteroaromatic”, “heteroaryl ring”, “heteroaryl group” and “heteroaromatic group”, used alone or as part of a larger moiety as in “heteroarylalkyl” or “heteroarylalkoxy”, refers to aromatic ring groups having five to fourteen ring atoms selected from carbon and at least one (typically 1-4, more typically 1 or 2) heteroatoms (e.g., oxygen, nitrogen or sulfur). They include monocyclic rings and polycyclic rings in which a monocyclic heteroaromatic ring is fused to one or more other carbocyclic aromatic or heteroaromatic rings. The term “5-14 membered heteroaryl” as used herein means a monocyclic, bicyclic or tricyclic ring system containing one or two aromatic rings and from 5 to 14 atoms of which, unless otherwise specified, one, two, three, four or five are heteroatoms independently selected from N, NH, N(C 1-6 alkyl), O and S.
[0057] The term “2-4 member polycyclyl is a cyclic compound with 2-4 hydrocarbon loop or ring structures (e.g., benzene rings). The term generally includes all polycyclic aromatic compounds, including the polycyclic aromatic hydrocarbons, the heterocyclic aromatic compounds containing sulfur, nitrogen, oxygen, or another non-carbon atoms, and substituted derivatives of these.
[0058] The term “Alkenyl” means a straight or branched hydrocarbon radical having a specified number of carbon atoms and includes at least one double bond. The (C 6 -C 10 )aryl(C 2 -C 6 )alkenyl group connects to the remainder of the molecule through the (C 2 -C 6 )alkenyl portion of (C 6 -C 10 )aryl(C 2 -C 6 )alkenyl.
[0059] Another embodiment of the present invention is a pharmaceutical composition comprising one or more pharmaceutically acceptable carrier and/or diluent and a compound disclosed herein or a pharmaceutically acceptable salt thereof.
[0060] “Pharmaceutically acceptable carrier” and “pharmaceutically acceptable diluent” means non-therapeutic components that are of sufficient purity and quality for use in the formulation of a composition of the invention that, when appropriately administered to an animal or human, typically do not produce an adverse reaction, and that are used as a vehicle for a drug substance (i.e. a compound of the present invention).
[0061] Pharmaceutically acceptable salts of the compounds of the present invention are also included. For example, an acid salt of a compound of the present invention containing an amine or other basic group can be obtained by reacting the compound with a suitable organic or inorganic acid, resulting in pharmaceutically acceptable anionic salt forms. Examples of anionic salts include the acetate, benzenesulfonate, benzoate, bicarbonate, bitartrate, bromide, calcium edetate, camsylate, carbonate, chloride, citrate, dihydrochloride, edetate, edisylate, estolate, esylate, fumarate, glyceptate, gluconate, glutamate, glycollylarsanilate, hexylresorcinate, hydrobromide, hydrochloride, hydroxynaphthoate, iodide, isethionate, lactate, lactobionate, malate, maleate, mandelate, mesylate, methylsulfate, mucate, napsylate, nitrate, pamoate, pantothenate, phosphate/diphosphate, polygalacturonate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, teoclate, tosylate, and triethiodide salts.
[0062] Salts of the compounds of the present invention containing a carboxylic acid or other acidic functional group can be prepared by reacting with a suitable base. Such a pharmaceutically acceptable salt may be made with a base which affords a pharmaceutically acceptable cation, which includes alkali metal salts (especially sodium and potassium), alkaline earth metal salts (especially calcium and magnesium), aluminum salts and ammonium salts, as well as salts made from physiologically acceptable organic bases such as trimethylamine, triethylamine, morpholine, pyridine, piperidine, picoline, dicyclohexylamine, N,N′-dibenzylethylenediamine, 2-hydroxyethylamine, bis-(2-hydroxyethyl)amine, tri-(2-hydroxyethyl)amine, procaine, dibenzylpiperidine, dehydroabietylamine, N,N′-bisdehydroabietylamine, glucamine, N-methylglucamine, collidine, quinine, quinoline, and basic amino acids such as lysine and arginine.
EXAMPLES
[0063] 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) has superior advantages to be one of the more versatile fluorophores, such as high quantum yield, tunable fluorescence characteristics, high photo stability, and narrow emission bandwidth. Since the first discovery of BODIPY dyes in 1968, chemical modification for BODIPY scaffold has been well explored. Thus great numbers of BODIPY dyes have been used to label biomolecules. A large numbers of sensors and markers based on BODIPY scaffold have also been developed. But BODIPY-based library synthesis has been rarely reported due to the synthetic challenge.
[0064] Here we disclose our invention of a novel diversity oriented fluorescence BODIPY active ester compound library synthesized via solution phase synthetic method and one of the compounds which has been identified as neural stem cell selective imaging probe.
[0065] To develop fluorescent imaging probes which selectively detect NSC, we have screened in-house-generated 3,160 Diversity Oriented Fluorescence Library (DOFL) compounds in E14 mouse embryonic stem cell (mESC), E14-derived NS5 NSC, differentiated NS5 into astrocyte (D-NS5) and mouse embryonic fibroblast (MEF). For high throughput screening, the 4 different types of cells were prepared side by side in 384-well plates and incubated with 0.5 or 1.0 μM of compounds. After 24 hr incubation, the bright field and fluorescence images of the cells were acquired on an automated imaging microscope system ImageXpress Micro™ and the fluorescence intensity of the stained cells was analyzed using MetaXpress® image processing software. Through the followed secondary and tertiary screenings CDr3 has been identified as the hit molecule that stains NS5 most selectively and brightly ( FIG. 1 ).
[0066] The intrinsic fluorescence property of our compounds makes it possible to track the target without any modification from the stained living cells through all processes for identification once it binds strongly to the target molecules. When we subjected CDr3-stained NS5 lysate to two-dimensional sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE (2DE)) for a fluorescence scanning, a major spot of approximately 15 kDa was detected ( FIG. 2A ).
[0067] Matrix-assisted laser desorption/ionization-time of flight/time of flight mass spectrometry (MALDI-TOF/TOF MS) and MS/MS analysis allowed us to identify the protein spot as FABP7 ( FIG. 2B ). Among the currently known 9 mammalian FABPs that play pivotal roles in transporting and trafficking of lipids in various tissues, FABP7 is particularly expressed in the central nervous system and a well-known marker of radial glial cells which play as NSC in the brain 6 . To confirm that FABP7 is the specific binding target of CDr3, we cloned both human and mouse FABP7 genes and fused them to EGFP constructs for expression in HEK293 cells. We incubated the cells with CDr3 and observed the signals of EGFP and CDr3 overlap in the cells that express either human or mouse FABP7 fused to EGFP ( FIG. 2C ).
[0068] With this result, we attempted to test CDr3 on a commercial ReNcell VM human NSC line derived from the ventral mesencephalon region of human foetal brain tissue. We first examined the expression level of FABP7 by real time RT-PCR and found a 540-fold higher level of FABP7 mRNA in ReNcell VM than in H1 human ESC. This expression was dramatically down-regulated (20-fold) by differentiation into neurons ( FIG. 3A ). Western blot analysis demonstrated a similar observation in protein expression levels with a strong FABP7 band at 14 kDa detected in ReNcell VM lysate while no FABP7 was detected in the lysates of H1 and ReNcell VM-derived neurons ( FIG. 3B ). In accordance with the Western blot data, ReNcell VM were strongly stained by FABP7 antibody while H1 and ReNcell VM-derived neurons were not stained ( FIG. 3C ). We then incubated the 3 types of cells with CDr3 to determine whether living ReNcell VM could be distinguished by the compound among others. As expected from the FABP7 expression analysis data, CDr3 selectively stained ReNcell VM in living cell cultures ( FIG. 3D ).
[0069] Next, we were interested to test whether CDr3 can be used for the isolation of NSC from the heterogeneous populations of cells. According to the protocol described by Bibel et al. 7 , we induced differentiation of E14 to generate FABP7-positive radial glial cells. The embryoid bodies generated from E14 in the absence of leukemia inhibitory factor were treated with retinoic acid for 2 days until dissociation into single cell suspension. The cells were stained with CDr3 and the CDr3bright and CDr3dim cells were collected separately by FACS. Each cell population was stained with FABP7 antibody and analyzed by flow cytometry. The overlay plot showed well-separated 2 clusters demonstrating that the cells isolated by CDr3 from the heterogeneous embryoid body cells were FABP7 expressing cells ( FIG. 4 ). For the NSC isolation from the brain tissue, we incubated the E14.5 fetal mouse brain primary cells with CDr3, and the CDr3 bright and CDr3 dim cells were collected separately by FACS for gene expression analysis by real time RT-PCR and neurosphere assay. The expression levels of FABP7, Hes1, Musashi, Nestin and Pax6 in CDr3 bright cells were more than 3-fold higher than in CDr3 dim cells, while the differences of Hes5, Sox2 and Bmi1 expression levels were less than 2-fold ( FIG. 5 ). In a neurosphere assay the CDr3 bright cells grew to generate 26.8±2.5 neurospheres while CDr3 dim cells generated only 0.25±0.5 neurospheres per well. As a separate study, we sorted the fetal mouse brain cells using CD133 antibody, SSEA-1 antibody, Aldefluor (BODIPY-aminoacetaldehyde) as well as CDr3 by FACS for neurosphere assay ( FIG. 6A ). We observed a big difference between all marker positive and negative cells in the numbers of generated neurospheres. Among the markers, largest number of neurospheres was generated in CDr3 positive cells followed by SSEA-1, Aldefluor and CD133 positive cells ( FIG. 6B ), while the sizes of neurospheres were all similar ( FIG. 6C ). This result shows highest correlation between neurosphere forming ability of the NSC and FABP7 level among the tested NSC markers.
[0070] Finally, we determined whether CDr3 affects NSC proliferation by culturing NS5 and neurosphere in the presence of CDr3. Total numbers of NS5 cells grown for 6 hr and 48 hr and the percentage of BrdU positive cells pulse-labeled in the CDr3-containing medium were not different from those of cells grown in DMSO only-containing medium which was used as a control ( FIG. 7 ). In accordance with the result of experiment with NS5 cells, the number and size of neurospheres generated in the presence of CDr3 were not different from control ( FIG. 8 ).
Materials and Methods
Cell Culture and Differentiation
[0071] E14 was maintained on gelatin-coated dishes in high-glucose DMEM supplemented with 10% FBS, 2 mM L-glutamine, 100 U/ml penicillin, 100 μg/ml streptomycin, 0.1 mM non-essential amino acids, 0.1% β-mercaptoethanol and 100 U/ml leukemia inhibitory factor (LIF, Chemicon). For differentiation, the cells were detached from their culture plates using 0.25% trypsin with 1mM EDTA solution (Invitrogen) and sub-cultured in non-adherent bacteria culture dishes in the E14 media but without LIF. Subsequently, 90% of the EBF media was changed on a daily basis for a total of 4 days and then retinoic acid (Sigma) was added to the final concentration of 1 μM. On day 6, the embryoid bodies were harvested and dissociated in 0.05% trypsin with 0.2 mM EDTA solution for 3 min at 37° C. to obtain a single cell suspension. NS5 was maintained in Euromed-N medium supplemented with 100 μg/ml Apo-transferin (Sigma), 5.2 ng/ml Sodium Selenite (Sigma), 19.8 ng/ml progesterone (Sigma), 16 μg/ml Putrescine (Sigma), 25 μg/ml insulin (Sigma), 50.25 μg/ml BSA (Gibco), 10 ng/ml bFGF (Gibco), 10 ng/ml EGF (Gibco), 100 U/ml penicillin (Gibco), 100 μg/ml streptomycin (Gibco) and 2 mM L-glutamine (Gibco). For differentiation of NS5 into astrocyte, the medium was changed to NS5 maintenance medium containing 5% FBS but without FGF and bEGF. MEF was maintained in the same media as used for E14 but without LIF. H1 was maintained in a feeder-free condition on matrigel-coated dishes in MEF-conditioned medium containing Knockout DMEM/10% serum replacement (Gibco), 0.1 mM MEM non-essential amino acids (Gibco), 1 mM L-glutamine (Gibco), 0.1 mM β-mercaptoethanol (Gibco), 8% plasmanate (NUH pharmacy), 12 ng/ml LIF, and 10 ng/ml human recombinant Basic Fibroblast Growth Factor (bFGF; Gibco). ReNcell VM (Millipore #SCC008) was maintained on laminin-coated dishes in ReNcell NSC Maintenance Medium (Millipore #SCM005) containing 20 ng/ml bFGF and 20 ng/m EGF. For neural differentiation, ReNcell VM were seeded on PLO/Laminin-coated plates and cultured for up to 3 weeks in media comprising a 1:1 mix of N2-DMEM/F12 and B27-Neurobasal media supplemented with 0.1 mM MEM non-essential amino acids and 1 mM L-glutamine, all obtained from Gibco/Invitrogen. For mixed primary brain cell culture, the brains of neonatal mouse pups were cut into small pieces and digested in 0.25% trypsin with 1mM EDTA solution (Invitrogen) for 30 min at 37° C. before neutralization with FBS. After washing with PBS by centrifugation and resuspension, the tissues were triturated using a 10 ml pipette fitted with 1 ml tip and the suspension was filtered through a strainer with 40 μm nylon mesh. The obtained single cells were plated on 35 mm cell culture dishes in OptiMEM-GlutaMAX™ containing 10% FBS. Unattached cells and cell debris were removed the next day by replacing medium. One-half of the medium was replaced twice a week thereafter.
DOFL High Throughput Screening
[0072] DOFL compounds were diluted from 1 mM DMSO stock solutions with the culture medium to make final concentration of 0.5 μM or 1.0 μM. The 4 different types of cells plated side by side on 384-well plates were incubated with the compounds overnight at 37° C. and the nuclei were stained with either Hoechst33342 or DRAQ5 the next day before image acquisition. The fluorescence cell images of 2 regions per well were acquired using ImageXpress Micro™ cellular imaging system (Molecular Device) with 10× objective lens and the intensity was analyzed by MetaXpress® image processing software (Molecular Device). The hit compounds which stained NS5 more brightly than other cells were selected based on the intensity data and manual screening of the raw images.
Live Cell Staining
[0073] The cells were incubated with 0.5 μM of CDr3 in Opti-MEM GlutaMAX™ for 1 hr and, if necessary, subsequently with 2μM of Hoechst 33342 for 15 min at 37° C. Then the cells were rinsed in the maintenance medium for 1 hr and the medium was replaced again with fresh one before image acquisition. The staining and destaining times were prolonged when necessary. The bright field and fluorescence images were acquired on ECLIPSE Ti microscope (Nikon Instruments Inc) or A1R confocal microscope (Nikon Instruments Inc) using NIS Elements 3.10 software or on Axio Observer D1 using AxioVision v 4.8 software (Carl Zeiss Inc).
Flow Cytometry and FACS
[0074] The cells incubated with CDr3 were harvested by trypsin treatment, washed and resuspended in PBS. The fluorescence intensity of the cells was measured on a flow cytometry (BD™ LSR II) or collected using a FACS machine (BD FACS Aria™). The data were analyzed and processed using FlowJo 7 software.
Two-Dimensional Gel Electrophoresis
[0075] CDr3-stained NS5 pellet was lysed in a lysis buffer (40 mM Trizma, 7M Urea, 2M thiourea and 4% CHAPS) premixed with 10 μl/ml Protease Inhibitor Cocktail (EDTA free, GE healthcare), 50 μg/ml DNase I and 50 μg/ml RNase A (Roche). The proteins of 0.2 mg and 1 mg were separated by 2DE for silver staining and fluorescent imaging, respectively. The fluorescence image of gels was acquired using a Typhoon 9400 scanner (GE healthcares) at excitation/emission wavelengths of 532 nm/610 nm with PMT at 500 v and a duplicate gel was stained using PlusOne™ Silver Staining Kit (GE healthcare) according to the manufacturer's protocol. The fluorescently 18abeled protein spots were directly excised from the gel for in-gel trypsin digestion and peptide extraction.
MALDI-TOF/TOF MS and MS/MS Analyses
[0076] Tryptic peptide of 0.6 μl was spotted onto Prespotted AnchorChip target plate (Bruker Daltonics Inc) according to manufacturer's protocol. The peptide mass fingerprint and selected peptide MS/MS fragment ion analysis were carried out on UltraFlex III TOF-TOF (Bruker Daltonics Inc) with the compass 1.2 software package including FlexControl 3.0 and FlexAnalysis 3.0 with PAC peptide calibration standards. The peak lists of MS and MS/MS were submitted to in-house Mascot server (phenyx.bii.a-star.edu.sg/search_form_select.html) through BioTools 3.2 with the database of SwissProt 57.8 (509,019 sequences) allowing peptide mass tolerance of 100 ppm and 0.5 Da with maximum 1 missed cleavage and considering variable modifications of carbamidomethyl at cysteine (C) and oxidation at methionine (M).
Chemical Synthesis
[0077] All reactions were performed in oven-dried glassware under a positive pressure of nitrogen. Unless otherwise noted, starting materials and solvents were purchased from Aldrich and Acros organics and used without further purification. Analytical TLC was carried out on Merck 60 F254 silica gel plate (0.25 mm layer thickness) and visualization was done with UV light. Column chromatography was performed on Merck 60 silica gel (230-400 mesh). NMR spectra were recorded on a Bruker Avance 300 NMR spectrometer. Chemical shifts are reported as δ in units of parts per million (ppm) and coupling constants are reported as a J value in Hertz (Hz). Mass of all the compounds was determined by LC-MS of Agilent Technologies with an electrospray ionization source. All fluorescence assays were performed with a Gemini XS fluorescence plate reader.
[0078] Synthesis of compound 1: The intermediate 1 in the Scheme 1 was synthesized as reported previously 8 .
[0079] Synthesis of CDr3: 1, (20 mg, 0.047 mM) and 3,4-dimethoxybenzaldehyde (16 mg, 0.094 mM) were dissolved in acetonitrile (4 ml), followed by the addition of the mixture of pyrrolidine (23.6 μl, 0.282 mM) and acetic acid (16.1 μl, 0.282 mM). The reaction was heated at 85° C. for 15 min and then cooled down to r.t. The resulting crude mixture was concentrated under vacuum and purified by normal-phase column chromatography (eluting system: hexane/ethyl acetate (6:1) to render CDr3 as purple solid (15 mg, 56% yield).
Characteristics of CDr3
1H and 13C NMR Spectra on CDr3
[0080] 1H NMR (300 MHz, CDCl3): 2.28 (s, 3H), 2.96 (t, J=7.5 Hz, 2H), 3.40 (t, J=7.5 Hz, 2H), 3.92 (s, 3H), 3.97 (s, 3H), 4.78 (s, 2H), 6.30 (d, J=3.9 Hz, 1H), 6.71 (s, 1H), 6.85 (d, J=3.9 Hz, 1H), 6.86 (d, J=8.1 Hz, 1H), 7.03 (s, 1H), 7.12 (d, J=1.8 Hz, 1H), 7.16 (dd, J=1.8, 8.4 Hz, 1H), 7.29 (d, J=16.2 Hz, 1H), 7.48 (d, J=16.2 Hz, 1H).
[0081] 13C NMR (75.5 MHz, CDCl3): 11.3, 23.7, 29.6, 33.0, 55.9, 56.0, 56.1, 74.0, 94.9, 109.6, 110.4, 111.1, 116.2, 116.6, 121.6, 122.1, 122.2, 126.7, 129.2, 133.6, 139.1, 143.0, 149.3, 150.8, 171.0.
[0082] ESI-MS m/z(C25H24BCl3F2N2O4) calculated: 571.1 (M+H)+, found: 551.1 (M−F).
Fluorescence Property Measurement
[0083] 10 μM solutions in DMSO was prepared and measured absorption and 2 μM solutions in DMSO was prepared and measured absorption emission of library compound. Spectrum of CDr3 is shown in FIG. 9 .
[0000] Neural Stem Cell Isolation from Fetal Mouse Brain Cell Suspension
[0084] E14.5 fetal mouse brains were trypsinized in 0.25% trypsin with 1 mM EDTA solution (Invitrogen) for 30 mins at 37° C. before neutralization with FBS. The tissues were triturated sequentially with a 10 ml pipette followed by a 1 ml blue tip and a 0.2 ml yellow tip attached to the 10 ml pipette until the cell suspension flows through smoothly. The tissue suspension was washed 3 times with PBS by repeated resuspension and centrifugation and filtered through a 40 μm strainer. The cells were stained using CDr3, CD133 antibody, SSEA-1 antibody or Aldefluor as described below and FACS sorted. The FACS sorted bright and dim cells of 2% at each end and unsorted (randomly harvested) cells were plated in a DMEM/F12 medium containing 10 ng/ml bFGF, 20 ng/ml EGF and B27 without vitamin A (Invitrogen) at a density of 10,000 cells/well in 6-well plate to grow forming spheres. The number and size of neurospheres generated from each group were measured after 6 days culture.
CDr3
[0085] Dissociated cells were incubated with 0.5 μM of CDr3 in neurosphere media for 1 hr and then spun down for resuspension in compound free neuropshere media for 30 minutes. The cells were then spun down and resuspended in PBS for FACS. For control group, the cells were incubated with 0.05% DMSO instead of CDr3.
CD133 Antibody
[0086] Dissociated cells were blocked in 1% BSA for 30 min and then incubated with CD133 antibody (1:500) for 1 hr. The cells were washed with PBS by centrifugation and resuspension and then incubated with Alexa fluor 488-conjugated anti-rat IgG (1:1,000) for 1 hr. The stained cell sample was washed again before resuspension in PBS for FACS. For control group, primary antibody was omitted.
SSEA-1 Antibody
[0087] Dissociated cells were blocked in 1% BSA for 30 min and then incubated with SSEA-1 antibody (1:500) for 1 hr. The cells were washed with PBS by centrifugation and resuspension and then incubated with Alexa fluor 633-conjugated anti-mouse IgM (Invitrogen) for 1 hr. The stained cell sample was washed again before resuspension in PBS for FACS. For control group, primary antibody was omitted.
Aldefluor
[0088] The cells were incubated with activated Aldefluor substrate (5 μl/ml) for 30 min at 37° C. The cells were then spun down and resuspended in Aldefluore assay buffer for FACS. For control, diethylaminobenzaldehyde, a specific inhibitor of ALDH was added (5 μl/ml) to the cells together with Aldefluore substrate.
Serial Neurosphere Assay
[0089] Neurospheres were generated from the fetal mouse brain cells prepared as described in above (Neural stem cell isolation). After expansion by 2 times of passages, the cells plated in triplicate in 6-well culture plates at a density of 3,000 cells per well and cultured in the presence of 1 μM CDr3 or 0.1% DMSO for 6 days. After 6 days, the numbers and sizes of neurospheres were determined. For serial assay, the neurospheres were further passaged in the medium containing 1 μM CDr3 or 0.1% DMSO.
NS5 Cell Proliferation Assay
[0090] NS5 were seeded into 96-well plates (Greiner) at a density of 1000 cells/well. The next day, DMSO and 1 mM DMSO stock of CDr3 was added into 32 wells for each to be diluted to 0.1% and 1 uM, respectively. At 6 hr and 48 hr time points, 1 ug/ml of Hoechst 33342 was added and incubated for 15 min for image acquisition using an ImageXpress Micro™ and MetaXpress Imaging system (Molecular Devices). Hoeschst33342 and CDr3 signals were detected via DAPI and Texas red filters, respectively, and the images of a total of 4 areas were captured per well. Multi wavelength scoring analysis was then run to quantify the number of cells based on Hoechst 33342-stained nuclei image. For the quantification of pulse-labeled cells with BrdU, the cells were stained using FITC conjugated anti-BrdU antibody (BD Pharmingen™) according to the manufacturer's instruction. Total numbers of Hoechst 33342-stained and BrdU-labeled nuclei were counted by image based analysis using ImageJ-ITCN software.
REFERENCES
[0000]
1. (a) Geddes, C. D.; Lakowicz, J. R. Topics in Fluorescence Spectroscopy, Vol. 9; Springer: New York, 2005. (b) Geddes, C. D.; Lakowicz, J. R. Topics in Fluorescence Spectroscopy, Vol. 10; Springer: New York, 2005.
2. Okano, H. & Sawamoto, K. Neural stem cells: involvement in adult neurogenesis and CNS repair. Philos Trans R Soc Lond B Biol Sci 363, 2111-22 (2008).
3. Falk, S. & Sommer, L. Stage- and area-specific control of stem cells in the developing nervous system. Curr Opin Genet Dev 19, 454-60 (2009).
4. Shimazaki, T. Biology and clinical application of neural stem cells. Horm Res 60 Suppl 3, 1-9 (2003).
5. Daadi, M. M., et al. Adherent self-renewable human embryonic stem cell-derived neural stem cell line: functional engraftment in experimental stroke model. PLoS One 3, e1644 (2008).
6. Malatesta, P., et al. Isolation of radial glial cells by fluorescent-activated cell sorting reveals a neuronal lineage. Development 127, 5253-63 (2000).
7. Bibel, M. et al. Differentiation of mouse embryonic stem cells into a defined neuronal lineage. Nat Neurosci 7, 1003-9 (2004).
8. Malan, S. F. et al. Fluorescent ligands for the histamine H2 receptor: synthesis and preliminary characterization. Bioorg Med Chem 12, 6495-503 (2004).
[0099] While this invention has been particularly shown and described with references to example embodiments thereof, it Will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
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The present invention is directed to a fluorescence compound represented by structural Formula (I), with specificity to neural stem cells: I or a pharmaceutically acceptable salt thereof. The variables for structural Formula (I) are defined herein. Also described are methods for detection of neural stem cells, comprising using a compound of structural Formula (I) or pharmaceutically acceptable salts thereof. Compounds of structural Formula (I) can detect and separate neural stem cells without immunostaining, providing a much shorter and more convenient method for detection of neural stem cells.
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This application is a continuation, of application Ser. No. 680,261, filed Nov. 1, 1984, filed as PCT FR84/00045 on Feb. 29, 1984, published as WO84/03468 on Sept. 13, 1984, abandoned.
DESCRIPTION
Method for packaging a permanent adhesive composition in the form of a block or section, apparatus therefor and packaged article obtained by implementing this method.
The present invention relates to a method for packaging a permanent adhesive material in the form of a block or section and, more particularly, to a method for packaging masses which can be melted by heat and physically have various shapes and are in a pasty, plastic, elastic, semi-solid or solid state, depending on their nature and their constituents.
The present invention also relates to an apparatus for implementing the said method, as well as to the various packaged articles resulting from this implementation.
During the course of numerous chemical and industrial activities, it is known, common and necessary to have to use permanent adhesive compositions, i.e. masses which, when cold, and more particularly at the normal handling temperature which is known to be close to 20° C., satisfy one or more of the following conditions:
intrinsic adhesiveness of the mass,
surface adhesion or "tack" in normal temperature and pressure conditions,
sensitivity to pressure,
occurrence of a change in the surface state (adhesiveness) due to a natural rise in temperature (summer period for example).
The generic term "permanent adhesive compositions" thus includes the following:
(a) adhesive resins (colophane, coumarone-indene and aliphatic resins),
(b) soft tacky waxes which develop a certain surface adhesiveness,
(c) certain grades of polymers (polypropylenes, polyisobutylenes) and copolymers,
(d) certain pitches and bitumens incapable of, i.e. unsuitable for, deformation,
(e) pitches and bitumens modified by resins, plasticizers and elastomers,
(f) certain elastomers, such as, for example, butyl rubber,
(g) the various formulations of adhesive hot-melts, comprising at least one polymer, at least one natural or synthetic resin, one plasticizer and, if necessary, a filler, and
(h) generally all products in their natural state and processed products containing, if appropriate, a filler, which develop adhesiveness, when cold, in accordance with the conditions defined above.
On account of the inherent nature of their adhesive properties when cold, it is obvious that the various compositions belonging to the above list must be protected both during handling and during transport or storage, so as to prevent them bonding together or else prevent impurities becoming attached to them.
To this end, numerous methods have been proposed and implemented in order to package permanent adhesive compositions and thus prevent them bonding together and prevent impurities becoming attached to them.
Firstly, it is known to package these types of composition in containers which have different volumes and shapes (small casks, boat-shaped receptacles and bags), the inner surface of which is lined with non-stick materials, such as special waxes, or more frequently coated with silicone-containing compositions. This method of protection, however, has the drawbacks that the containers are costly and that the user himself is required to remove the packaged masses from the molds.
Secondly, it is known to protect permanent adhesive compositions by packaging them in containers which have different volumes and shapes (small casks, drums and buckets), are generally cylindrical in shape, mostly metallic, and unprotected internally.
In this second method, the contents obviously adhere to the container. This second method of protection consequently has two obvious drawbacks: (a) in order to remove the contents so as to supply the applicators of the user, special means (heating plates or other devices ensuring fusion of the product and special delivery pumps) are required, all of this special equipment, i.e. heating plates, melters and special pumps, being very costly, and (b) the method of protection used gives rise to a considerable loss of protected material since a large amount of material is present on the walls of the container and in particular on the bottom of the latter and cannot be pumped off since it is stuck there.
Thirdly, it is known to package these types of composition in containers which have different volumes and shapes, but which, however, have smaller volumes, such as plates, in which there are cavities suitable for containing 100 to 1,000 grams of adhesive in block form. Such plates are made of a special plastic material such that the walls of the cavities have non-stick properties, and these plates are thus used to package the processed composition.
This method of protection also has two major drawbacks: (a) the high cost of containers of the plate type and (b) the need for the user himself to remove the articles from the molds, an operation which is often quite difficult particularly when the permanent adhesive compositions retract little or not at all during their change of state.
Fourthly, it is known to provide permanent adhesive compositions in the form of rods, blocks, miniature blocks, strips, sections and slabs, which are enveloped in a thin film usually made of polyethylene or polypropylene or of a compound of polyethylene and polypropylene. This method of wrapping using film is, however, also costly.
Furthermore, the choice of films suitable for such protection is fairly limited since, on the one hand, the films must not melt during casting of the composition to be covered which can be supplied at 160° C. and sometimes at a higher temperature, and since, on the other hand, it is absolutely essential that they blend perfectly with the composition during re-melting of the latter when used, as the protected composition from now on is inseparable from its protective film.
Finally, this fourth method, despite everything, remains limited to a few types of adhesive materials which can be melted by heat, since it is obvious that only those products whose viscosity is suitable for this principle can be covered.
Fifthly, it is known to coat, by advanced mixing in a powdery medium, pellets or blocks consisting of a material which can be melted by heat and which is slightly adhesive, namely atactic polypropylene. This method of protection by coating, however, has numerous drawbacks, including (a) the irregularity and general surplus of the powdery coating material, (b) the high percentage of this powdery protective material, especially in the case of coating pellets which have a high specific surface area, and (c) the problems which can arise from the application of atactic polypropylene thus coated, precisely because the coating material, which is known to be different from the coated material, represents a high and not insignificant percentage capable of impeding or disrupting the operations which the user must perform on the permanent adhesive composition thus protected.
The object of the present invention is to reduce all of the abovementioned drawbacks and, to this end, it proposes a packaging method and apparatus which make it possible to protect permanent adhesive compositions at a low cost, without having to remove the protected compositions from the molds when required for use, thus saving a considerable amount of time, without loss of material and without having to invest in special equipment for heating and/or transferring the protected compositions, and which, finally and above all, are very flexible since all of the permanent adhesive compositions mentioned in this text can be packaged and protected using the method and apparatus according to the invention.
A first subject of the present invention, therefore, is a method for packaging a permanent adhesive composition in the form of a block or section, the said method comprising the known stages of casting the said composition in a mold, in order to shape the packaged article, and protecting the said packaged article removed from the mold or transported still inside the mold, so as to prevent it, during storage and handling, sticking to another packaged article or prevent impurities becoming attached to it, wherein, before casting, a screen of powdery material is provided over the entire inner surface of the mold, wherein the said screen is kept coherent during the entire casting operation so that there is permanent mutual bonding of the grains of the powdery material, and wherein, after hardening and shaping, a packaged article is removed from the mold, all of the surfaces of the said packaged article which were previously opposite the inner surface of the mold being protected by the screen of powdery material.
By implementing such a method, it is obvious that each packaged and protected article is perfectly and completely enveloped by a screen of powdery material, the thickness of which is uniform and fine and in any case very precisely proportioned, so much so that the quantity of powdery material required for protection is small and represents a percentage, in relation to the coated composition, of which the user is fully aware.
Thus, the powdery material, if it is chemically inert, is unable to create problems when the permanent adhesive composition is applied. On the other hand, if the powdery coating material is chosen as having to form part of the formulation for which the permanent adhesive composition is intended, it can be applied in advance in the form of a protective screen in a quantity such that it will no longer be necessary to add any in order to complete the formulation, or else it will be provided in an insufficient but perfectly defined quantity so that it can be brought up to the ideal percentage when all of the other constituents belonging to the said formulation are subsequently added.
In a preferred method of implementation, the screen is provided before casting and kept coherent for the entire duration of bonding (sic) by electrostatic means. Using this method, it is clearly possible to form a powdery, uniform, homogeneous and continuous screen, whatever the shapes (hollow or raised) of the inner surface of the mold, thus ensuring the provision of a protective screen, the thickness of which is precisely related to the mass of the permanent adhesive composition to be packaged. Moreover, as a result of this method, it is possible to cast any permanent adhesive composition which can be melted by heat, without displacing nor deforming the screen of powdery material, since the latter is "fixed electrically".
In another variation in implementation, the screen is obtained by superimposing several layers of grains of powdery material, the outermost layers of which, if necessary, are recovered after removal of the composition from the molds.
As a result of this method, it is possible to use as little of the powdery material as possible for the protective screen and also reduce the percentage of this powdery material, in relation to the permanent adhesive composition which is completely coated, to the ideal value, if required.
In a variation of implementation, in which the permanent adhesive composition is cast in a mold, the upper part of which is open, the upper substantially horizontal surface of the packaged article which has been shaped is protected after hardening and before removal from the mold, either by sprinkling with grains of a powdery material identical to or different from that provided as the screen or by coating with a fatty liquid material.
In this variation , the powdery material intended to protect the upper surface of the packaged article is, as chosen by the user, identical to or different from that provided as the screen between the inner surface of the mold and the surfaces opposite the packaged article.
Another subject of the present invention is an apparatus for implementing the method as claimed above, which comprises a mold for casting the permanent adhesive composition and shaping the packaged article to be made from this composition, means for forming a screen of powdery material over the entire inner surface of this mold, means for keeping this screen coherent during the entire molding operation, and means for removing the packaged article from the mold so that all of the surfaces which were previously opposite the inner surface of the mold are protected by the screen of powdery material.
In a preferred embodiment, the apparatus also comprises means for grounding the mold, as well as means for providing each grain of the powdery material with a positive electrical charge.
In a first variation of embodiment, the apparatus comprises at least one mold consisting of two parts, called the base and lid respectively, over the entire inner surface of each of which a screen of powdery material is provided and kept coherent and which each receive a casting of the permanent adhesive composition.
In this case, the apparatus also comprises means for bringing together the two parts of the mold and bringing into contact the upper surfaces of each packaged half shaped in the two parts of the mold, and means for bonding the two packaged halves tightly together after, if necessary, reactivating their interface.
In another variation of embodiment, the apparatus according to the invention comprises a mold, the upper part of which is open, means for forming a screen of powdery material over the entire inner surface of this mold and keeping it coherent there, means for casting the permanent adhesive composition inside the mold whilst keeping the screen of powdery material perfectly coherent, means for protecting the substantially horizontal upper surface of the packaged article which has been shaped, either by sprinkling with grains of a powdery material or by coating with a fatty liquid material, and means for removing the thus totally protected and packaged article from the mold.
A third subject of the invention is a packaged article in the form of a block or section, consisting of a permanent adhesive composition and obtained by implementing any one of the methods claimed above, the said packaged article having externally, on its surface, a screen of powdery material, of fine and regular thickness, which perfectly and completely protects the permanent adhesive composition.
In another variation of embodiment, the packaged article has externally, on its surface, a screen of powdery material, of fine and uniform thickness, which protects perfectly all of the surfaces of the permanent adhesive composition, except for the upper surface of the block or section which it defines, the said upper surface itself being protected by coating with a fatty liquid material or by sprinkling with grains of a powdery material different from that which forms the screen.
Advantageously, the screen of powdery material, of fine and uniform thickness, which envelops all or only part of the permanent adhesive composition, is deposited and kept on the inner surface of the mold by the phenomenon of static electricity.
The material which forms this screen of powdery material is advantageously a part of the filler, in the special case where a filler must be added to the composition, or else all or part of one of the constituents of the ideal formulation, for example an antioxidant or a flame-retarding product.
So that the subject of the present invention can be better understood, a description is given below, by way of purely illustrative and non-limiting examples, of various forms of embodiment, with reference to the attached drawings in which:
FIGS. 1a and 1b are schematic cross-sectional drawings of apparatuses permitting the implementation of the invention, and comprizing an open mold and a mold with two symmetrical parts, respectively,
FIG. 2 is a longitudinal section through a packaging line using the molds shown in FIG. 1b,
FIG. 3 is a detailed cross-sectional view of the operation for forming blocks consisting of a permanent adhesive composition by bonding two symmetrical packaged halves,
FIG. 4 is a detailed cross-sectional view of the operation involving removal of the blocks, obtained during the operation shown in FIG. 3, from the molds,
FIG. 5 is a perspective schematic view of a packaged article obtained from the apparatus shown in FIG. 1b and FIGS. 2 to 4, and
FIG. 6 is a perspective view of a variation of the apparatus, operating continuously in order to bond together the two packaged halves and then remove them from their molds.
With reference to the drawings, it can be seen that 1 designates in its entirety a mold with one or n chambers for shaping one to n blocks of a permanent adhesive composition, the mold consisting either of one part, which is open at the top (indicated by 2 in FIG. 1a), or of two parts, a base 3 and a lid 4 respectively, as can be seen in particular in FIG. 1b and FIGS. 2 to 4. The chambers are indicated respectively by 5 for the open mold 2, and by 6 and 7 for the base 3 and the lid 4 of the mold consisting of two parts. The said two parts are preferably the same and symmetrical, as is shown in the drawings, or, as a variation, different from each other, the lid being for example flat and the base defining on its own the chamber for shaping the block; as a result of this third variation of embodiment, it is possible to introduce, for example by injection, the permanent adhesive composition into the bottom chamber, the internal surfaces of the base and the lid having been protected beforehand by a powdery screen according to the invention, the lid simply being removed from the base after shaping and hardening of the block and the base being upturned so as to permit removal of the said block from the mold.
However, this third variation of implementation using a mold with two non-matching half-molds will not be described in detail because it is more complex to carry out, in particular with regard to the injecting operation which is known to be always more difficult to perform than a simple casting operation.
When each molding chamber 5, 6 and 7 is clean, electrostatic powdering of the said chamber is performed using any known method from a similar technique, for example that used for coating electrical cables or for painting radiators, bicycles and generally all objects with a complicated shape.
To this end, all of the parts 2, 3 and 4 of the mold are grounded, as indicated by 8, while the molds are sprayed using a gun or passed through a fluidization bed, so as to deposit on the internal surface of all the parts of the mold, by the phenomenon of static electricity, grains of a powdery material which are each provided with a positive electrical charge. The grains of the powdery material will have thus been provided with a very high electrical charge (+) using a high potential of the order of 20,000 to 80,000 volts, for example, thus resulting in their being strongly attracted to the internal surface of the chambers of the molds which form a pole with a sign opposite to that of all the charged grains.
It is obvious that, using this method, it is possible to form, as indicated by 9, a powdery, uniform, homogeneous and continuous screen which is relatively fine in thickness and in any case uniform whatever the shape (hollow, raised or recessed) of the chambers 5, 6 and 7 to be filled. Moreover, using this method of forming a powdery screen by electrostatic means, it is possible to determine a screen with a thickness of the order of 10 to 80 μ, exactly related to the masses to be packaged.
After the operation of electrostatic powdering indicated by A in FIG. 2, there follows the operation of casting the permanent adhesive composition in all of the chambers of the molds, the internal surfaces of which are thus protected by a powdery screen. Casting of the composition, indicated by the arrows 10 in FIGS. 1 and 2, is determined volumetrically so that, in each chamber, the composition is substantially level with the top of the said chamber and forms there a surface plane 11 horizontal to the top of this chamber.
For the entire duration of the casting operation, the powdery screen 9, which has been "fixed electrically", therefore remains perfectly coherent, without the risk of dissociation, so much so that the permanent adhesive composition never comes into contact with the inner surface of the molds and therefore is in no danger of adhering to it (indicated by B in FIG. 2).
The grains of powdery material constitute, as it were, a screen with one layer or several superimposed layers, which is completely impermeable to the cast composition; this screen is thus represented by the thin continuous line 12 shown in FIG. 1a.
The blocks of material, 12, 23 and 33 respectively, thus formed in the chambers 5, 6 and 7, are cooled, for example, by the blowing of cold air, so as to accelerate their hardening and shaping (indicated by C in FIG. 2).
At this point, various methods for completing protection of the unfinished articles to be packaged can be used.
In the apparatus shown in FIGS. 2 to 4, in which the mold consists of two parts, care was taken to design the two said parts as two matching half-molds, the left-hand mold 3 and right-hand mold 4 respectively, which are both articulated about their longitudinal median axis 14. The two said half-molds are raised symmetrically about their common axis 14, as is indicated in particular by 34 and 35 in FIG. 3, which is a detail of FIG. 2, until they assume a new substantially vertical position in which the upper surfaces 11 of each packaged half, 23 and 33 respectively, come into contact and are bonded tightly together on account of the unprotected nature of the said surfaces.
After bonding together of the packaged halves, the blocks are removed from the molds by tilting the assembly consisting of the two half-molds, the left-hand one 3 and the right-hand one 4, in the direction of the arrow 15, then separating the left-hand half-mold from the right-hand half-mold by tilting and pivoting in an opposite direction about the axis 14, as indicated by the arrow 16, and finally removing the packaged articles in the form of blocks from the chambers 7 of the half-molds 4 using any suitable gripping means 17, the said processed articles each having been obtained by bonding the two packaged halves together via their bare upper surfaces, i.e. their surfaces which are not protected by the screen of powdery material.
Each block 18 thus obtained (FIG. 5) externally thus has the appearance of a mass of grains which, in reality, consists of a very fine simple screen (represented by the crosses 19) which envelops completely the two packaged halves 20 and 21 so that their interface 22 is barely visible.
Since this protective screen 19 covers completely each block 18 of adhesive material, it prevents any further sticking of the latter to another adhesive mass as well as any impurities becoming attached to it. Each block 18, therefore, can be transported, as is indicated by the arrow 24, towards a packing line, for example, where it is packed in cardboard boxes, or else towards a marking line where it receives all of the instructions relating to the coated composition (indicated by D in FIG. 2).
During the operation where the two upper surfaces 11 of the packaged halves 23 and 33 are stuck together, it may occur that the adhesiveness of each surface is insufficient to ensure definitive bonding of the two packaged halves. This will be the case, for example, when there has been excessive cooling during phase C or else when the adhesive nature of the materials is insufficient. In these two cases, it is merely required to reactivate superficially the surfaces 11, for example by supplying heat in the form of hot air, thereby enabling the material to change partially its surface state, become pasty and hence adhere better.
After removing the packaged articles 18 from the molds, the dust is removed from the chambers 6 and 7 of the half-molds 3 and 4, as is indicated by 25 in phase E of FIG. 2, and the said half-molds are brought back to the start of the packaging line, as is indicated by the arrow 26, where they are again protected internally by means of electrostatic powdering before being filled with fresh cast masses consisting of an adhesive composition.
The cycle: electrostatic powdering, fixing electrically, casting, cooling, contact between the two packaged halves via their bare horizontal upper surfaces so as to ensure bonding together, removal from the molds, removal of the dust from the empty molds, is performed again continuously on the packaging line shown in FIGS. 2 to 4.
In a second variation of embodiment of a line permitting the continuous packaging of self-protected adhesive masses, such as that shown in FIG. 6, the molds 36 each consist of several cavities 27 which have the shape of a truncated pyramid and the bottom 38 of which is the small base and the top of which is open. There are for example three cavities with the shape of a truncated pyramid, per mold 36.
During the first phase, the internal surfaces of each cavity 37--the bottom 38 and side walls - are protected by a screen 39 of powdery material which is deposited and kept coherent using any of the electrostatic methods described above. Electrostatic powdering is performed, for example, by spraying with a gun, the grains of powder being conveyed by air as far as the spray head, which itself is provided with a gun inside which each grain is positively charged using a high potential of the order of 20,000 to 80,000 volts and a very low current of the order of 2.5 microamperes. This operation of electrostatic powdering is indicated by the reference numbers 40.
Each mold 36 is then moved, in the direction of the arrow 41, from the powdering station to the casting station along the continuously operating line. Casting 42 of the adhesive composition is determined volumetrically so that the horizontal surface plane 43 of the cast mass of a composition is level with the top of each cavity 37. During the entire casting operation, the powdery screen 39, which is fixed electrically, has obviously retained completely its coherent nature, so much so that the adhesive mass is perfectly isolated from the walls of the cavity by the continuous and homogeneous screen 39.
From the casting station, the molds 36 are moved, in the direction of the arrow 44, towards a cooling station which is indicated in its entirety by the reference number 45. As they pass through this station, the cast masses 46 are cooled, for example by the blowing of fresh air or by passing the molds through a cooling channel, so as to accelerate the hardening and permanent shaping of each packaged mass.
Advantageously, the molds 36, which are absolutely identical to each other, move in twos along the cooling station so as to supply as uniformly as possible the bonding station indicated in its entirety by 47.
At this moment, the force of attraction of the grains of the powdery screen 39 with respect to the walls of each cavity 37 is lessened and even becomes nonexistent, whereas the adhesiveness of the cast composition 46 increases. Thus, the screen of powdery material gradually detaches itself from the inner surface of the cavity and adheres preferentially to the surface of the cast mass, thereby protecting it. The removal of each cast mass from its mold and the bonding of the cast mass, via its bare upper surface, to another packaged half which is exactly the same can therefore be performed without difficulty.
To this end, the molds 36, which are cooled in pairs, supply, in the direction of the arrows 48 and 49, a conveyor consisting of two symmetrical belts, 50 and 51 respectively, which are placed end to end. The belts 50 and 51 perform two movements which are rectilinear, equal in speed and opposite in direction, as indicated by the arrows 52 and 53 respectively, such that, in the zone where the belts meet, the said movements are symmetrical and in a downwards direction.
The full molds 36 are located alongside each other on each belt 50, 51 and therefore move forwards at the same speed towards the zone where the ends of the belts meet and where the bare upper surfaces 43 of two packaged halves filling two opposite cavities 37 come into contact with each other under pressure.
At the end of the downwards movement, after two opposite packaged halves have come into contact with each other under pressure, the blocks 18 of an adhesive composition, which are totally and perfectly coated with the screen of powdery material, fall under the effect of gravity, in the direction of the arrow 54, onto a conveyor belt 55 which transports the said blocks, in the direction of the arrow 56, towards a packing or marking station.
At the same time, the empty half-molds 36, which, for example, are held magnetically on the belts 50 and 51, are conveyed from the bottom sides of the belts to the top sides, in the directions indicated by 57 and 58 respectively, then ejected, in the directions indicated by 59 and 60 respectively, and brought back, after cleaning, to the station where electrostatic powdering is performed.
The abovementioned operations are carried out according to the complete cycle described above.
In the device shown in FIG. 1a, in which the mold consists of a single part and opens upwards, it is obvious that, after casting 10 followed by hardening inside the mold containing the mass 13 of an adhesive composition, the upper horizontal surface of this mass 13 is not protected and is therefore sticky. In such an embodiment, the surface 11 of the block 13 is protected, before the packaged article is removed from the mold, either by coating with a fatty liquid material such as that which is marketed under the tradename "Teepol", or by sprinkling (by means of spraying with a gun or by means of a screen supplied by a screw-type distributing device or an electrostatic distributing device) with grains 27 of a suitable powder, which can be the same as that used for formation of the screen 9 or different from this protective screen, whilst belonging to a range of materials which are also compatible with the adhesive composition for the applications envisaged by the user.
In this context, the powdery materials used to make the protective screens 9, and if necessary 27, will advantageously have the following properties:
they are suitable in the natural state, or after treatment, for the electrical charge required for electrostatic spraying,
they preferably can be melted,
they are compatible with the packaged adhesive composition,
they do not modify the intrinsic properties of this composition as regards its typical features, such as the viscosity and solidification point.
Numerous powdery materials which are mineral, organic, organometallic or vegetable are suitable in this respect, including:
calcium carbonate and bentonite which, when incorporated in a formulation, decrease the price of the composition,
barium sulfate, which makes the adhesive mass radio-detectable,
titanium oxide and zinc oxide, which represent the most important fillers in the composition,
antimony oxide, for making the composition flame-resistant,
talc, which is used to control the tack of the formulation, and chalk,
colloidal silicas and others,
hard waxes, polyethylene waxes, modified polyethylene waxes,
a polymer in powder form (polyethylene, polypropylene, EVA),
a hot-melt or a resin in powder form,
an anti-oxidant or an anti-UV agent, for example a phenol derivative,
a natural gum (gum arabic),
starch, bonemeal, guar flour.
The quantity of powdery material which protects any block 13 or 18 or any section resulting from implementation of the method described above, constitutes in theory a minute quantity in weight compared to the protected mass of the adhesive composition. Whether application of this powdery material results from formation of the screen 19 by electrostatic means or whether it results from formation of the screen 27 by sprinkling, it is thus of considerable advantage for the quantity of material constituting the screen 19 and/or the screen 27 to be proportioned very precisely in relation to the weight of the packaged mass, in particular if the material forming the screen 19 and/or the screen 27 is not an inert filler and, for example, has the function of protecting the adhesive composition (anti-oxidant, anti-UV agent or flame-retarding agent) or of simplifying its use by the end user (plasticizer). It is therefore desirable, in certain applications, for the quantity of material constituting the screens 19 and/or 27 to be proportioned as precisely as possible. To this end, one solution consists in forming the screen 9 by superimposing screens of reduced thickness, i.e. by the successive application (using the gun-spraying or fluidization technique) of grains of powdery material which, since they are all fixed electrically, then bind together to form a homogeneous film with a thickness which is greater and also easier to determine with precision than the thickness of a screen resulting from a single operation involving spraying with a gun or fluidization.
In the case where there is a surplus quantity of grains of powdery material used to form the screen 19 and/or the screen 27 in one or more layers and where this surplus prevents subsequent handling operations being properly carried out, the said surplus quantity is recovered, after removal of each block 13, 18 from the molds, from the outermost layers and, if necessary, is recycled for other electrostatic powdering operations, in particular in the case where the protective material in question has a high price per unit of volume.
It is obvious that removal of the outermost layer or layers of the screen 19 and/or of the screen 27 will never affect the layer which is directly in contact with the packaged material, the said layer being irreversibly bonded to the said material on account of the intrinsic properties of adhesiveness of the latter.
From the above description it can be seen that implementation of the method according to the invention has several advantages compared to the methods of the prior art which were summarized in the preamble.
Thus, with respect to the first method of protection mentioned in the preamble, the invention has the advantage of decreasing considerably the cost of packaging (container no longer required) and of eliminating all the operations relating to removal of the molds at the time of use, thereby achieving a considerable saving in time.
Compared to the second method, the invention avoids any loss of material and does not require the user to invest in special material and equipment for transfer of the packaged article.
Compared to the third method mentioned, the invention has the advantage of reducing the cost of packaging, by substituting a protective screen of powdery material for the packages in the form of plates made of a special treated non-stick material, and of eliminating the operations involving removal of the packaged articles from the molds, since, when required for use, the adhesive composition provided in the form of a block 18, 13 or a section is used as it stands.
With respect to the fourth method, the invention permits a great deal of flexibility on account of the wide choice as to the nature and properties of the powder intended to form the protective screen. Moreover, as a result of the invention, it is possible to package almost all of the permanent adhesive compositions described here. In practice, the invention applies to protection, by means of isolation, of all adhesive compositions, except for those which flow excessively since, in the event of excessive variation in the initial shape of the block or section, it is not certain whether the powdery protective screen will remain uniformly distributed.
Compared to the fifth method, the invention makes it possible to package all adhesive compositions, whatever the adhesive properties of these compositions. Moreover, the method according to the invention ensures perfect uniformity and perfect homogeneity of the powdery protective layer, which cannot be guaranteed by the coating method performed in a mixer. Finally, for similar protected masses consisting of an adhesive composition, the method according to the invention ensures a considerable reduction in the mass of powdery material required to form effective protective screens, i.e. the method according to the invention requires a quantity of powdery material which is approximately thirty times less than that of the method for coating pellets of atactic polypropylene. Furthermore, since the quantity of powdery material required to ensure a good degree of protection represents a minute quantity of the protected mass, according to certain applications of the present invention, it is possible to use for this screen a material belonging to the ideal final formulation; on the other hand, the fact that a large quantity of powdery material is required to protect the atactic polypropylene pellets excludes straight away that the protective material in question can belong to the ideal formulation, except as a filler.
Obviously, the invention is not limited to the methods of application nor to the embodiments which have been mentioned and different variations are possible without, however, departing from the scope of the said invention.
This is particularly the case as regards the form of the mold which can consist of two or more than two parts, the latter moreover being integral and articulated with each other or else separate and in this case capable of being assembled by means of snap engagement, fastening with bolts or screws or using any other method. Thus, the base may have for example a height which is different from that of the lid, the main thing being that the bare upper surfaces of each packaged half, obtained after hardening, in this base and in this lid respectively, should be the same so that they can be stuck to one another so as to form a smooth block.
The same applies to the molds which can be used for casting by means of injection. In this case, the mold consists of a base in the form of a bowl and of a flat lid, the said base and the said lid being joined by a fastening with screws or bolts before injection takes place, so as to resist the pressure exerted by the injected product. The injection orifice is provided in the middle of the lid or in the upper part of one of the side walls of the bowl forming the base.
Such a design consisting of a hollow base and a flat lid can also be used for the conventional casting operation where the composition to be packaged is cast simply by means of gravity, the mold in this case being open at the time of casting, whereas the inner surfaces of the base and the lid are protected by powdering, the lid then being lowered onto and rigidly fixed to the base so that the upper surface of the cast mass is protected in an identical manner to that of its other surfaces.
The base and the lid are separated after hardening and shaping of the cast mass provided with a protective screen.
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An open-topped casting mold and a matching mold are hingedly connected and are electrostatically coated with a powder screen; casting material is then poured into the molds without disturbing the powder by holding the powder in position with static electricity. The molds are pivoted together to provide a composite body of the hardened casting material formed by the bonding of the material from the two molds.
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BACKGROUND
[0001] The electrophoretic display (EPD) is a non-emissive device based on the electrophoresis phenomenon influencing charged pigment particles suspended in a colored dielectric solvent. This general type of display was first proposed in 1969. An EPD typically comprises a pair of opposed, spaced-apart plate-like electrodes, with spacers predetermining a certain distance between the electrodes. At least one of the electrodes, typically on the viewing side, is transparent. For the passive type of EPDs, row and column electrodes on the top (the viewing side) and bottom plates respectively are needed to drive the displays. In contrast, an array of thin film transistors (TFT) on the bottom plate and a common, non-patterned transparent conductor plate on the top viewing substrate are required for the active type EPDs. An electrophoretic fluid composed of a colored dielectric solvent and charged pigment particles dispersed therein is enclosed between the two electrodes.
[0002] When a voltage difference is imposed between the two electrodes, the pigment particles migrate by attraction to the plate of polarity opposite that of the pigment particles. Thus, the color showing at the transparent plate, determined by selectively charging the plates, can be either the color of the solvent or the color of the pigment particles. Reversal of plate polarity will cause the particles to migrate back to the opposite plate, thereby reversing the color. Intermediate color density (or shades of gray) due to intermediate pigment density at the transparent plate may be obtained by controlling the plate charge through a range of voltages. No backlight is needed in this type of reflective EPD displays.
[0003] A transmissive EPD is disclosed in U.S. Pat. No. 6,184,856 in which a backlight, color filters, and substrates with two transparent electrodes are used. The electrophoretic cells serve as a light valve. In the collected state, the particles are positioned to minimize the coverage of the horizontal area of the cell and allow the backlight to pass through the cell. In the distributed state, the particles are positioned to cover the horizontal area of the pixel and scatter or absorb the backlight. However, the backlight and color filter used in this device consume a great deal of power and are not desirable for hand-held devices such as PDAs (personal digital assistants) and e-books.
[0004] Besides the normal top/bottom electrode switching mode of EPDs, reflective “in-plane” switching EPDs have been disclosed in E. Kishi, et al., “5.1: development of In-Plane EPD”, Canon Research Center, SID 00 Digest, pages 24-27 (2000) and Sally A. Swanson, et al., “5.2: High Performance Electrophoretic Displays”, IBM Almaden Research Center, SID 00 Digest, pages 29-31, (2000). However, only monochrome in-plane switching EPDs are disclosed in these references. To prepare a multicolor display, either color filters or isolated color pixels or cell structures are needed for color separation and rendition. Color filter is typically expensive and not power-efficient. On the other hand, the preparation of isolated pixels or cells for color separation and rendering in the in-plane switching mode has not been taught previously.
[0005] EPDs of different pixel or cell structures have been reported in prior art, for example, the partition-type EPD (M. A. Hopper and V. Novotny, IEEE Trans. Electr. Dev., Vol ED 26, No. 8, pp 1148-1152 (1979)) and the microencapsulated EPD (U.S. Pat. Nos. 5,961,804 and 5,930,026), and each of these has its own problems as noted below.
[0006] In a partition-type EPD, there are partitions between the two electrodes for dividing the space into smaller cells in order to prevent undesired movements of the particles such as sedimentation. However, difficulties are encountered in the formation of the partitions, the process of filling the display with the fluid, enclosing the fluid in the display, and keeping the suspensions of different colors separated from each other.
[0007] The microencapsulated EPD has a substantially two dimensional arrangement of microcapsules each having therein an electrophoretic composition of a dielectric fluid and a dispersion of charged pigment particles that visually contrast with the dielectric solvent. The microcapsules are typically prepared in an aqueous solution and, to achieve a useful contrast ratio, their mean particle size is relatively large (50-150 microns). The large microcapsule size results in a poor scratch resistance and a slow response time for a given voltage because a large gap between the two opposite electrodes is required for large capsules. Also, the hydrophilic shell of microcapsules prepared in an aqueous solution typically results in sensitivity to high moisture and temperature conditions. If the microcapsules are embedded in a large quantity of a polymer matrix to obviate these shortcomings, the use of the matrix results in an even slower response time and/or a lower contrast ratio. To improve the switching rate, a charge-controlling agent is often needed in this type of EPDs. However, the microencapsulation process in an aqueous solution imposes a limitation on the type of charge-controlling agents that can be used. Other drawbacks associated with the microcapsule system include poor resolution and poor addressability for color applications.
[0008] An improved EPD technology was recently disclosed in co-pending applications, U.S. Ser. No. 09/518,488, filed on Mar. 3, 2000 (corresponding to WO01/67170), U.S. Ser. No. 09/759,212, filed on Jan. 11, 2001, U.S. Ser. No. 09/606,654, filed on Jun. 28, 2000 (corresponding to WO02/01281) and U.S. Ser. No. 09/784,972, filed on Feb. 15, 2001, all of which are incorporated herein by reference. The improved EPD comprises closed isolated cells formed from microcups of well-defined shape, size and aspect ratio and filled with charged pigment particles dispersed in a dielectric solvent. The electrophoretic fluid is isolated and sealed in each microcup.
[0009] The microcup structure, in fact, enables a format flexible, efficient roll-to-roll continuous manufacturing process for the preparation of EPDs. The displays can be prepared on a continuous web of conductor film such as ITO/PET by, for example, (1) coating a radiation curable composition onto the ITO/PET film, (2) making the microcup structure by a microembossing or photolithographic method, (3) filling the electrophoretic fluid and sealing the microcups, (4) laminating the sealed microcups with the other conductor film, and (5) slicing and cutting the display to a desirable size or format for assembling.
[0010] One advantage of this EPD design is that the microcup wall is in fact a built-in spacer to keep the top and bottom substrates apart at a fixed distance. The mechanical properties and structural integrity of microcup displays are significantly better than any prior art displays including those manufactured by using spacer particles. In addition, displays involving microcups have desirable mechanical properties including reliable display performance when the display is bent, rolled, or under compression pressure from, for example, a touch screen application. The use of the microcup technology also eliminates the need of an edge seal adhesive which would limit and predefine the size of the display panel and confine the display fluid inside a predefined area. The display fluid in a conventional display prepared by the edge sealing adhesive method will leak out completely if the display is cut in any way, or if a hole is drilled through the display. The damaged display will be no longer functional. In contrast, the display fluid in the display prepared by the microcup technology is enclosed and isolated in each cell. The microcup display may be cut to almost any dimension without the risk of damaging the display performance due to the loss of display fluids in the active areas. In other words, the microcup structure enables a format flexible display manufacturing process, wherein the process produces a continuous output of displays in a large sheet format which can be sliced and diced to any desired format. The isolated microcup or cell structure is particularly important, when cells are filled with fluids of different specific properties such as colors and switching rates. Without the microcup structure, it will be very difficult to prevent the fluids in adjacent areas from intermixing, or being subject to cross-talk during operation.
[0011] Multi-color displays may thus be manufactured by using a spatially adjacent array of small pixels formed of microcups filled with dyes of different colors (e.g., red, green or blue). However there is a major deficiency in this type of system with the traditional top/bottom electrode switching mode. The white light reflected from the “turned-off” colored pixels greatly reduces the color saturation of the “turned-on” colors. More details in this regard are given in the following “Detailed Description” section.
[0012] While this deficiency may be remedied by an overlaid shutter device such as a polymer dispersed liquid crystal to switch each pixel to the black color, the disadvantage of this approach is the high cost of the overlaid device and the complicated driving circuit design.
[0013] Thus, there is still a need for an EPD with improved properties that can also be prepared in an efficient manner.
SUMMARY OF THE INVENTION
[0014] The present invention relates to an improved EPD which comprises the in plane switching mode for image formation. More specifically, the EPD of the present invention comprises isolated cells formed from microcups of well defined size, shape and aspect ratio and the movement of the particles in the cells is controlled by the in-plane switching mode. The EPDs of the present invention may be produced in a continuous roll-to-roll manufacturing process, and the resultant displays have improved color saturation and contrast ratio.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] It is noted that all figures are shown as schematic and are not to scale.
[0016] [0016]FIG. 1 illustrates the common deficiency of the traditional EPD with only the top/bottom switching mode.
[0017] [0017]FIG. 2 illustrates a typical electrophoretic cell of the present invention and the general locations of the in-plane switching electrodes.
[0018] [0018]FIGS. 3A and 3B illustrate the monochrome display of the present invention.
[0019] FIGS. 4 A- 4 D illustrate the various multiple color scenarios of the present invention.
[0020] [0020]FIGS. 5A and 5B illustrate the manufacture of microcups involving imagewise photolithographic exposure through a photomask.
DETAILED DESCRIPTION OF THE INVENTION
[0021] Unless defined otherwise in this specification, all technical terms are used herein according to their conventional definitions as they are commonly used and understood by those of ordinary skill in the art. The terms “cell”, “microcup”, “well-defined”, “aspect ratio”, and “imagewise exposure” are as defined in the co-pending applications identified above.
[0022] The term “isolated” refers to the electrophoretic cells which are individually sealed and the fluid in the cells may not be transferred from one cell to the other cells.
[0023] I. The Disadvantages of Electrophoretic Display with the Traditional Top/Bottom Switching
[0024] The EPD of FIG. 1 has conventional top/bottom electrode switching mode. The cells are filled with a suspension in which white charged particles are dispersed in a colored (red, green and blue) dielectric solvent. All three cells in FIG. 1 are shown charged with a voltage difference between the top and bottom electrodes (not shown). In the green and blue cells, the white particles migrate to the top viewing electrode which is transparent, and as a result, the color of the particles (i.e., white) is reflected to the viewer through the transparent conductor film in the two cells. In the red cell, the white particles migrate to the bottom of the cell, and the color of the solvent (i.e., red) is seen through the top transparent conductor film. In FIG. 1, the white light reflected from the green and blue cells dramatically reduces the saturation and contrast ratio of the red color.
[0025] In addition to the above mentioned problem, low solubility and poor fastness of the dyes in dielectric solvents of very low polarity, such as perfluoro and hydrocarbon solvents, have been a challenge for achieving high contrast ratio in the top/down type of EPDs.
[0026] II. Electrophoretic Display of the Present Invention
[0027] [0027]FIG. 2 illustrates a typical electrophoretic cell of the present invention. The cell ( 20 ) comprises a top layer ( 21 ) and a bottom layer ( 22 ). The bottom layer has the in-plane switching electrodes ( 23 ) and ( 24 ) and the background layer ( 25 ). There is a common electrode ( 29 ) between the two in-plane electrodes separated by gaps ( 30 ). Alternatively, the bottom layer may have only one in-plane switching electrode, and one common electrode with a gap in between. Another alternative is where the background layer ( 25 ) is on top of the electrodes in the bottom layer (not shown). The in-plane electrode layer may also serve as the background layer and in this case the in-plane electrode(s) may be white or colored.
[0028] Typically, the cells of FIG. 2 are filled with a dispersion of colored particles ( 31 ) in a clear dielectric solvent ( 32 ). The particles may be white, black or colored (i.e., red, green or blue). The background layer ( 25 ) may be colorless, white, black or colored. The filled cells are subsequently sealed with a sealing layer ( 26 ). The top layer ( 21 ) having a transparent insulator layer ( 27 ) and preferably an adhesive layer ( 28 ) is then laminated over the sealed cells.
[0029] Preferably the microcup array is prepared in an up-side-down manner. In this scenario, the microcup array is prepared on the top transparent insulator substrate by either microembossing or photolithography as disclosed in the co-pending patent applications, U.S. Ser. No. 09/518,488, filed on Mar. 3, 2000 (corresponding to WO01/67170), U.S. Ser. No. 09/759,212, filed on Jan. 11, 2001, U.S. Ser. No. 09/606,654, filed on Jun. 28, 2000 (corresponding to WO02/01281) and U.S. Ser. No. 09/784,972, filed on Feb. 15, 2001, all of which are incorporated herein by reference. The microcups are filled with the electrophoretic fluid and sealed subsequently with a sealing layer. The bottom layer which contains the patterned electrodes and preferably an adhesive layer is then laminated over the sealed microcup. The color background may be added by painting, printing, coating or laminating a color layer to the bottom electrode substrate.
[0030] One of the advantages of the in-plane switching mode is the possibility of making the microcups on a clear plastic insulator substrate. This eliminates the risk of breaking the brittle conductor electrode such as ITO/PET during the microembossing and other web handling steps. The patterned in-plane conductor film will only be used at the last step for lamination onto the filled and sealed microcups to complete the making of the display panel.
[0031] (1) Reflective Monochrome Display
[0032] In the cell as shown in FIG. 3A, white particles are dispersed in a clear, colorless dielectric solvent. The background of all cells is of the same color (black, blue, cyan, red, magenta, etc.). When there is a voltage difference between the common (not shown) and the two in-plane switching electrodes (not shown), the white particles migrate to the sides of the cells, resulting in the color of the background being seen through the top transparent opening. When there is no voltage difference between the common and the two in-plane electrodes, the white particles are distributed in the dielectric solvent and as a result, the color of the particles (i.e., white) is seen through the top transparent insulator layer.
[0033] Alternatively, as shown in FIG. 3B, particles of the same color are dispersed in a clear, colorless dielectric solvent in all cells and the background of the cells is white. When there is a voltage difference between the common (not shown) and the two in-plane switching electrodes (not shown), the colored particles migrate to the sides of the cells, resulting in the color of the background (i.e., white) being seen through the top transparent opening. When there is no voltage difference between the two in-plane electrodes, the colored particles are distributed in the dielectric solvent and as a result, the color of the particles is seen through the top transparent layer.
[0034] (2) Reflective Multiple Color Display
[0035] FIGS. 4 A- 4 D illustrate the multiple color displays of the present invention.
[0036] In FIG. 4A, the cells are filled with a colorless dielectric solvent with white charged particles dispersed therein, and have different background colors (i.e., red, green or blue). When there is a voltage difference between the in-plane electrodes (not shown), the white particles migrate to either side of the cell, the color of the background (i.e., red, green or blue) is seen from the top transparent opening. When there is no voltage difference between the in-plane electrodes, the particles are distributed in the dielectric solvent resulting in the white color (i.e., the color of the particles) being seen from the top transparent opening.
[0037] In FIG. 4B, the cells are filled with a colorless dielectric solvent with black particles dispersed therein, and have different background colors (i.e., red, green or blue). When there is a voltage difference between the in-plane electrodes (not shown), the particles migrate to either side of the cell, the color of the background (i.e., red, green or blue) is seen from the top transparent opening. When there is no voltage difference between the in-plane electrodes, the particles are distributed in the dielectric solvent, resulting in the black color (i.e., the color of the particles) being seen from the top transparent opening.
[0038] [0038]FIG. 4C shows the cells filled with a colorless dielectric solvent with particles of different colors (i.e., red, green or blue) dispersed therein. The background of the cells is black. When there is a voltage difference between the in-plane electrodes (not shown), the colored charged particles migrate to either side of the cell, the color of the background (i.e., black) is seen from the top transparent opening. When there is no voltage difference between the in-plane electrodes, the colored particles are distributed in the dielectric solvent, resulting in the color of the particles (i.e., red, green or blue) being seen from the top transparent opening. In this design, the black state is of high quality.
[0039] In FIG. 4D, the cells are filled with a colorless dielectric solvent with particles of different colors (red, green or blue) dispersed therein. The background of the cells is white. When there is a voltage difference between the in-plane electrodes (not shown), the particles migrate to either side of the cell, the color of the background (i.e., white) is seen from the top transparent opening, resulting in a high quality white state. When there is no voltage difference between the in-plane electrodes, the particles are distributed in the dielectric solvent, resulting in the color of the particles (i.e., red, green or blue) being seen from the top transparent opening.
[0040] As shown in FIGS. 4 A- 4 D, the in-plane switching mode allows the particles to move in the planar (left/right) direction, and different color combinations of particles, background, and fluid, wherein each is individually white, black, red, green or blue, can be used to generate various multi-color EPDs.
[0041] In addition, the particles in the dielectric solvent may be of mixed colors and the cells have the same background color.
[0042] In an alternative reflective display of the present invention, the top transparent viewing layer of the display may be colored or by adding a color filter. In this case, the cells are filled with an electrophoretic composition comprising white charged particles in a clear colorless or colored dielectric solvent and the background of the cells may be black. In a monochrome display, the transparent viewing layer on each pixel is of the same color (such as black, red, green, blue, yellow, cyan, magenta, etc.). In a multiple color display, the transparent viewing layers may be of different colors.
[0043] III. Preparation of Microcup Array of the Present Invention
[0044] The microcups generally may be manufactured by microembossing or photolithography as disclosed in U.S. patent application Ser. Nos. U.S. Ser. No. 09/518,488 filed Mar. 3, 2000 (corresponding to WO01/67170) and U.S. Ser. No. 09/784,972 filed on Feb. 15, 2001.
[0045] III(a) Preparation of the Microcup Array by Microembossing Preparation of the Male Mold
[0046] The male mold may be prepared by any appropriate method, such as a diamond turn process or a photoresist process followed by either etching or electroplating. A master template for the male mold may be manufactured by any appropriate method, such as electroplating. With electroplating, a glass base is sputtered with a thin layer (typically 3000 Å) of a seed metal such as chrome inconel. It is then coated with a layer of photoresist and exposed to radiation, such as ultraviolet (UV). A mask is placed between the UV and the layer of photoresist. The exposed areas of the photoresist become hardened. The unexposed areas are then removed by washing them with an appropriate solvent. The remaining hardened photoresist is dried and sputtered again with a thin layer of seed metal. The master is then ready for electroforming. A typical material used for electroforming is nickel cobalt. Alternatively, the master can be made of nickel by electroforming or electroless nickel deposition as described in “Continuous manufacturing of thin cover sheet optical media”, SPIE Proc. Vol. 1663, pp. 324 (1992). The floor of the mold is typically between about 50 to 400 microns thick. The master can also be made using other microengineering techniques including e-beam writing, dry etching, chemical etching, laser writing or laser interference as described in “Replication techniques for micro-optics”, SPIE Proc. Vol. 3099, pp. 76-82 (1997). Alternatively, the mold can be made by photomachining using plastics, ceramics or metals.
[0047] The male mold thus prepared typically has protrusions between about 1 to 500 microns, preferably between about 2 to 100 microns, and most preferably about 4 to 50 microns. The male mold may be in the form of a belt, a roller, or a sheet. For continuous manufacturing, the belt type of mold is preferred. Prior to applying a UV curable resin composition, the mold may be treated with a mold release to aid in the demolding process.
[0048] Microcups may be formed either in a batchwise process or in a continuous roll-to-roll process as described in U.S. Ser. No. 09/784,972 filed on Feb. 15, 2001.
[0049] In the first step of the microembossing process, a UV curable resin is first coated on a substrate, preferably a transparent insulator, by any appropriate means, such as roller coating, die coating, slot coating, slit coating, doctor blade coating, and the like. Suitable transparent insulator substrates include polyethylene terephthalate, polyethylene naphthate, polyaramid, polyimide, polycycloolefin, polysulfone, epoxy and their composites. The radiation curable material used is a thermoplastic or thermoset precursor, such as multifunctional acrylate or methacrylate, vinylether, epoxide and their oligomers, polymers and the like. Multifunctional acrylates and their oligomers are the most preferred. A combination of a multifunctional epoxide and a multifunctional acrylate is also very useful to achieve desirable physico-mechanical properties. The UV curable resin may be degassed prior to dispensing and may optionally contain a solvent. The solvent, if present, readily evaporates.
[0050] The radiation curable material coated on the substrate is embossed by the male mold under pressure. If the male mold is metallic and opaque, the plastic insulator is typically transparent to the actinic radiation used to cure the resin. Conversely, the male mold can be transparent and the plastic insulator can be opaque to the actinic radiation. The plastic insulator is preferably transparent because it is typically the viewing side. In this case, the electrodes can be opaque. Alternatively, the microembossing can be performed on the substrate containing the electrodes.
[0051] After exposure to radiation, the radiation curable material becomes hardened. The male mode is then removed exposing the microcups formed.
[0052] III(b) Preparation of Microcup Array by Photolithography
[0053] The photolithographic process for preparation of the microcup array is shown in FIGS. 5A and 5B.
[0054] As shown in FIGS. 5A and 5B, the microcup array ( 50 ) may be prepared by exposure of a radiation curable material ( 51 a ), coated by any known methods onto an insulator substrate base ( 53 ), to UV light (or alternatively other forms of radiation, electron beams and the like) through a mask ( 56 ) to form walls ( 51 b ) corresponding to the image projected through the mask ( 56 ).
[0055] In the photomask ( 56 ) in FIG. 5A, the dark squares ( 54 ) represent the area opaque to the radiation employed, and the space ( 55 ) between the dark squares represents the radiation-transparent area. The UV radiates through the opening area ( 55 ) onto the radiation curable material ( 51 a ).
[0056] As shown in FIG. 5B, the exposed areas ( 51 b ) become hardened and the unexposed areas (protected by the opaque area ( 54 ) of the mask ( 56 )) are then removed by an appropriate solvent or developer to form the microcups ( 57 ). The solvent or developer is selected from those commonly used for dissolving or dispersing radiation curable materials such as methylethylketone, toluene, acetone, isopropanol or the like.
[0057] Alternatively, the exposure can be done by placing the photomask underneath the insulator substrate. In this case, the substrate must be transparent to the radiation wavelength used for exposure.
[0058] The openings of the microcups prepared according to the methods described above may be round, square, rectangular, hexagonal, or any other shape. The partition area between the openings is preferably kept small in order to achieve a high color saturation and contrast while maintaining desirable mechanical properties. Consequently the honeycomb-shaped opening is preferred over, for example, the circular opening.
[0059] For reflective electrophoretic displays, the dimension of each individual microcup may be in the range of about 10 2 to about 1×10 6 μm 2 , preferably from about 10 3 to about 1×10 5 μm 2 . The depth of the microcups is in the range of about 5 to about 200 microns, preferably from about 20 to about 100 microns. The opening to the total area ratio, total area being defined as that of one cup including walls measured from wall centers, is in the range of from about 0.2 to about 0.95, preferably from about 0.5 to about 0.9. The distances of the openings usually are in the range of from about 15 to about 450 microns, preferably from about 25 to about 300 microns from edge to edge of the openings.
[0060] III(c) Sealing of the Microcups
[0061] the microcups are filled with an eletrophoretic fluid, they are sealed. The critical step of sealing of the microcups may be accomplished in a number of ways. A preferred approach is to disperse a UV curable composition into an electrophoretic fluid comprising charged pigment particles dispersed in a colored dielectric solvent. The suitable UV curable materials include acrylates, methacrylates, styrene, alpha-methylstyrene, butadiene, isoprene, allyacrylate, polyvalent acrylate or methacrylate, cyanoacrylates, polyvalent vinyl including vinylbenzene, vinylsilane, vinylether, polyvalent epoxide, polyvalent isocyanate, polyvalent allyl, and oligomers or polymers containing crosslinkable functional groups. The UV curable composition is immiscible with the dielectric solvent and has a specific gravity lower than that of the electrophoretic fluid, i.e., the combination of the dielectric solvent and the pigment particles. The two components, UV curable composition and the electrophoretic fluid, are thoroughly blended in an in-line mixer and immediately coated onto the microcups with a precision coating mechanism such as Myrad bar, gravure, doctor blade, slot coating or slit coating. Excess fluid is removed by a wiper blade or a similar device. A small amount of a weak solvent or solvent mixture such as isopropanol or methanol may be used to clean the residual electrophoretic fluid on the top surface of the partition walls of the microcups. Volatile organic solvents may be used to control the viscosity and coverage of the electrophoretic fluid. The thus-filled microcups are then dried and the UV curable composition floats to the top of the electrophoretic fluid. The microcups may be sealed by curing the supernatant UV curable layer during or after it floats to the top. UV or other forms of radiation such as visible light, IR and electron beam may be used to cure the sealing layer and seal the microcups. Alternatively, heat or moisture may also be employed to cure the sealing layer and seal the microcups, if heat or moisture curable compositions are used.
[0062] A preferred group of dielectric solvents exhibiting desirable density and solubility discrimination against acrylate monomers and oligomers are halogenated hydrocarbons and their derivatives. Surfactants may be used to improve the adhesion and wetting at the interface between the electrophoretic fluid and the sealing materials. Surfactants include the FC surfactants from 3M Company, Zonyl fluorosurfactants from DuPont, fluoroacrylates, fluoromethacrylates, fluoro-substituted long chain alcohols, perfluoro-substituted long chain carboxylic acids and their derivatives.
[0063] Alternatively, the electrophoretic fluid and the sealing precursor may be coated sequentially into the microcups to prevent intermixing, if the sealing precursor is at least partially compatible with the dielectric solvent. Thus, the sealing of the microcups may be accomplished by overcoating a thin layer of sealing material which is hardenable by radiation, heat, moisture or interfacial reactions on the surface of the filled microcups. Volatile organic solvents may be used to adjust the viscosity and the thickness of the coatings. When a volatile solvent is used in the overcoat, it is preferred that it is immiscible with the dielectric solvent to reduce the degree of intermixing between the sealing layer and the electrophoretic fluid. To further reduce the degree of intermixing, it is highly desirable that the specific gravity of the overcoating is significantly lower than that of the electrophoretic fluid. In the copending patent application, U.S. Ser. No. 09/874,391, filed Jun. 4, 2001, thermoplastic elastomers have been disclosed as the preferred sealing material.
[0064] Examples of useful thermoplastic elastomers include ABA, and (AB)n type of di-block, tri-block, and multi-block copolymers wherein A is styrene, α-methylstyrene, ethylene, propylene or norbonene; B is butadiene, isoprene, ethylene, propylene, butylene, dimethylsiloxane or propylene sulfide; and A and B cannot be the same in the formula. The number, n, is ≧1, preferably 1-10. Particularly useful are di-block or tri-block copolymers of styrene or α-methylstyrene such as SB (poly(styrene-b-butadiene)), SBS (poly(styrene-bbutadiene-b-styrene)), SIS (poly(styrene-b-isoprene-b-styrene)), SEBS (poly(styrene-b-ethylene/butylenes-b-styrene)) poly(styrene-b-dimethylsiloxane-b-styrene), poly((α-methylstyrene-b-isoprene), poly(α-methylstyrene-b-isoprene-b-α-methylstyrene), poly(α-methylstyrene-b-propylene sulfide-b-α-methylstyrene), poly(α-methylstyrene-b-dimethylsiloxane-b-α-methylstyrene).
[0065] Alternatively, interfacial polymerization followed by UV curing has been found very beneficial to the sealing process. Intermixing between the electrophoretic layer and the overcoat is significantly suppressed by the formation of a thin barrier layer at the interface by interfacial polymerization. The sealing is then completed by a post curing step, preferably by UV radiation. The two-step overcoating process is particularly useful when the dye used is at least partially soluble in the thermoset precursor.
[0066] III(d) Lamination of the Microcups
[0067] The sealed microcups are then laminated with a top layer comprising a patterned in plane conductor film and preferably an adhesive layer. Suitable adhesive materials include acrylic and rubber types of pressure sensitive adhesives, UV curable adhesives containing for example, multifunctional acrylates, epoxides, or vinylethers, and moisture or heat curable adhesives such as epoxy, polyurethane, and cyanoacrylate.
[0068] The cells prepared from the methods of Sections III(a)-III(d) may be used in an up-side-down manner with the transparent viewing layer at the top and the layer with the in-plane electrodes at the bottom.
[0069] III(e) Alternative Methods
[0070] Alternatively, in the microembossing process, the UV curable resin is dispensed over the male mold by any appropriate means, such as coating, dipping, pouring and the like. The dispenser may be moving or stationary. A patterned in-plane conductor film on a plastic substrate such as polyethylene terephthalate, polyethylene naphthate, polyaramid, polyimide, polycycloolefin, polysulfone, epoxy and their composites is then overlaid on the UV curable resin. Pressure may be applied to ensure proper bonding between the resin and the plastic substrate and to control the thickness of the floor of the microcups. If the male mold is metallic and opaque, the plastic substrate is typically transparent to the actinic radiation used to cure the resin. Conversely, the male mold can be transparent and the plastic substrate can be opaque to the actinic radiation.
[0071] After exposure to UV radiation, the UV curable resin becomes hardened, and the male mode may then be removed. The microcup arrays formed are filled and sealed as described above. The sealed microcups are then laminated with a transparent insulator layer preferably using an adhesive.
[0072] Although less preferred, the photolithographic exposure may also be performed on the substrate having the in-plane electrodes. A radiation curable material is coated on the patterned conductor film. The microcups are formed by exposure of the radiation curable material to radiation through a photomask as shown in FIG. 5 and described in Section III(b) above.
[0073] The microcups thus prepared are then filled and sealed as described above and laminated with a transparent insulator layer, preferably with an adhesive.
[0074] In any of the methods for the preparation of the microcups disclosed in this section, a substrate containing an array of thin film transistors (TFT) may be used as the bottom in-plane electrode layer and in this case the TFT layer also provides an active driving mechanism.
[0075] IV. Preparation of the Suspensions
[0076] The suspensions filled in the microcups comprise a dielectric solvent with charged pigment particles dispersed therein and the particles migrate under the influence of an electric field. The suspensions may optionally contain additional colorants which do not migrate in the electric field. The dispersion may be prepared according to methods well known in the art, such as U.S. Pat. Nos. 6,017,584, 5,914,806, 5,573,711, 5,403,518, 5,380,362, 4,680,103, 4,285,801, 4,093,534,4,071,430, and 3,668,106, and as described in IEEE Trans. Electron Devices, ED-24, 827 (1977), and J. Appl. Phys. 49(9), 4820 (1978).
[0077] The suspending fluid medium is a dielectric solvent which preferably has a low viscosity and a dielectric constant in the range of about 2 to about 30, preferably about 2 to about 15 for high particle mobility. Examples of suitable dielectric solvents include hydrocarbons such as decahydronaphthalene (DECALIN), 5-ethylidene-2-norbornene, fatty oils, paraffin oil, aromatic hydrocarbons such as toluene, xylene, phenylxylylethane, dodecylbenzene and alkylnaphthalene, halogenated solvents such as dichlorobenzotrifluoride, 3,4,5-trichlorobenzotrifluoride, chloropentafluoro-benzene, dichlorononane, pentachlorobenzene, and perfluoro solvents such as perfluorodecalin, perfluorotoluene, perfluoroxylene, FC-43, FC-70 and FC-5060 from 3M Company, St. Paul Minn., low molecular weight fluorine containing polymers such as poly(perfluoropropylene oxide) from TCI America, Portland, Oreg., poly(chlorotrifluoroethylene) such as Halocarbon Oils from Halocarbon Product Corp., River Edge, N.J., perfluoropolyalkylether such as Galden , HT-200, and Fluorolink from Ausimont or Krytox Oils and Greases K-Fluid Series from DuPont, Del. In one preferred embodiment, poly(chlorotrifluoroethylene) is used as the dielectric solvent. In another preferred embodiment, poly(perfluoropropylene oxide) is used as the dielectric solvent.
[0078] The non-migrating fluid colorant may be formed from dyes or pigments. Nonionic azo and anthraquinone dyes are particularly useful. Examples of useful dyes include, but are not limited to: Oil Red EGN, Sudan Red, Sudan Blue, Oil Blue, Macrolex Blue, Solvent Blue 35, Pylam Spirit Black and Fast Spirit Black (Pylam Products Co., Arizona), Thermoplastic Black X-70 (BASF), anthraquinone blue, anthraquinone yellow 114, anthraquinone reds 111 and 135, anthraquinone green 28 and Sudan Black B (Aldrich). Fluorinated dyes are particularly useful when perfluorinated solvents are used. In the case of a pigment, the pigment particles for generating the non-migrating fluid colorant may also be dispersed in the dielectric solvent and these colored particles are preferably uncharged. If the pigment particles for generating the non-migrating fluid colorant are charged, they preferably carry a charge which is opposite from that of the charged migrating pigment particles. If both types of pigment particles carry the same charge, then they should have different charge density or different electrophoretic mobility. The dye or pigment for generating the non-migrating fluid colorant must be chemically stable and compatible with other components in the suspension.
[0079] The charged migrating pigment particles are preferably white, and may be organic or inorganic pigments, such as TiO 2 .
[0080] If colored migrating particles are used, they may be formed from phthalocyanine blue, phthalocyanine green, diarylide yellow, diarylide AAOT yellow, and quinacridone, azo, rhodamine, perylene pigment series (Sun Chemical), Hansa yellow G particles (Kanto Chemical), and Carbon Lampblack (Fisher). Submicron particle size is preferred. These particles should have acceptable optical characteristics, should not be swollen or softened by the dielectric solvent, and should be chemically stable. The resulting suspension must also be stable against sedimentation, creaming or flocculation under normal operating conditions.
[0081] The migrating pigment particles may exhibit a native charge, or may be charged explicitly using a charge control agent, or may acquire a charge when suspended in the dielectric solvent. Suitable charge control agents are well known in the art; they may be polymeric or non-polymeric in nature, and may also be ionic or non-ionic, including ionic surfactants such as Aerosol OT, sodium dodecylbenzenesulfonate, metal soaps, polybutene succinimide, maleic anhydride copolymers, vinylpyridine copolymers, vinylpyrrolidone copolymers (such as Ganex, International Specialty Products), (meth)acrylic acid copolymers, and N,N-dimethylaminoethyl (meth)acrylate copolymers. Fluorosurfactants are particularly useful as charge controlling agents in perfluorocarbon solvents. These include FC fluorosurfactants such as FC-170C, FC-171, FC-176, FC430, FC431 and FC-740 from 3M Company and Zonyl fluorosurfactants such as Zonyl FSA, FSE, FSN, FSN-100, FSO, FSO-100, FSD and UR from Dupont.
[0082] Suitable charged pigment dispersions may be manufactured by any of the well-known methods including grinding, milling, attriting, microfluidizing, and ultrasonic techniques. For example, pigment particles in the form of a fine powder are added to the suspending solvent and the resulting mixture is ball milled or attrited for several hours to break up the highly agglomerated dry pigment powder into primary particles. Although less preferred, a dye or pigment for producing the non-migrating fluid colorant may be added to the suspension during the ball milling process.
[0083] Sedimentation or creaming of the pigment particles may be eliminated by microencapsulating the particles with suitable polymers to match the specific gravity to that of the dielectric solvent. Microencapsulation of the pigment particles may be accomplished chemically or physically. Typical microencapsulation processes include interfacial polymerization, in-situ polymerization, phase separation, coacervation, electrostatic coating, spray drying, fluidized bed coating and solvent evaporation.
[0084] For pigment suspensions, there are many possibilities. For a subtractive color system, the charged TiO 2 particles may be suspended in a dielectric fluid of cyan, yellow or magenta color. The cyan, yellow or magenta color may be generated via the use of a dye or a pigment. For an additive color system, the charged TiO 2 particles may be suspended in a dielectric solvent of red, green or blue color generated also via the use of a dye or a pigment. The red, green, blue color system is preferred for most applications.
[0085] While the present invention has been described with reference to the specific embodiments thereof, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, materials, compositions, processes, process step or steps, to the objective, spirit and scope of the present invention. All such modifications are intended to be within the scope of the claims appended hereto.
[0086] It is therefore wished that this invention to be defined by the scope of the appended claims as broadly as the prior art will permit, and in view of the specification.
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The present invention relates to an improved EPD which comprises the in plane switching mode. More specifically, the EPD of the present invention comprises isolated cells formed from microcups of well defined size, shape and aspect ratio and the movement of the particles in the cells is controlled by the in-plane switching mode. The EPD of the present invention may be produced in a continuous manufacturing process, and the display gives improved color saturation.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to an apparatus for the production of hydrogen by steam reforming. In particular, the invention relates to a furnace outlet system for transferring a stream of reactants including hydrogen from a heating furnace towards a manifold conduit of the apparatus for the production of hydrogen.
BACKGROUND OF THE INVENTION
[0002] Purified hydrogen is an important gas source for many energy conversion process devices and can be produced by a steam reforming process implementing chemical reaction which results in producing hydrogen and certain byproducts or impurities later removed.
[0003] Under steam reforming, steam and a hydrocarbon react in the presence of a catalyst. Steam reforming requires elevated temperature, e g, up 1500° F., and produces primarily hydrogen and carbon dioxide. Some trace quantities of unreacted reactants, and byproducts such as carbon monoxide also result from steam reforming.
[0004] Typically, the steam reforming process includes distributing a mixture of hydrocarbons and steam over many parallel passes of the catalyst-filled reaction tubes which are subjected to elevated temperatures sufficient to perform the reforming reaction in a primary reformer section. At the furnace outlet system, parallel part streams are passing through downstream portions of the reaction tubes and are further collected in a single stream guided towards a waste heat boiler in which hydrocarbons and hydrogen are quenched for further separation.
[0005] Steam reforming catalytic apparatuses are classified as either side-fired or top-fired implement the steam reforming process. A side-firing construction results in long and narrow boxes and often in several furnace boxes that have a common convection bank. Top-fired furnaces, however, can be built for very large capacities just by adding more tube rows in a common box.
[0006] Regardless of the type of the steam reforming apparatus, hydrogen purification attempts to always maximize production of hydrogen from the reforming process. To increase the amount of hydrogen obtained, attempts have been made to decrease thermal exposure of the reaction tubes and, thus, to minimize their potential failure.
[0007] A structure illustrated in FIGS. 1 and 2 is representative of the steam reforming catalytic reaction apparatus, as disclosed in U.S. Pat. Nos. 3,467,503 and 3,600,141 In particular, the steam reforming catalytic apparatus 10 includes a reaction tube 12 extending through and below the floor of the furnace (not shown) and shaped to conduct a stream of gas mixed with steam through a removable catalyst support grid 16 above where decomposition of hydrocarbons takes place in the presence of a nickel-containing catalyst. A mixture of CO, CO 2 , H 2 , some other minor reactants, and steam thus leave the furnace and is further conducted through an outlet system into a refractory-lined collector manifold 38 (FIG. 2).
[0008] There is no reformer design that can avoid exposing the reformed tubes to very high temperatures approximating 1600° F. as the mixture leaves the furnace. The greater the temperature differential between the inside and outside temperatures, the greater the chance for the tube's failure.
[0009] To establish a relatively smooth and gradual temperature transition and to minimize the axial and radial expansion of the reaction tube, its inner surface is lined with a thermal insulating layer. Thus, the inlet reaction tube 12 and an outlet reaction tube 18 , which is welded to the inlet reaction tube 12 and to a wall 20 of the collector manifold 38 , as indicated by a reference numeral 30 , are provided with first 26 , second 28 , third 32 and forth 34 thermal insulating internal layers. These thermal insulating layers are aligned with one another along a longitudinal direction of the reaction tube between a cone 24 and a lower portion of the outlet reaction tube 18 and are composed of various thermal insulations. Such a structure allows a temperature to decrease gradually from approximately 1600° F. inside the reaction tube to approximately 300° F. corresponding to the outside temperature of the wall.
[0010] Still another temperature differential that affects structural integrity of the reaction tube and its expansion in both axial and radial directions is observed between the wall 20 of the collector manifold 38 and the inner space of the collector manifold 38 , which is in flow communication with a plurality of the reaction tubes. More particular, the outlet reaction tube 18 is provided with a gas conducting tube 22 positioned centrally and guiding the stream of the reactants and being in flow communication with a plug system 36 , which extends into the collector manifold 38 . Accordingly, while the wall 20 of the collector manifold 38 is about 300° F., the temperature inside the manifold reaches 1600° F. To minimize the chance of the conduit's failure, its inner wall has a single thermal insulating layer 40 .
[0011] Overall, the steam reforming catalytic reaction apparatus 10 has a complex structure, which is difficult to assemble and maintain. Numerous internal thermal insulating layers are difficult to install and the reaction tube's shape, which is cylindrical and has a uniform diameter along its entire length, is not instrumental in reducing the gas temperature. Furthermore, a single thermal insulating layer provided on the inner side of the collector manifold is not always sufficient to prevent the overheating of this inner wall.
[0012] It is, therefore, desirable to provide a steam reforming catalytic reaction apparatus having a simple, cost-efficient structure, which can be easily assembled and maintained A furnace outlet system facilitating relatively rapid cooling of reactants flowing from the furnace of the steam reforming catalytic reaction apparatus is also desirable.
SUMMARY OF THE INVENTION
[0013] A reforming catalytic reaction apparatus for cracking hydrocarbons for the production of hydrogen (H 2 ) constructed in accordance with this invention attains these objectives.
[0014] In particular, an outlet system of the inventive reaction apparatus has a multiplicity of reaction tubes, each of which includes differently dimensioned inlet and outlet portions attached to and in flow communication with one another.
[0015] It is known that radiant heat flux, not reaction kinetics, is the controlling factor in determining the effectiveness of the reaction tubes. The efficient reaction tube heat transfer surface area for the specified average heat flux is associated with the high velocities of reactants guided along the reaction tubes, an optimal volume of catalyst required to affect the endothermic steam reforming reaction and with a relatively uniform, acceptable temperature of the walls of the reaction tubes. A structure of the inventive reaction tube including differently dimensioned portions provides such an effective heat transfer surface area.
[0016] In accordance with another aspect of the invention, an outlet portion of a reaction tube is an assembly of an intermediate tube, which extends from the furnace of the reaction apparatus furnace and is provided with at least one external layer of thermal insulating material. The outlet portion further has a bottom tube attached to a collector manifold, which receives multiple streams of reactants exiting a plurality of reaction tubes.
[0017] In practice, application of thermal insulating material to the outer surface of the intermediate tube requires a relatively short installation time. Furthermore, by eliminating an inner insulating layer associated with the known prior art, the flow path, along which the reactants flow inside this tube, is straight forward.
[0018] According to still another aspect of the invention, the collector manifold is thermally insulated by utilizing multiple internal layers of thermal insulating material
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The above and other objects, features and advantages will become more readily apparent from the detailed description of the preferred embodiment illustrated by the following drawings, in which:
[0020] [0020]FIG. 1 is an axial sectional view of an outlet system of a reforming catalytic reaction apparatus for cracking hydrocarbons for the production of hydrogen in accordance with the known prior art;
[0021] [0021]FIG. 2 is a sectional view of a collector manifold of the reforming catalytic reaction apparatus illustrated in FIG. 1;
[0022] [0022]FIG. 3 is an axial sectional view of the outlet system of the reforming catalytic reaction apparatus for cracking hydrocarbons for the production of hydrogen in accordance with the present invention;
[0023] [0023]FIG. 4 is an axial sectional view of the collector manifold of the inventive apparatus shown in FIG. 3; and
[0024] [0024]FIG. 5 is a cross-sectional view of the inlet portion of the reaction tube of the inventive apparatus shown in FIG. 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0025] Referring to FIGS. 3 - 5 , a reforming catalytic reaction apparatus 50 for cracking hydrocarbons for the production of hydrogen receives a mixture of a reformable hydrocarbon and steam fed in a direction indicated by arrows 51 as the raw materials (feedstock) into a plurality of reaction tubes Each of the reaction tubes is a combination of an elongated fired portion 52 including a fire tube 78 , and an unfired outlet portion 76 having an intermediate tube 56 and a bottom tube 57 , which fire 78 , intermediate 56 and bottom 57 tubes are spaced apart along a longitudinal direction of the apparatus 50 To provide the reaction tube with an efficient flow velocity, the intermediate tube 56 has an outer diameter which is smaller than a uniform outer diameter of the fire 78 and bottom 57 tubes.
[0026] The mixture of hydrocarbon feedstock and steam flows through the catalyst bed supported in the fire box by the reaction tube 78 on a ledge, and as the mixture passes through the catalyst bed, it receives heat from a heating furnace 70 . As a result of the endothermic steam reforming reaction, the hydrocarbon feedstock is converted into hydrogen (H 2 ), carbon dioxide (CO 2 ) and carbon monoxide (CO), which collectively form a stream of reactants flowing downwards through the outlet portion 76 of the reaction tube at a high temperature of about 1600° F.
[0027] An upper cone 54 and a lower cone 60 serve as connecting elements between the fire, intermediate and bottom tubes and are field-welded, as denoted by 62 , to opposing ends of these tubes. Due to the geometry of the catalyst tube 78 , intermediate 56 and bottom 57 tubes, the upper cone 54 has a peripheral surface converging downwards from the catalyst tube, whereas the lower cone 60 has an inverted structure with a peripheral wall diverging downwards from a lower end of the intermediate tube 56 .
[0028] The catalyst tube 78 disposed within the heating furnace and terminating approximately at the level of the furnace floor 70 does not have an inner layer of insulating material. However, as shown in FIG. 5, the catalyst tube 78 is thermal insulated along its outer periphery by a multi-layer insulating structure including layers 86 , 90 , 88 and 94 composed of high temperature cloth seal which is made up of silica inner layer, ceramic fiber and chopped fiber, as well as a firebrick layer 92 The penetration of the inlet portion 52 of the reaction tube through the furnace floor 70 is sealed completely by resilient elements such as flexible bellows 68 allowing the compensating axial and radial thermal expansion of the reactor tube due thermal loads applied to this tube.
[0029] As shown in FIG. 3, to minimize thermal effects of heat produced by the stream of reactants that flows along the outlet portion 76 of the reactor tube, the intermediate tube 56 has an external layer 64 of heat insulating material The heat insulating material can be selected from ceramic fiber blanket, chopped fiber, firebrick of their combinations and can include a few sub-layers concentrically attached to one another. The external layers 64 extends preferably between the upper 54 and lower 60 cones and is surrounded by a jacket 66 made from stainless steel. The jacket 66 covers a part of the intermediate tube 56 stretching between the bellows 68 the lower cone 60 .
[0030] Covering the intermediate tube 56 by the external layer 64 offers a simple and reliable structure reducing a temperature from about 1600° F. inside the reactor tube to about 300° F. on the outside of the external layer 64 . Accessible from outside, the external layer can be easily modified by adding additional sub-layers of insulating material. Furthermore, if a reaction tube fails, isolation of tube can be easily provided in a very short down time without cooling down the heating surface by removing the external layer 64 , the jacket 66 and either replacing the failed tube with a new one or providing a cap on the bottom tube 57 .
[0031] The outlet portion 76 has a mixture conducting tube 58 positioned centrally in the bottom tube 57 and projecting into a collector manifold 69 which supports a multiplicity of reaction tubes having a construction identical to the one disclosed above and guides multiple streams of reactants to a waste heat boiler (not shown). The inner surface of the collector manifold 69 is insulated by multiple concentric layers of thermal insulating material including an outer layer 84 and an inner layer 82 . The outer layer 84 extends from the collector manifold upwards into a space formed between the mixture conducting tube 58 and the bottom tube 57 and includes insulating quality castable material. The inner layer which has heat-insulating properties inferior to the outer layer 84 is made up of high temperature erosion resistant castable material.
[0032] Overall, the reforming catalytic reaction apparatus 50 featuring a combination of the inventive variously dimensioned reaction tube, external layers of thermal insulating material covering the intermediate tube of the outlet portion of the reaction tube and the concentric thermal insulating layers mounted in the collector manifold has a simple structure which is easy to assemble and maintain. The invention is not limited to the disclosed preferred embodiments subject to numerous modifications without, however, departing from the scope of the invention as recited in the following claims.
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An outlet system in a reforming catalytic reaction apparatus for cracking hydrocarbons for the production of hydrogen (H 2 ) includes differently dimensioned inlet and outlet reaction tubes attached to and in flow communication with one another; and an external layer of thermal insulation material surrounding a part of the outlet reaction tube
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BACKGROUND
[0001] 1. Field
[0002] The present invention relates generally to communication systems, and more specifically to a method and an apparatus for processing shared sub-packets in a communication system.
[0003] 2. Background
[0004] Communication systems have been developed to allow transmission of information signals from an origination station to a physically distinct destination station. In transmitting information signal from the origination station over a communication channel, the information signal is first converted into a form suitable for efficient transmission over the communication channel. Conversion, or modulation, of the information signal involves varying a parameter of a carrier wave in accordance with the information signal in such a way that the spectrum of the resulting modulated carrier is confined within the communication channel bandwidth. At the destination station the original information signal is replicated from the modulated carrier wave received over the communication channel. Such a replication is generally achieved by using an inverse of the modulation process employed by the origination station.
[0005] Modulation also facilitates multiple-access, i.e., simultaneous transmission and/or reception, of several signals over a common communication channel. Multiple-access communication systems often include a plurality of remote subscriber units requiring intermittent service of relatively short duration rather than continuous access to the common communication channel. Several multiple-access techniques are known in the art, such as time division multiple-access (TDMA), frequency division multiple-access (FDMA), and amplitude modulation multiple-access (AM). Another type of a multiple-access technique is a code division multiple-access (CDMA) spread spectrum system that conforms to the “TIA/EIA/IS-95 Mobile Station-Base Station Compatibility Standard for Dual-Mode Wide-Band Spread Spectrum Cellular System,” hereinafter referred to as the TIA/EIA/IS-95 standard. The use of CDMA techniques in a multiple-access communication system is disclosed in U.S. Pat. No. 4,901,307, entitled “SPREAD SPECTRUM MULTIPLE-ACCESS COMMUNICATION SYSTEM USING SATELLITE OR TERRESTRIAL REPEATERS,” and U.S. Pat. No. 5,103,459, entitled “SYSTEM AND METHOD FOR GENERATING WAVEFORMS IN A CDMA CELLULAR TELEPHONE SYSTEM,” both assigned to the assignee of the present invention.
[0006] A multiple-access communication system may be a wireless or wire-line and may carry voice and/or data. An example of a communication system carrying both voice and data is a system in accordance with the TIA/EIA/IS-95 standard, which specifies transmitting voice and data over the communication channel. A method for transmitting data in code channel frames of fixed size is described in detail in U.S. Pat. No. 5,504,773, entitled “METHOD AND APPARATUS FOR THE FORMATTING OF DATA FOR TRANSMISSION”, assigned to the assignee of the present invention. In accordance with the TIA/EIA/IS-95 standard, the data or voice is partitioned into code channel frames that are 20 milliseconds wide with data rates as high as 14.4 Kbps. Additional examples of a communication systems carrying both voice and data comprise communication systems conforming to the “3rd Generation Partnership Project” (3GPP), embodied in a set of documents including Document Nos. 3G TS 25.211, 3G TS 25.212, 3G TS 25.213, and 3G TS 25.214 (the W-CDMA standard), or “TR-45.5 Physical Layer Standard for cdma2000 Spread Spectrum Systems” (the IS-2000 standard).
[0007] An example of a data only communication system is a high data rate (HDR) communication system that conforms to the TIA/EIA/TIA/EIA/IS-895 industry standard, hereinafter referred to as the TIA/EIA/IS-895 standard. This HDR system is based on a communication system disclosed in co-pending application Ser. No. 08/963,386, entitled “METHOD AND APPARATUS FOR HIGH RATE PACKET DATA TRANSMISSION,” filed Nov. 3, 1997, assigned to the assignee of the present invention. The HDR communication system defines a set of data rates, ranging from 38.4 kbps to 2.4 Mbps, at which an access point (AP) may send data to a subscriber station (access terminal, AT). Because the AP is analogous to a base station, the terminology with respect to cells and sectors is the same as with respect to voice systems.
[0008] Existing voice/data communication systems generally utilize voice traffic channels for conducting voice telephony or data communications including small file transfer, electronic mail, and facsimile. Consequently, the data transmission rate is limited. For example, in the above-mentioned communication system in accordance with the TIA/EIA/IS-95 standard provides for establishing multiple traffic channels, each having a rate of data up to 14.4 kilobits per second. While 14.4 kilobits per second is adequate for the above-mentioned types of lower data rate applications, the increasing popularity of more data intensive applications such as worldwide web and video conferencing has created a demand for much higher data transmission rates. The communication system in accordance with the TIA/EIA/IS-895 standard satisfies the data rate requirement, but allows for data transmission only. To satisfy the demand for data transmission while retaining voice service capability, several communication systems have been proposed.
[0009] One such a communication system is the above mentioned communication system in accordance with the W-CDMA standard. Another communication system is described in a proposal submitted by LG Electronics, LSI Logic, Lucent Technologies, Nortel Networks, QUALCOMM Incorporated, and Samsung to the 3 rd Generation Partnership Project 2 (3GPP2). The proposal is detailed in documents entitled “Updated Joint Physical Layer Proposal for 1xEV-DV,” submitted to 3GPP2 as document number C50-20010611-009, Jun. 11, 2001, and “Updated Joint Physical Layer Proposal for 1xEV-DV,” file L3NQS_Physical_Layer_v09.doc, Aug. 20, 2001, hereinafter referred to as 1xEV-DV proposal. Yet another communication system is described in a proposal to the 3GPP2 submitted by Motorola, Nokia, Texas Instruments, and LSI Logic. The proposal is detailed in document entitled “1XTREME Physical Layer Specification for Integrated Data and Voice Services in cdma2000 Spread Spectrum Systems,” submitted to 3GPP2 as document number C50-20001204-021, Dec. 8, 2000.
[0010] The 1xEV-DV proposal provides an air interface between a plurality of subscriber stations and a plurality of subscriber stations enabling a simultaneous voice and data services. For that purpose, the 1xEV-DV proposal defines a set of forward and reverse channels.
[0011] The structure of a reverse channels transmitted by a base stations is illustrated in FIG. 1. The reverse Pilot Channel, the Dedicated Control Channel, and the Fundamental Channel remain unchanged. The Supplemental Channel structure remains unchanged for Radio Configurations 1 through 6. The new reverse control channels are the Reverse Rate Indicator Channel (R-RICH), the Reverse Channel Quality Indicator Channel (R-CQICH), and the Reverse Acknowledgment Channel (R-ACKCH).
[0012] The structure of a forward channels transmitted by a base stations 104 ( i ) is illustrated in FIG. 2. The Forward Pilot Channel, Transmit Diversity Pilot Channel, Auxiliary Pilot Channel, Auxiliary Transmit Diversity Pilot Channel, Synch Channel, Paging Channel, Broadcast Control Channel, Quick Paging Channel, Common Power Control Channel, Common Assignment Channel, Dedicated Control Channel, Forward Fundamental Channel, Forward Supplemental Channel, and Forward Supplemental Code Channels are the same as their counterparts in the above-mentioned IS-2000 standard. The Forward Packet Data Channel, the optional Forward Primary Packet Data Control Channel, and the Forward Secondary Packet Data Control Channel are channels defined for 1xEV-DV packet data operation.
[0013] The data services are provided to a subscriber station on a Forward Packet Data Channel (F-PDCH), which is shared by packet data users based on time multiplexing. The F-PDCH is composed of a number of code-division-multiplexed Walsh sub-channels. The number of sub-channels varies in time depending on the demands of the circuit-switched voice and data users. The F-PDCH structure is illustrated in FIG. 3. The information bit stream 302 to be transmitted is segmented into packets of several sizes. A 16-bit cyclic redundancy check (CRC) is added to each packet in block 302 , and 6-bit turbo encoder tail allowance is added in block 306 yielding an encoder packet. In one embodiment, the encoder packets are of sizes 384 bits, 768 bits, 1,536 bits, 2,304 bits, 3,072 bits, and 3,840 bits. The encoder packets are encoded by block 308 . Each encoded packet is then scrambled in blocks 310 by a scrambling pattern generated by block 312 and interleaved by block 314 . Some or all of the interleaved symbols are then selected to form sub-packets in block 316 . Depending on the length of the sub-packet, the sub-packet comprises 1, 2, 4, or 8 slots. In one embodiment, the slot is 1.25 ms long. The sub-packet are QPSK, 8-PSK, or 16-QAM modulated by block 318 and demultiplexed into a variable number of pairs (In-phase and Quadrature) of parallel streams by block 320 . Each of the parallel streams is covered with a distinct 32-ary Walsh function by blocks 322 ( i ). The Walsh-coded symbols of all the streams are summed together to form a single In-phase stream and a single Quadrature stream by block 324 . The In-phase stream and the Quadrature streams are provided to a block 326 , which adjusts the channel's gain. Several forward link channels, both data and voice are then summed in block 328 , quadrature spread in block 330 , and the resultant In-phase and Quadrature streams are baseband filtered in block 332 ( i ), upconverted in blocks 334 ( i ) and summed in block 336 .
[0014] The F-PDCH is controlled by a Forward Primary Packet Data Control Channel (F-PPDCCH) if used and by a Forward Secondary Packet Data Control Channel (F-SPDCCH).
[0015] The F-PPDCCH is transmitted during the first slot of F-PDCH transmissions, and carries a 2-bit field that indicates the F-PDCH sub-packet length. One of ordinary skills in the art recognizes that because the F-PPDCCH carries only information of the F-PDCH sub-packet length, the use of the F-PPDCCH is optional. The subscriber station may use other means for determining the F-PDCH sub-packet length. Thus, for example, the subscriber station may decode the sub-packet for all sub-packet length hypotheses, and select the most likely one of the hypothesis.
[0016] The F-SPDCCH is transmitted over 1, 2, or 4 slots, and the starts of the F-SPDCCH transmissions are aligned with the starts of the corresponding F-PDCH transmissions. The F-SPDCCH carries bits specifying a medium access control (MAC) identifier (ID), the Automatic Repeat reQuest (ARQ) channel ID, the encoder packet size, and the F-PDCH sub-packet ID.
[0017] The 1xEV-DV proposal thus allows the base station to send data to multiple mobiles only on a single slot granularity. Furthermore, the highest sub-packet data rate that is allowed for 384-bit packets is 307.2 kbps with one slot per sub-packet. So even when mobiles are capable of receiving higher data rates, they are limited to at most 307.2 kbps and use at least one slot.
[0018] Similarly, the 1XTREME proposal provides an air interface between a plurality of subscriber stations and a plurality of subscriber stations enabling a simultaneous voice and data services. The 1XTREME proposal uses a fixed sub-packet size of 5 ms for the packet data channels and for the control channels associated with the packet data channels. The packet data sub-packets can be CDM shared, but there is no flexibility on the duration of the data or control sub-packets. The packet data channel is controlled with a dedicated CDM channel for each user, called the Forward Dedicated Pointer Channel, and with a shared control channel, called the Forward Shared Control Channel.
[0019] The fixed-duration shared packet data sub-packet and limited control of the 1XTREME or 1xEV-DV proposals waste resources and limits the system throughput performance. Consequently, there is a need in the art for a method and an apparatus for improving the throughput of the system by allowing multiple forward-link transmissions per a slot.
SUMMARY
[0020] In one aspect of the invention, the above-stated needs are addressed by generating a first control channel comprising an indicator that a traffic channel is to be shared and a parameters of a traffic channels; and generating at least one second control channel, each of said at least one second control channel comprising an identity of at least one subscriber station and information enabling the subscriber station to demodulate the traffic channel.
[0021] In another aspect of the invention, the above-stated needs are addressed by demodulating a first control channel to determine whether a traffic channel is to be shared; determining a number of subscriber stations sharing a traffic channel and multiplexing of the traffic channel in accordance with said demodulated control channel if the traffic channel is to be shared; demodulating a second control channel comprising identity of a subscriber station, and information enabling a subscriber station to demodulate a traffic channel; and demodulating the traffic channel in accordance with said determined multiplexing and the enabling information if the acquired identity is identical to an identity of the subscriber station.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] [0022]FIG. 1 illustrates a structure of a reverse channels transmitted by a base stations;
[0023] [0023]FIG. 2 illustrates a structure of a reverse channels transmitted by a base stations;
[0024] [0024]FIG. 3 an exemplary forward packet data channel;
[0025] [0025]FIG. 4 illustrates sub-packet structure in accordance with one embodiment;
[0026] [0026]FIG. 5 illustrates sub-packet structure in accordance with one embodiment;
[0027] [0027]FIG. 6 illustrates a control channel structure in accordance with one embodiment;
[0028] [0028]FIG. 7 illustrates a control channel structure in accordance with another embodiment;
[0029] [0029]FIG. 8 illustrates a control channel structure in accordance with another embodiment;
[0030] [0030]FIG. 9 illustrates a CDM channel structure in accordance with one embodiment;
[0031] [0031]FIG. 10 illustrates a control channel structure in accordance with another embodiment;
[0032] [0032]FIG. 11 illustrates a control channel structure in accordance with another embodiment;
[0033] [0033]FIG. 12 illustrates a control channel structure in accordance with another embodiment; and
[0034] [0034]FIG. 13 illustrates a control channel structure in accordance with another embodiment.
DETAILED DESCRIPTION
Definitions
[0035] The word “exemplary” is used exclusively herein to mean “serving as an example, instance, or illustration.” Any embodiment described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments.
[0036] The term packet is used exclusively herein to mean a group of bits, including data (payload) and control elements, arranged into a specific format. The control elements comprise, e.g., a preamble, a quality metric, and others known to one skilled in the art. Quality metric comprises, e.g., a cyclical redundancy check (CRC), a parity bit, and others known to one skilled in the art.
[0037] The term access network is used exclusively herein to mean a collection of access points (AP) and one or more access point controllers. The access network transports data packets between multiple access terminals (AT). The access network may be further connected to additional networks outside the access network, such as a corporate intranet or the Internet, and may transport data packets between each access terminal and such outside networks.
[0038] The term base station, referred to herein as an AP in the case of an HDR communication system, is used exclusively herein to mean the hardware with which subscriber stations communicate. Cell refers to the hardware or a geographic coverage area, depending on the context in which the term is used. A sector is a partition of a cell. Because a sector has the attributes of a cell, the teachings described in terms of cells are readily extended to sectors.
[0039] The term subscriber station, referred to herein as an AT in the case of an HDR communication system, is used exclusively herein to mean the hardware with which an access network communicates. An AT may be mobile or stationary. An AT may be any data device that communicates through a wireless channel or through a wired channel, for example using fiber optic or coaxial cables. An AT may further be any of a number of types of devices including but not limited to PC card, compact flash, external or internal modem, or wireless or wireline phone. An AT that is in the process of establishing an active traffic channel connection with an AP is said to be in a connection setup state. An AT that has established an active traffic channel connection with an AP is called an active AT, and is said to be in a traffic state.
[0040] The term communication channel/link is used exclusively herein to mean a single route over which a signal is transmitted described in terms of modulation characteristics and coding, or a single route within the protocol layers of either the AP or the AT.
[0041] The term reverse channel/link is used exclusively herein to mean a communication channel/link through which the AT sends signals to the AP.
[0042] A forward channel/link is used exclusively herein to mean a communication channel/link through which an AP sends signals to an AT.
[0043] The term soft hand-off is used exclusively herein to mean a communication between a subscriber station and two or more sectors, wherein each sector belongs to a different cell. In the context of TIA/EIA/IS-95 standard, the reverse link communication is received by both sectors, and the forward link communication is simultaneously carried on the two or more sectors' forward links. In the context of the TIA/EIA/IS-895 standard, data transmission on the forward link is non-simultaneously carried out between one of the two or more sectors and the AT.
[0044] The term softer hand-off is used exclusively herein to mean a communication between a subscriber station and two or more sectors, wherein each sector belongs to the same cell. In the context of the TIA/EIA/IS-95 standard, the reverse link communication is received by both sectors, and the forward link communication is simultaneously carried on one of the two or more sectors' forward links. In the context of the TIA/EIA/IS-895 standard, data transmission on the forward link is non-simultaneously carried out between one of the two or more sectors and the AT.
[0045] The term re-pointing is used exclusively herein to mean a selection of a sector that is a member of an ATs' active list, wherein the sector is different than a currently selected sector.
[0046] The term soft/softer hand-off delay is used exclusively herein to indicate the minimum interruption in service that a subscriber station would experience following a handoff to another sector. Soft/Softer handoff delay is determined based on whether the sector, (currently not serving the subscriber station), (non-serving sector) to which the subscriber station is re-pointing is part of the same cell as the current serving sector. If the non-serving sector is in the same cell as the serving sector then the softer handoff delay is used, and if the non-serving sector is in a cell different from the one that the serving sector is part of then the soft-handoff delay is used.
[0047] The term non-homogenous soft/softer hand-off delay is used exclusively herein to indicate that the soft/softer hand-off delays are sector specific and therefore may not uniform across the sectors of an Access Network.
[0048] The term credit is used exclusively herein to mean a dimensionless attribute indicating a quality metric of a reverse link, a quality metric of a forward link, or a composite quality metric of both forward and reverse links.
[0049] The term erasure is used exclusively herein to mean failure to recognize a message.
[0050] The term outage is used exclusively herein to mean a time interval during which the likelihood that a subscriber station will receive service is reduced.
[0051] The term fixed rate mode is used exclusively herein to mean that a particular sector transmits a Forward Traffic Channel to the AT at one particular rate.
DESCRIPTION
[0052] The present invention utilizes the sub-packet structure as defined in the 1xEV-DV proposal, but further divides the sub-packet granularity. Throughout the following description, the channels are discussed in terms of structure required for understanding the concept of the invention. Consequently, one of ordinary skills in the art appreciates that the channel structure may contain additional elements required for transmission, e.g., CRC, encoder tail bits, and other blocks known to one of ordinary skills in the art.
[0053] [0053]FIG. 4 illustrates sub-packet structure in accordance with one embodiment. The sub-packet 400 comprises one or more slots 402 ( i ). Each of the slots 402 ( i ) is further time-divided into sub-slots 404 ( i ). (Only one slot sub-division is shown.) In one embodiment, there are 2, 4 or 8 equal sub-slots 404 ( i ). However, one skilled in the art understands that the sub division is an implementation choice and other sub-divisions are within the scope of the invention. The data to a subscriber station are provided in one or more of the sub-slots 404 ( i ). Each subscriber station can use a number of sub-slots 404 ( i ), and the number of sub-slots for each of the subscriber station utilizing each of the sub-packets 402 ( i ) can be different.
[0054] In accordance with another embodiment, illustrated in FIG. 5, the slot(s) 502 ( i ) of the sub-packet 500 contain data for several subscriber stations. Data from all the slots 502 ( i ) of the sub-packet 500 for a particular mobile are sent using one or more of the available Walsh channels. As illustrated in FIG. 5, slots 402 ( 1 )- 402 ( n ) contain data encoded by Walsh codes 504 ( 1 )- 504 ( m ), therefore, carry data for m subscriber stations. Consequently, the number of subscriber stations receiving information concurrently may be changed on a sub-packet to sub-packet basis.
[0055] Control Structures
[0056] Due to the variability of the structure of the F-PDCH as described above, a subscriber station must be provided with information enabling the subscriber station to demodulate the F-PDCH. In one embodiment utilizing the code-division of the sub-packets, the existing structures of the F-PPDCCH and the F-SPDCCH can be utilized. One skilled in the art appreciates that although the following description describes modifications of the F-PPDCCH and the F-SPDCCH, this is for tutorial purposes only, and new channels in accordance with the described embodiments can be defined. Additional information is carried on one or more new channels.
[0057] [0057]FIG. 6 illustrates a control channel structure in accordance with one embodiment, comprising the F-PPDCCH 600 , the F-SPDCCH 602 , and one CDM control channel 608 ( i ) for each of the subscriber stations sharing the sub-packet. The F-PPDCCH 600 is utilized as defined in the 1xEV-DV proposal. One of ordinary skills in the art recognizes that because the F-PPDCCH carries only information about the F-PDCH sub-packet length, the use of the F-PPDCCH is optional. The subscriber station may use other means for determining the F-PDCH sub-packet length. Thus, for example, the subscriber station may decode the sub-packet for all sub-packet length hypotheses, and select the most likely one of the hypothesis.
[0058] Similarly, the F-SPDCCH 602 is utilized as defined in the 1xEV-DV proposal with the following modification. One of the values of the MAC ID of block 604 is reserved to identify that a sub-packet of the F-PDCH is to be shared. In accordance with one embodiment, the MAC ID value identifies that the sub-packet is to be shared is all ones. Because all the subscriber stations for which the shared sub-packets are intended must reliably receive the information content of channel 602 , channel 602 is transmitted at power determined by the power requirement of the subscriber station, for which the control channel 602 is intended, with the worst forward link quality metric. Upon receiving the channel 602 , each of the subscriber stations demodulates and decodes the MAC ID of block 604 . If the MAC ID indicates that the sub-packet is for one of the subscriber stations, the identified subscriber station processes the sub-packet in accordance with the procedures outlined in the 1xEV-DV proposal.
[0059] If the MAC ID indicates that the sub-packet is to be shared, the remaining bits of block 606 are interpreted to indicate parameters of the shared sub-packet. The parameters comprise a number of subscriber stations sharing the sub-packet. Consequently, each of the subscriber stations acquires this information, and then starts receiving the CDM channels 608 ( i ). Because each of the CDM channels 608 ( i ) is modulated by a Walsh code, the subscriber stations need to know these Walsh codes. In one embodiment, pre-determined Walsh codes are reserved for the CDM channels 608 ( i ). In another embodiment, the subscriber stations are notified about the Walsh codes by signaling messages. Only the number of CDM channels 608 ( i ) equal to the number of subscriber stations sharing the sub-packet is transmitted, and the transmission occurs only when the sub-packet is shared. In one embodiment, the CDM channels 608 ( i ) are transmitted concurrently, consequently, each of the subscriber stations accumulates data from all the CDM channels 608 ( i ), and then post processes the accumulated data. Because each of the CDM channels 608 ( i ) is intended for one of the subscriber stations and the base station has an information about the subscriber station forward link quality metric, the base station transmits each of the CDM channels 608 ( i ) at the minimum power determined by power requirement of the subscriber station.
[0060] Each of the CDM channels 608 ( i ) comprises information enabling the subscriber station to determine which of the CDM channels 608 ( i ) is intended for the subscriber station and information enabling the subscriber station to demodulate the F-PDCH. The information enabling the subscriber station to determine which of the CDM channels 608 ( i ) is intended for the subscriber station comprises a MAC ID 610 ( i ). The information enabling the subscriber station to demodulate the F-PDCH comprises an ARQ ID 612 ( i ), a sub-packet ID 616 ( i ), a packet size 618 ( i ), and a number of Walsh channels used 620 ( i ). In one embodiment, the current F-PDCCH coding and modulation is used for each of the CDM channels 608 ( i ). During the post processing, each of the subscriber stations demodulates the MAC ID 610 ( i ) of a CDM channel 608 ( i ). If the MAC ID 610 ( i ) indicates that the CDM channel 608 ( i ) does not contain information for the subscriber station, the subscriber station ceases further post processing of the channel and repeats the procedure for the next CDM channel 608 ( i+ 1). If a subscriber demodulates a MAC ID 610 ( i ) indicating that the CDM channel 608 ( i ) contains information for the subscriber station, the subscriber station demodulates the remaining information, and processes the sub-packet on the F-PDCH in accordance to the gathered information.
[0061] In another embodiment utilizing the code-division of the sub-packets, the information is provided on the F-PPDCCH, the F-SPDCCH, and one CDM channel for all the subscriber stations sharing the sub-packet. Consequently, the F-PPDCCH and the F-SPDCCH have the structure as described with reference to FIG. 6. The structure of the CDM channel carries the information enabling each of the subscriber stations to demodulate the F-PDCH. The information for all the subscriber stations is time multiplexed and then encoded and modulated. Consequently, the CDM channel comprises concatenation of the CDM channels 608 ( i ) as described in FIG. 6. In one embodiment, the current F-SPDCCH coding and modulation is used for the CDM channel. Consequently, the method of acquiring the information is the same as described above, with the exception that all the subscriber stations demodulate and decode the whole information carried on the CDM channel. The subscriber station then examines the MAC IDs. If the subscriber station fails to find a MAC ID indicating that the subscriber station is to share the sub-packet, the subscriber station ceases further processing. If a subscriber finds a MAC ID indicating that the following portion of the CDM channel contains information for the subscriber station, the subscriber station demodulates the information, and processes the sub-packet on the F-PDCH in accordance with the gathered information.
[0062] One of ordinary skill in the art appreciates that limiting number of subscriber station sharing the sub-packet yields further simplification of the above-described embodiments. Consequently, in one embodiment allowing only two subscriber station to share the sub-packet, the existing structure of the F-PPDCCH and a modified structure of the F-SPDCCH can be utilized. Thus, there is no need for an additional control channel.
[0063] The F-PPDCCH is utilized as defined in the 1xEV-DV proposal. One of ordinary skills in the art recognizes that because the F-PPDCCH carries only information about the F-PDCH sub-packet length, the use of the F-PPDCCH is optional. The subscriber station may use other means for determining the F-PDCH sub-packet length. Thus, for example, the subscriber station may decode the sub-packet for all sub-packet length hypotheses, and select the most likely one of the hypothesis.
[0064] [0064]FIG. 7 illustrates a structure of the modified F-SPDCCH 700 . The modified F-SPDCCH 700 comprises information enabling the two subscriber stations to demodulate the F-PDCH. Therefore, the F-SPDCCH 700 comprises and MAC IDs for each subscriber stations 702 ( 1 ), 702 ( 2 ), ARQ IDs 702 ( 1 ), 704 ( 2 ), sub-packet IDs 706 ( 1 ), 706 ( 2 ), encoder packet sizes 708 ( 1 ), 708 ( 2 ), and number of Walsh channels used 710 ( 1 ), 710 ( 2 ). The structure can be further simplified if the second subscriber station is assumed to use a number of Walsh channels less than or equal to the number of Walsh channels of the second subscriber station. Then the modified F-SPDCCH 700 comprises only one of the blocks 710 ( 1 ), 710 ( 2 ).
[0065] Because all the subscriber stations intended to share the sub-packet must reliably receive the modified F-SPDCCH 700 , the modified F-SPDCCH 700 is transmitted at a power determined by the power requirement of the subscriber station with the worst forward link quality metric for which the modified F-SPDCCH 700 is intended. Upon receiving the modified F-SPDCCH 700 , each of the subscriber stations demodulates the modified F-SPDCCH 700 and decodes the MAC IDs in the blocks 702 ( 1 ), 702 ( 1 ). If the MAC ID of the subscriber station is identical to either of the decoded MAC IDs, the subscriber station acquires the remaining information from the modified F-SPDCCH 700 , and processes the sub-packet of the F-PDCH in accordance with the information.
[0066] The modified F-SPDCCH 700 is transmitted even if the F-PDCH is intended for only one subscriber station. In this case, the MAC ID 702 ( 2 ), is identical to the MAC ID 702 ( 1 ). Consequently, the subscriber stations ignore the interpretation of block 704 ( 2 ) as ARQ ID, 706 ( 2 ) as sub-packet ID, 708 ( 2 ) as encoder packet size, and 710 ( 2 ) as number of Walsh channels used 710 ( 1 ). Consequently, these blocks can be used for any additional information. The subscriber a MAC ID of which is identical to the decoded MAC ID acquires the remaining information from the modified F-SPDCCH 700 , and processes the sub-packet of the F-PDCH in accordance with procedures outlined in the 1xEV-DV proposal.
[0067] In accordance with another embodiment, the existing structures of the F-PPDCCH and the F-SPDCCH can be utilized. The F-PPDCCH is utilized as defined in the 1xEV-DV proposal. One of ordinary skills in the art recognizes that because the F-PPDCCH carries only information about the F-PDCH sub-packet length, the use of the F-PPDCCH is optional. The subscriber station may use other means for determining the F-PDCH sub-packet length. Thus, for example, the subscriber station may decode the sub-packet for all sub-packet length hypotheses, and select the most likely one of the hypothesis. The F-SPDCCH comprises information enabling one of the two subscriber stations to demodulate the F-PDCH and an indicator to specify whether another CDM control channel is transmitted. The CDM control channel comprises information enabling one subscriber station to demodulate the F-PDCH.
[0068] [0068]FIG. 8 illustrates a control channel structure the F-SPDCCH 800 , and the CDM control channel 802 . The F-SPDCCH 800 comprises an MAC ID 804 , ARQ ID 806 , sub-packet ID 808 , encoder packet size 810 , and numbers of Walsh channels used 812 for one of the possible two shared channels, and the a CDM indicator 814 .
[0069] The CDM channel 802 comprises an MAC ID 816 , ARQ ID 818 , sub-packet ID 820 , encoder packet size 822 , and number of Walsh channels used 824 for the second shared channel if it is used. If the F-PDCH sub-packet is not shared, the CDM channel 802 is not transmitted for that sub-packet
[0070] In one embodiment, the F-SPDCCH 800 and, if used, the CDM control channel 802 are transmitted concurrently. Because the subscriber stations do not know, whether the CDM control channel 802 is transmitted or not, each of the subscriber stations accumulates data from both the F-SPDCCH 800 and all the CDM channel 802 , and then post processes the accumulated data. Because both subscriber stations to share the sub-packet must reliably receive the F-SPDCCH 800 , the F-SPDCCH 800 is transmitted at a power determined by power requirement of the subscriber station with the worst forward link quality metric fro which the F-SPDCCH 800 is intended. Because the CDM control channel 802 is intended for one of the subscriber stations and the base station has an information about the subscriber station's forward link quality metric, the base station transmits the CDM control channel 802 at the minimum power determined by power requirement of the subscriber station.
[0071] Upon receiving the modified F-SPDCCH 800 , each of the subscriber stations decodes the MAC ID 802 . If the decoded MAC ID is identical to the subscriber station's MAC ID, the subscriber station decodes the remaining information from the F-SPDCCH 800 , and processes the sub-packet of the F-PDCH in accordance with the information.
[0072] The subscriber stations, MAC IDs of which are not identical with the decoded MAC ID, decode the CDM indicator 814 . If the CDM indicator X 214 indicates that no CDM control channel 802 is transmitted, the subscriber stations cease further processing; otherwise the subscriber stations decode the MAC ID 816 . The subscriber station, a MAC ID of which is identical with the decoded MAC ID acquires the remaining information from the CDM control channel 802 , and processes the sub-packet of the F-PDCH in accordance with the information. The subscriber stations, MAC IDs of which are not identical with the decoded MAC ID cease further processing.
[0073] In another embodiment utilizing the time-division of the F-PDCH sub-packets, the control information is provided on the F-PPDCCH, the F-SPDCCH, and one CDM channel for each of the subscriber stations sharing the sub-packet.
[0074] The function and the structure of the F-PPDCCH is identical to the function and the structure of the F-PPDCCH as described above with regards to the CDM based F-PDCH sub-packet sharing.
[0075] Similarly, the function and the structure of the F-PSDCCH is identical to the function and the structure of the F-PSDCCH as described above with regards to the CDM based sub-packet sharing with the following modification. If the MAC ID indicates that a sub-packet of the F-PDCH is to be shared, the remaining bits of the F-SPDCCH are interpreted to indicate parameters of the shared sub-packet, which comprise number of sub-slots into which the sub-packet is subdivided and the number of subscriber stations sharing the sub-packet. Consequently, each of the subscriber stations demodulates the modified F-SPDCCH and decodes the MAC ID. If the MAC ID indicates that the sub-packet is for the subscriber station, the identified subscriber station processes the sub-packet in accordance to procedures outlined in the 1xEV-DV proposal.
[0076] If the MAC ID indicates that the sub-packet is to be shared, the subscriber stations will use the remaining bits of the F-SPDCCH to determine the number of sub-slots into which the sub-packet is subdivided and the number of subscriber stations sharing the sub-packet. Consequently, each of the subscriber stations acquires this information, and then starts receiving the TDM channels 900 ( i ), as illustrated in FIG. 9. Because each of the CDM channels 900 ( i ) is modulated by a Walsh code, the subscriber stations need to know these Walsh codes. In one embodiment, pre-determined Walsh codes are reserved for the CDM channels 900 ( i ). In another embodiment, the subscriber stations is notified about the Walsh codes by signaling messages. Only the number of CDM channels 900 ( i ) equal to the number of subscriber stations sharing the sub-packet is transmitted, and the transmission occurs only when the sub-packet is shared. In one embodiment, the CDM channels 900 ( i ) are transmitted concurrently, consequently, each of the subscriber stations accumulates data from all the TDM channels 900 ( i ), and then post processes the accumulated data. Because each of the CDM control channels 900 ( i ) for the TDM-shared F-PDCH is intended for one of the subscriber stations and the base station has a information about the subscriber station forward link quality metric, the base station transmits each of the CDM control channels 900 ( i ) at just enough power to reach the intended subscriber station reliably.
[0077] Each of the CDM control channels 900 ( i ) comprises information enabling the subscriber station to determine which of the CDM channels 900 ( i ) is intended for the subscriber station and information enabling the subscriber station to demodulate a F-PDCH. The information enabling the subscriber station to determine which of the CDM channels 900 ( i ) is intended for the subscriber station comprises a MAC ID 902 ( i ). The information enabling the subscriber station to demodulate the F-PDCH comprises an ARQ ID 904 ( i ), a sub-packet ID 906 ( i ), a format of the shared sub-packet 908 ( i ), and a starting sub-slot 910 ( i ) for each of the mobiles. In one embodiment, the current F-PDCCH coding and modulation is used for each of the CDM channels 900 ( i ). During the post processing, each of the subscriber stations demodulates the MAC ID 902 ( i ) of a control channel 900 ( i ). If the MAC ID 902 ( i ) indicates that the control channel 900 ( i ) does not contain information for the subscriber station, the subscriber station ceases further post processing of the channel and repeats the procedure for the next control channel 900 (i+1). If a subscriber demodulates a MAC ID 902 ( i ) indicating that the control channel 900 ( i ) contains information for the subscriber station, the subscriber station reads the remaining information, and processes the sub-packet on the F-PDCH in accordance to the gathered information.
[0078] In another embodiment utilizing the time-division of the slots, the information is provided on the F-PPDCCH, the F-SPDCCH, and one TDM channel for all the subscriber stations sharing the sub-packet. The TDM channel is modulated by the information enabling each of the subscriber stations to demodulate the F-PDCH. The information for all the subscriber station is time multiplexed and then encoded and modulated. Consequently, the CDM channel comprises concatenation of the CDM channels 900 ( i ) as described in FIG. 9. In one embodiment, the current F-SPDCCH coding and modulation is used for the CDM channel. Consequently, the method of acquiring the information is the same as described above, with the exception that all the subscriber stations tune to the CDM channel, demodulate and decode the whole information. The subscriber station then examines the MAC IDs. If the subscriber station fails to find a MAC ID indicating that the subscriber station is to share the sub-packet, the subscriber station ceases further processing. If a subscriber finds a MAC ID indicating that the following portion of the CDM channel contains information for the subscriber station, the subscriber station reads the rest of the information, and processes the sub-packet on the F-PDCH in accordance to the gathered information. Furthermore, each of the subscriber stations examines each portion of the F-SPDCCH containing the information about sub-slot positions. Consequently, the CDM channel does not need to contain the starting sub-slot for each subscriber station because the subscriber stations have acquired the information on the duration of sub-slots intended for the other subscriber stations.
[0079] The control channels' structure in accordance with another embodiment is illustrated in FIG. 10. Control channel 1002 comprises an indication of a number of control channels 1008 ( i ) in block 1004 . Furthermore, each of blocks 1006 ( i ) identifies a MAC ID of a subscriber station for which information is sent on a F-PDCH. To receive the control channel 1002 the subscriber stations must know modulation parameters of the control channel 1002 . In one embodiment, the modulation parameters are pre-determined. In another embodiment, the modulation parameters are provided to the subscriber stations by signaling messages. Because all subscriber stations must reliably receive the control channel 1002 , the control channel 1002 is transmitted at power determined by a power requirement of the subscriber station with the worst forward link quality metric. Upon receiving the control channel 1002 , each of the subscriber stations demodulates and decodes the control channel 1002 . Each of the subscriber stations with MAC ID identical to the MAC IDs acquired from block 1006 ( i ) then acquires one of the control channel 1008 ( i ). Consequently, the number of the transmitted control channels 1008 ( i ) is equal to the number of MAC IDs in the channel 1002 . The subscriber stations with MAC IDs different from the MAC IDs acquired from block 1006 ( i ) cease further control channel processing.
[0080] Each of the additional control channels 1008 ( i ) comprises information enabling a subscriber station identified by one of the MAC IDs to demodulate the F-PDCH. Therefore, in one embodiment, each of the control channels comprises an ARQ channel ID, the encoder packet size, and the F-PDCH sub-packet ID, as well as information for sub-packet TDM/CDM sharing as described above.
[0081] To acquire information enabling the subscriber station identified by one of the MAC IDs in control channel 1002 to demodulate the F-PDCH, there must exist a relationship between the subscriber station MAC ID and the control channel 1008 ( i ) comprising the information for the subscriber station. In one embodiment, the relationship is determined by a position of the blocks 1006 ( i ) within the channel 1002 , and an index of the Walsh code encoding the control channel 1008 ( i ). Thus, for example increasing order of MAC ID position in the control channel 1002 means increasing index of the Walsh code encoding the control channel 1008 ( i ). The relationship between the control channel's Walsh code and a MAC ID may be pre-determined or changeable by signaling messages. However, one of ordinary skills in the art appreciates that other relationships are within the scope of the invention. Because each of the additional control channel 1008 ( i ) is intended for one of the subscriber stations and the base station has an information about the subscriber station forward link quality metric, the base station transmits each of the channels 1008 ( i ) at the minimum power determined by power requirement of the subscriber station.
[0082] Once a subscriber station demodulates the appropriate control channel 1008 ( i ), the subscriber station decodes the information enabling the demodulation of the F-PDCH, and processes the sub-packet on the F-PDCH in accordance to the gathered information.
[0083] The control channel(s) structure in accordance with another embodiment is illustrated in FIG. 11. Each of the control channels 1102 ( i ) contains all the information a subscriber station needs to decode the F-PDCH. Therefore, in one embodiment, each of the channels 1102 ( i ) comprises a MAC ID block 1104 , an ARQ channel ID block 1106 , the encoder packet size block 1108 , and the F-PDCH sub-packet ID block 1110 , as well as information for sub-packet TDM/CDM sharing as described above, collectively identified as block 1112 . Because each of the control channels 1102 ( i ) is intended for one of the subscriber stations and the base station has an information about the subscriber station forward link quality metric, the base station transmits each of the channels 1108 ( i ) at the minimum power determined by power requirement of the subscriber station.
[0084] To receive the control channels 1102 ( i ) the subscriber stations must know modulation parameters of the control channels 1102 ( i ). In one embodiment, the modulation parameters and the number of possible control channels are pre-determined. In one embodiment, the modulation parameters comprise different Walsh codes. Because in accordance with the embodiment, there is no relationship between one subscriber station and one control channel 1102 ( i ), the subscriber stations must demodulate all the control channels 1102 ( i ). Although a number of transmitted control channels 1102 ( i ) is equal to a number of subscriber stations for which information is send on a F-PDCH because the number of subscriber stations may change in accordance with the granularity of the F-PDCH as described above, the number of transmitted control channels 1102 ( i ) changes.
[0085] In one embodiment, the control channels 1108 ( i ) are transmitted concurrently, consequently, each of the subscriber stations accumulates data for all the channels 1108 ( i ), and then post processes the accumulated data. During the post processing, each of the subscriber stations demodulates one of the control channels 1102 ( i ) and decodes a MAC ID of block 1104 ( i ). The subscriber station with MAC ID identical to the MAC ID of block 1104 ( i ) demodulates the remaining information, and processes the sub-packet on the F-PDCH in accordance to the gathered information. If the MAC ID of block 1104 ( i ) indicates that the channel 1108 ( i ) does not contain information for the subscriber station, the subscriber station ceases further post processing of the channel and repeats the procedure for the next channel 1108 ( i ). Because as discussed, the subscriber station does not have information about the number of transmitted control channels 1108 ( i ), unless the subscriber station finds a MAC ID indicating that the channel 1108 ( i ) contains information for the subscriber station, the subscriber station must attempt to demodulate all possible control channels 1108 ( i ).
[0086] The control channel(s) structure in accordance with another embodiment is illustrated in FIG. 12. Each of the control channels 1202 ( i ) contains all the information a subscriber station needs to decode the F-PDCH. Therefore, in one embodiment, each of the channels 1202 ( i ) comprises a MAC ID block 1204 , an ARQ channel ID block 1206 , the encoder packet size block 1208 , and the F-PDCH sub-packet ID block 1210 , as well as information for sub-packet TDM/CDM sharing as described above, collectively identified as block 1212 . In addition, one of the control channels 1202 ( i ), e.g., control channel 1202 ( 1 ) comprises a block 1214 , which identifies number of transmitted control channels 1202 ( i ). Because it is desirable that all subscriber stations receive reliably the information content of the control channel 1202 ( 1 ), in one embodiment the control channel 1202 ( 1 ) is transmitted at power determined by power requirement of the subscriber station with the worst forward link quality metric. Because each of the control channels 1202 ( 2 )- 1202 ( m ) is intended for one of the subscriber stations and the base station has an information about the subscriber station forward link quality metric, the base station transmits each of the channels 1202 ( 2 )- 1202 ( m ) at the minimum power determined by power requirement of the subscriber station.
[0087] To receive the control channels 1202 ( i ) the subscriber stations must know modulation parameters of the control channels 1202 ( i ). In one embodiment, the modulation parameters and the number of possible control channels are pre-determined. Furthermore, there exists a relationship between the control channels 1202 ( i ) and the modulation parameters. In one embodiment, the modulation parameters comprise different Walsh codes, and the transmitted control channels 1202 ( i ) are encoded by Walsh codes with sequential indexes. However, one of ordinary skill in the art appreciates that other relationships are within the scope of the invention. Because in accordance with the embodiment, there is no relationship between one subscriber station and one control channel 1202 ( i ), the subscriber stations must demodulate all the transmitted control channels 1202 ( i ). Although a number of transmitted control channels 1202 ( i ) is equal to a number of subscriber stations for which information is send on a F-PDCH because the number of subscriber stations may change in accordance with the granularity of the F-PDCH as described above, the number of transmitted control channels 1202 ( i ) changes.
[0088] In one embodiment, the channels 1202 ( i ) are transmitted concurrently, consequently, each of the subscriber stations accumulates data from all the channels 1202 ( i ), and then post processes the accumulated data. During the post processing, each of the subscriber stations first demodulates the control channel 1202 ( 1 ) and decodes a MAC ID of block 1204 . The subscriber station with MAC ID identical to the MAC ID of block 1204 decodes the remaining information, and processes the sub-packet on the F-PDCH in accordance with the gathered information. The subscriber stations whose MAC IDs are not identical to the MAC ID of block 1204 decode the number of transmitted control channels 1202 ( i ) of block 1214 , cease further post processing of the control channel 1202 ( 1 ), and repeat the procedure for the next channel 1208 ( i ). Therefore, the subscriber stations have information about the number of transmitted control channels 1208 ( i ). Because as discussed there exists a relationship between the number of transmitted control channels 1208 ( i ), unless the subscriber station finds a MAC ID indicating that the channel 1208 ( i ) contains information for the subscriber station, the subscriber station attempts to demodulate only the transmitted channels 1208 ( i ).
[0089] The control channel structure in accordance with another embodiment is identical to the control channel structure as illustrated in FIG. 12, with the exception of the relationship between the control channels 1202 ( i ) and the modulation parameters. As explained above, it is desirable that all subscriber stations receive reliably the information content of the control channel 1202 ( 1 ), in one embodiment the control channel 1202 ( 1 ) is transmitted at power determined by power requirement of the subscriber station with the worst forward link quality metric. Furthermore, each of the control channels 1202 ( 2 )- 1202 ( m ) is intended for one of the subscriber stations and the base station has an information about the subscriber station forward link quality metric, consequently, the base station transmits each of the channels 1202 ( 2 )- 1202 ( m ) at the minimum power determined by power requirement of the subscriber station. The transmitted control channels 1202 ( i ) are ordered in accordance with the transmit power, and are modulated by an ordered set of modulation parameters. In one embodiment, the modulation parameters comprise different Walsh codes, and the control channel 1202 ( i ) are encoded by Walsh codes with increasing indexes in relation to the increasing transmit power. However, one of ordinary skills in the art appreciates that other relationships are within the scope of the invention.
[0090] In one embodiment, the channels 1202 ( i ) are transmitted concurrently, consequently, each of the subscriber stations accumulates data from all the channels 1202 ( i ), and then post processes the accumulated data. During the post processing, each of the subscriber stations first demodulates the control channel 1202 ( 1 ) and decodes a MAC ID of block 1204 . The subscriber station with MAC ID identical to the MAC ID of block 1204 decodes the remaining information, and processes the sub-packet on the F-PDCH in accordance with the gathered information.
[0091] The subscriber stations whose MAC IDs are not identical to the MAC ID of block 1204 decode the number of transmitted control channels 1202 ( i ) of block 1214 , cease further post processing of the control channel 1202 ( 1 ), and determine the control channel 1202 ( 2 )- 1202 ( m ) to be demodulated next. Because of the above-described relationship between the control channel's 1202 ( i ) power and index of the Walsh code by which the control channel's 1202 ( i ) is encoded, when a subscriber station attempts to decode one of the control channels 1202 ( 2 )- 1202 ( m ) and the decoding fails, then the subscriber station knows that decoding of any of the channels 1202 ( 2 )- 1202 ( m ) sent at lower power is likely to fail too. Consequently, the subscriber station next attempts to decode one of the control channels 1202 ( 2 )- 1202 ( m ) sent at a higher power. Therefore, one of ordinary skills in the art appreciates that any determination method based on ordered set may be used.
[0092] For example, in accordance with one embodiment, the determination method may utilize binary search method. If the subscriber station experiences the forward link with a good quality metric, the subscriber station demodulates the control channel with the lowest power 1202 ( m ), thus encoded by Walsh code with the highest index m. If the decoding fails, the subscriber station repeats the process with the control channel with the medium power 1202 ( m/ 2), thus encoded by Walsh code with the index m/2. If the decoding is successful, but the MAC ID indicates that the control channel 1202 ( m/ 2) does not contain information for the subscriber station, the subscriber station repeats the process with a control channel between 1202 ( m/ 2) and 1202 ( m ). The method is repeated until the subscriber station exhaust all the control channels between 1202 ( m/ 2) and 1202 ( m ), or finds a control channel 1202 ( i ) with MAC ID indicating that the control channel 1202 ( i ) is intended for the subscriber station.
[0093] In another embodiment, the subscriber station whose MAC ID is not identical to the MAC ID of block 1204 measure the power of the control channel 1202 ( i ) from the range 1202 ( 2 )- 1202 ( m ). If the measured power is higher than the power required by the subscriber station, the control channel 1202 ( i ) containing the information for the subscriber station is likely in the range 1202 ( i )- 1202 ( m ). The subscriber station can continue measuring the power, using any determination method, e.g., the above-described binary search or select a control channel from the determined range and attempt a demodulation.
[0094] The control channel structure in accordance with another embodiment is identical to the control channel structure as illustrated in FIG. 12, with the exception of the relationship between the control channels 1202 ( i ) and the modulation parameters. In accordance with the embodiment, the transmitted control channels 1202 ( i ) are ordered in accordance with the value of MAC IDs in block 1204 , and are modulated by an ordered set of modulation parameters. In one embodiment, the modulation parameters comprise different Walsh codes, and the control channel 1202 ( i ) are encoded by Walsh codes with increasing indexes in relation to the increasing value of MAC IDs in block 1204 . However, one of ordinary skills in the art appreciates that other relationships are within the scope of the invention.
[0095] Consequently, a subscriber station may use ant determination method applicable for ordered set, e.g., one of the above-described methods.
[0096] The control channel(s) structure in accordance with another embodiment is illustrated in FIG. 13. Each of the control channels 1302 ( i ) contains all the information a subscriber station needs to decode the F-PDCH. Therefore, in one embodiment, each of the channels 1302 ( i ) comprises a MAC ID block 1306 ( i ) identifying a subscriber station for which the channel 1302 ( i ) is intended, a partial MAC ID block 1308 ( i ) identifying subscriber stations for which another control channel 1302 ( i ) is intended, and information block 1310 ( i ), enabling a subscriber station identified by the MAC ID of block 1306 ( i ) to demodulate the F-PDCH. In addition, one of the control channels 1302 ( i ), e.g., a control channel 1302 ( 1 ) comprises a block 1304 identifying number of control channels 1302 ( i ). The identification of partial MAC ID is an implementation issue. In one embodiment, the MAC ID is expressed as an 8-bit number. Therefore, a subset of the bits identifies a partial MAC ID. In one embodiment, the subset comprises the most significant bits of a MAC ID.
[0097] To receive the control channels 1302 ( i ) the subscriber stations must know modulation parameters of the control channels 1302 ( i ). In one embodiment, the modulation parameters and the number of possible control channels are pre-determined. In one embodiment, the modulation parameters comprise different Walsh codes. However, one of ordinary skills in the art appreciates that other relationships are within the scope of the invention. Furthermore, there exists a relationship between the control channels 1302 ( 2 )- 1302 ( m ) and the partial MAC IDs. The relationship is determined by a method the subscriber stations with MAC ID matching the partial MAC ID a control channel 1302 ( i ) use to select the next control channel 1302 ( i ) to demodulate. One of ordinary skills in the art appreciates that such a method, consequently, the relationships is an implementation issue. In accordance with one embodiment, the partial MAC ID from block 1308 ( i ) of channel 1302 ( i ) identifies a control channel 1302 ( m - i− 1).
[0098] Because all subscriber stations must reliably receive the control channel 1302 ( 1 ), the control channel 1302 ( 1 ) is transmitted at power determined by power requirement of the subscriber station with the worst forward link quality metric. Because each of the control channel 1302 ( 2 )- 1302 ( m ) is intended for one of the subscriber stations and the base station has an information about the subscriber station forward link quality metric, the base station transmits each of the channels 1308 ( i ) at the minimum power determined by power requirement of the subscriber station.
[0099] In one embodiment, the channels 1302 ( i ) are transmitted concurrently, consequently, each of the subscriber stations accumulates data from all the channels 1202 ( i ), and then post processes the accumulated data. During the post processing, each of the subscriber stations first demodulates the control channel 1202 ( 1 ) and decodes a MAC ID of block 1306 ( 1 ). The subscriber station with MAC ID identical to the MAC ID of block 1306 ( 1 ) decodes the remaining information, and processes the sub-packet on the F-PDCH in accordance with the gathered information.
[0100] If the block 1304 indicates that there are no additional control channels 1302 ( i ), the determination method ends.
[0101] If the block 1304 indicates that there are m additional control channels 1118 ( i ), the determination proceeds as follows.
[0102] The subscriber stations with MAC ID matching the partial MAC ID of block 1108 ( 1 ) demodulate and decode the control channel 1302 ( m ), to acquire the MAC ID of block 1306 ( m ). The subscriber station with MAC ID identical to the MAC ID of block 1306 ( m ) demodulates and decodes the remaining information of the control channel 1302 ( m ), and processes the sub-packet on the F-PDCH in accordance to the gathered information. The subscriber station with MAC ID not matching the MAC ID of block 1316 ( m ) demodulates the next control channel 1302 ( 2 ) as described below. Since the subscriber station has already processed the control channel 1302 ( m ), the subscriber station continuing processing and encountering control channel 1302 ( m ) can cease further processing.
[0103] The subscriber stations with MAC ID not matching the partial MAC ID of block 1308 ( 1 ) demodulate the next control channel 1302 ( i ), i.e., the control channel 1302 ( 2 ). The subscriber station with MAC ID identical to the MAC ID of block 1316 ( 2 ) decodes the remaining information of the control channel 1302 ( 2 ), and processes the sub-packet on the F-PDCH in accordance to the gathered information. The subscriber stations with MAC ID matching the partial MAC ID of block 1318 ( 2 ) follow the processing as outlined with respect to MAC ID in block 1308 . (Thus, the subscriber stations demodulate and decode the control channel 1318 ( m− 1), to acquire the MAC ID of block 1314 ( m− 1)).
[0104] The method is repeated until the subscriber station exhaust all the control channels 1302 ( i ), or finds a control channel 1302 ( i ) with MAC ID indicating that the control channel 1302 ( i ) is intended for the subscriber station.
[0105] Code Channel Assignment Signaling
[0106] As discussed, the control channel structure of the invention may utilize the control channels of the 1xEV-DV proposal, according to the above-described embodiment. Consequently, the control channel structure of the invention must preserve or improve the functionality of the control channels of the 1xEV-DV proposal.
[0107] In accordance to the 1xEV-DV proposal, the F-PDCH sub-packet de-multiplexed into a variable number of pairs (In-phase and Quadrature) of parallel streams, and each of the parallel streams is covered with a distinct 32-ary Walsh code. The F-PDCH Walsh codes are assigned from a Walsh Space List of 28 possible assignments, starting from the top of this list.
TABLE 1 Default F-PDCH Walsh Space List 32-ary Walsh Codes 31 15 23 7 27 11 19 3 29 13 21 5 25 9 30 14 22 6 26 10 18 2 28 12 20 4 24 8
[0108] When using the F-PDCH the Walsh code assignment for the F-PPDCCH, F-SPDCCH, and the F-PDCH. Furthermore, for the F-PDCH, number of such codes and the Walsh assignments of such codes are required. The number of Walsh codes in use for the F-PDCH is transmitted on the F-SPDCCH. A system and a method for signaling the Walsh space assignment is disclosed in co-pending application serial No. 60/297,105 entitled “HANDLING THE WALSH SPACE INDICATOR FOR 1XEV-DV,” filed Jun. 7, 2001, and assigned to the assignee of the present invention.
[0109] In accordance with one embodiment of the present invention, the Walsh space is assigned in accordance with a power of the F-SPDCCH. In one embodiment, the assignment starts with a highest power F-SPDCCH and the lowest Walsh space. Accordingly, the lowest portion of the Walsh space is assigned by the highest power F-SPDCCH, the next lower portion of the Walsh space is assigned by the second highest power F-PDCH, until all the F-SPDCCH are exhausted. To save power and capacity of the F-SPDCCH, instead of listing the individual Walsh code indexes, each in the F-SPDCCH comprises the number of Walsh codes used.
[0110] For example, referring to Table 1, if the highest power F-SPDCCH assigns the Walsh space comprising the Walsh codes with indexes 31, 15, 23, 7, 27, and 11, the highest power F-SPDCCH comprises the number 6, which is the number of Walsh codes. Similarly, if the second highest power F-SPDCCH assigns the Walsh space comprising the Walsh codes with indexes 19, 3, 29, 13, 21, 5, 25, the second highest power F-SPDCCH comprises the number 6.
[0111] The subscriber station processes the plurality of F-SPDCCHs in accordance with the above-disclosed embodiments, to obtain the number of Walsh codes from each of the plurality of the F-SPDCCHs. The subscriber station further measures power of each of the plurality of the F-SPDCCH, and orders the obtained numbers of Walsh codes with the measured power. Because the subscriber station is provided with the Walsh Space List, the subscriber station can associate each of the obtained number of Walsh codes with the Walsh codes.
[0112] Those of skill in the art would understand that information and signals may be represented using any of a variety of different technologies and techniques. For example, data, instructions, commands, information, signals, bits, symbols, and chips that may be referenced throughout the above description may be represented by voltages, currents, electromagnetic waves, magnetic fields or particles, optical fields or particles, or any combination thereof.
[0113] Those of skill would further appreciate that the various illustrative logical blocks, modules, circuits, and algorithm steps described in connection with the embodiments disclosed herein may be implemented as electronic hardware, computer software, or combinations of both. To clearly illustrate this interchangeability of hardware and software, various illustrative components, blocks, modules, circuits, and steps have been described above generally in terms of their functionality. Whether such functionality is implemented as hardware or software depends upon the particular application and design constraints imposed on the overall system. Skilled artisans may implement the described functionality in varying ways for each particular application, but such implementation decisions should not be interpreted as causing a departure from the scope of the present invention.
[0114] The various illustrative logical blocks, modules, and circuits described in connection with the embodiments disclosed herein may be implemented or performed with a general purpose processor, a digital signal processor (DSP), an application specific integrated circuit (ASIC), a field programmable gate array (FPGA) or other programmable logic device, discrete gate or transistor logic, discrete hardware components, or any combination thereof designed to perform the functions described herein. A general purpose processor may be a microprocessor, but in the alternative, the processor may be any conventional processor, controller, microcontroller, or state machine. A processor may also be implemented as a combination of computing devices, e.g., a combination of a DSP and a microprocessor, a plurality of microprocessors, one or more microprocessors in conjunction with a DSP core, or any other such configuration.
[0115] The steps of a method or algorithm described in connection with the embodiments disclosed herein may be embodied directly in hardware, in a software module executed by a processor, or in a combination of the two. A software module may reside in RAM memory, flash memory, ROM memory, EPROM memory, EEPROM memory, registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art. An exemplary storage medium is coupled to the processor such the processor can read information from, and write information to, the storage medium. In the alternative, the storage medium may be integral to the processor. The processor and the storage medium may reside in an ASIC. The ASIC may reside in a user terminal. In the alternative, the processor and the storage medium may reside as discrete components in a user terminal.
[0116] The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
[0117] A portion of the disclosure of this patent document contains material, which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office patent file or records, but otherwise reserves all copyright rights whatsoever.
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Method and Apparatus for Processing Shared Sub-packets in a Communication System are disclosed. A communication system providing both voice and data services allows for a plurality of subscriber station to share a data sent in a unit of a forward traffic channel. To provide information required by the subscriber stations to determine that a unit of the forward traffic channel is shared, and to correctly decode the data, different control channel structures are described. Additionally, the control channel structures provides for more efficient signaling of code channel assignment.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of priority under 35 U.S.C. § 119 of German Application DE 10 2004 002 245.3 filed Jan. 15, 2004, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention pertains to a metering pump, with which, for example, liquid fuel can be delivered to a heater in a vehicle.
BACKGROUND OF THE INVENTION
Such metering pumps comprise, in general, a delivery plunger, which can be moved to and fro for delivering the liquid fuel and is accommodated and guided for this purpose, for example, in a guide sleeve. Due to its reciprocating movement, the plunger dips more or less deeply into the guide sleeve depending on its movement cycle. The liquid fuel is ejected in this manner from a pump ejection chamber, which is also defined by an inner surface of the guide sleeve, namely, when the delivery plunger is being moved in the direction in which the pump ejection chamber volume is minimized, or fuel can be taken up in the chamber, namely, when the delivery plunger is being moved in the direction in which the pump ejection chamber volume is maximized.
This guide sleeve is carried, in general, firmly in a carrier element, which may be part of a housing of the metering pump or in such a housing. To make it possible to guide the liquid fuel in the direction of the pump ejection chamber, a circumferential distance is present between an outer surface of the guide sleeve and the carrier element, which carries the guide sleeve per se, so that an annular flow space is formed. This leads in the direction of the pump ejection chamber. In another length area, the guide sleeve is in contact with the carrier element essentially over the entire circumferential area, so that stable mounting of the guide sleeve is ensured by press fit, on the hand, and, on the other hand, the annular channel area is axially defined and it is ensured that no liquid fuel can escape in the transition between the carrier element and the guide sleeve. To achieve the stable mounting of the guide sleeve, the latter must be made, in general, of a metallic material, so that this mounting is brought about in a comparatively short length area by the contact between the guide sleeve and the carrier element, while the annular intermediate space, in which there is no contact between the guide sleeve and the carrier element, is then formed in a longer section. This is also due to the fact that such guide sleeves are brought, in general, to the desired dimensions by a turning operation, so that, in principle, a rotationally symmetrical outer surface is obtained, as a consequence of which the load-bearing contact with the carrier element is present only in a predetermined length area.
SUMMARY OF THE INVENTION
The primary object of the present invention is to provide a metering pump which has improved operating characteristics along with a simplified and less expensive design.
This object is accomplished according to the present invention by a metering pump, especially for feeding fuel to a vehicle heater, comprising a delivery plunger, which can be moved to and fro to deliver liquid medium; a guide sleeve, which partially accommodates the delivery plunger and guides same for the reciprocating movement, wherein the guide sleeve with an inner surface thereof defines a pump ejection chamber and it defines with an outer surface thereof a channel arrangement leading to the pump ejection chamber, wherein the guide sleeve is carried in a carrier element and is in contact by its outer surface with the carrier element in a first length area essentially over the entire circumference and is located at a spaced location with its outer surface from the carrier element in a second length area, wherein the channel arrangement is provided between the carrier element and the guide sleeve in its second length area, wherein the guide sleeve has at least one support area in its second length area, with which said support area the guide sleeve is supported in relation to the carrier element.
Various advantageous aspects are obtained with the metering pump according to the present invention. Thus, the embodiment of the guide sleeve with at least one support section in the length area in which the guide sleeve also defines the channel arrangement makes it possible to achieve better distribution of the supporting or carrying action in relation to the carrier element over the length of the guide sleeve. This means that the length area in which there is essentially a full-area circumferential contact in relation to the carrier element is relieved of its support function, which is also significant for the correct functionality of the metering pump, because better distribution can be obtained over the entire length area of the guide sleeve. This in turn makes it possible not to manufacture the guide sleeve of metal, but, e.g., of a plastic. In case of the configuration known from the state of the art, the use of a guide sleeve made of plastic implies, in principle, the problem that if the carrying function is limited to a comparatively short length area, namely, the length area in which no annular channel is formed, there is a risk of tilting of the guide sleeve because of the markedly higher elasticity and flexibility of the plastic material compared with metallic material. However, this risk of tilting can also be prevented from occurring even when a plastic material is used due to the fact that additional supporting is provided in the metering pump according to the present invention in the length area that is also used to feed the fuel. On the other hand, the use of plastic material makes it possible to design the guide sleeve as is specified in the metering pump according to the present invention, i.e., with support sections in certain length areas, i.e., with a shape that is, in principle, not rotationally symmetrical, e.g., by manufacturing according to an injection molding method. Due to the possibility of using materials other than metal due to the preset shape, the material can in turn be selected such that the operating characteristics are improved, namely concerning the frictional characteristics between the delivery plunger movable to and fro and the guide sleeve. Especially low-friction plastics can be used here, so that the service life of a metering pump designed according to the present invention can be markedly increased.
Provisions may be made, for example, in the metering pump according to the present invention for the guide sleeve to have an outer surface that is set back in relation to the first length area in its second length area in at least one circumferential area. It is possible now, for example, to provide a support section projecting over the set-back outer surface in the area of the set-back outer surface.
To obtain a support function in the second length area as well, which approximately corresponds to the support in the first length area, it is proposed, furthermore, that the support section project over the set-back outer surface up to the level of the outer surface in the first length area.
To provide a transition between the channel arrangement and the pump ejection chamber, it is proposed that at least one passage opening leading to the pump ejection chamber be provided in the area in which the first length area adjoins the second length area.
To obtain the largest possible flow cross section in the area of the channel arrangement despite the possibility of also providing a support for the guide sleeve in relation to the carrier element in the second length area, it is proposed, furthermore, that a set-back outer surface be provided at two circumferential areas, which are located essentially opposite each other, in the second length area.
Furthermore, the metering pump according to the present invention may be designed such that the guide sleeve defines the pump ejection chamber essentially in its first length area and it defines the channel arrangement essentially in its second length area.
According to another aspect of the present invention, the guide sleeve in the metering pump may be designed such that in its second length area, the guide sleeve has an outer contour that corresponds to the outer contour of the guide sleeve in the first length area and is interrupted at at least one circumferential area by a depression, which is open toward the outside and forms the channel arrangement at least partially.
As was already mentioned above, it is a special aspect of the present invention that, especially also due to the design embodiment, the guide sleeve can be made of a plastic material, with the advantage that it is possible not only to use a material that is less expensive and can also be processed more easily and can be handled in an easier manufacturing process, but also to markedly improve the sliding properties during the guiding of the delivery plunger.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which a preferred embodiment of the invention is illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be described below with reference to the drawings attached. In the drawings:
FIG. 1 is a longitudinal sectional view of a metering pump, cut along line I-I in FIG. 2 ;
FIG. 2 is a cross-sectional view of the metering pump shown in FIG. 1 , cut along line II-II in FIG. 1 ;
FIG. 3 is an enlarged detail of III in FIG. 2 ; and
FIG. 4 is a perspective view of a guide sleeve used in the metering pump according to FIG. 1 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings in particular, a metering pump designed according to the present invention is generally designated by 10 in FIG. 1 . This metering pump 10 can be used to deliver liquid fuel from a tank provided in a motor vehicle in the direction of a heater, e.g., a parking heater or an auxiliary heater.
The metering pump 10 comprises a housing arrangement 12 , which is composed of a plurality of components. Thus, a housing end part 14 is provided, on which an inlet pipe connection 16 , which is to be connected with a flexible tube connection, is provided. Furthermore, a filter 18 is provided in the housing end part 14 . A housing outer wall 20 is rigidly connected with the housing end part 14 in the outer circumferential area, and the housing outer wall 20 is connected with another housing end part 22 at its other axial end area, axially being related to a longitudinal axis of the entire metering pump 10 . An elongated, sleeve-like carrier element 24 is carried at this additional housing end part 22 in the radially inner area, radially being again related to the longitudinal axis A. This sleeve-like carrier element 24 carries, in turn, a nonreturn discharge valve 26 , which comprises a part 28 providing essentially a valve seat and an outlet pipe connection 30 that can be connected with a flexible tube. A spring-pretensioned valve ball 32 , which prevents the liquid fuel being delivered into the outlet pipe connection 30 from flowing back, is seated on the valve.
An electromagnet coil designated generally by 34 is carried on the housing end part 14 and the carrier element 24 . The housing end part 14 , a coil carrier 36 of the electromagnet coil 34 and the carrier element 24 define a pump inlet chamber 38 , to which an inlet opening 40 provided in the housing end part 14 leads.
The carrier element 24 , which has, as can be recognized from FIG. 2 , generally an annular cross section, carries with its inner surface a guide sleeve 42 . This guide sleeve 42 , which likewise has a generally annular cross section and will be described in detail below with reference to FIGS. 3 and 4 , has an interior space 44 , which has, for example, a circular cross section. This interior space 44 , which is defined by an inner surface 46 , defines a pump ejection chamber 48 in cooperation with the part 28 of the valve arrangement 26 and is used, furthermore, to guide a delivery plunger 50 for moving to and fro in the direction of the longitudinal axis A. In its area not engaging the guide sleeve 42 , the delivery plunger 50 carries an armature 52 . Furthermore, the delivery plunger 50 is pretensioned by a pretensioning spring 54 such that it tends to move as far out of the interior space 44 of the guide sleeve 42 and to close the inlet opening 40 in the process with a sealing element 56 , which is carried, for example, at the armature.
The guide sleeve 42 , which is preferably made of a plastic material according to the principles of the present invention, is of an elongated shape and has essentially two length areas. The guide sleeve 42 is shaped in a first length area 58 such that the circumferential contour of an outer surface 60 of the guide sleeve corresponds to the circumferential contour of an inner surface 62 of the carrier element 24 . This inner surface 62 is provided, for example, with an essentially circular contour in the example being shown, so that the guide sleeve 42 is likewise made with a circular outer surface in the first length area 58 . Provisions may be made in this connection for the outside dimension of the guide sleeve 42 to have a certain oversize compared with the inner dimension of the carrier element 24 at least in this length area 58 , so that a press fit is provided, in particular, in this first length area 58 with the guide sleeve 42 inserted into the carrier element 24 and stable mounting of the guide sleeve 42 is thus ensured.
In a second length area 64 , the shape of the outer surface of the guide sleeve 42 differs from the shape of the inner surface 62 of the carrier element 24 . It is recognized especially in FIG. 2 that the guide sleeve 42 is flattened at two circumferential areas located opposite each other, so that essentially flat, i.e., noncurved outer surface areas 70 , 72 are formed. These outer surface areas 70 , 72 are located at spaced locations from the inner surface 62 of the carrier element 24 , so that a channel arrangement 74 is created between the carrier element 24 and the guide sleeve 42 in this second length area 64 . This channel arrangement 74 joins the inlet chamber 38 and leads to passage openings 76 , which are provided in the outer surface areas 70 , 72 in the adjoining area to the first length area 58 of the guide sleeve 42 and lead into the interior space 44 . The position of these openings 76 relative to the longitudinal extension of the guide sleeve 42 is selected to be such that when the delivery plunger 50 is maximally moved out of the guide sleeve 42 , the end of the delivery plunger still engaging the guide sleeve 42 does not cover the openings 76 any longer or it does so only incompletely. With the delivery plunger 50 dipping maximally into the guide sleeve 42 , i.e., in case of the minimum volume of the pump ejection chamber 58 , the delivery plunger 50 covers the openings 76 , so that a connection between the pump ejection chamber 48 and the channel arrangement 74 and consequently the pump inlet chamber 38 is now interrupted.
It is, furthermore, recognized from FIGS. 3 and 4 that a support section 78 , 80 is provided in each of the flattened surface areas 70 , 72 . The support sections 78 , 80 extend in the example being shown from the end area of the guide sleeve 42 located close to the inlet chamber 38 into the area in which a particular passage opening 76 is formed. The amount of projection of the support sections 78 , 80 over the respective flattened surface area 70 , 72 is selected to be such that these support sections 78 , 80 extend radially approximately up to the level of the outer surface 60 in the first length area 58 , doing so in the circumferential area in which a corresponding support section 78 , 80 will then also adjoin.
Thus, not only is a stable hold of the guide sleeve, which is secured against evading movements, achieved in the first length area 58 when the guide sleeve 42 is inserted into the carrier element 24 , but it is also ensured, despite the fact that the channel arrangement 74 is provided, that stable supporting is provided for the guide sleeve 42 in the second length area 64 as well in practically any direction, so that the guide sleeve 42 can nevertheless provide a stable guiding function for the delivery plunger 50 despite the fact that it can be made of a plastic material, which is considerably more flexible than a metallic material.
The function of the metering pump 10 according to the present invention will be described below.
If the delivery plunger 50 is in the position shown in FIG. 1 , in which the volume of the pump ejection chamber 48 has its maximum, and the electromagnet arrangement 34 is then excited, the armature 52 moves together with the delivery plunger 50 in the direction in which the volume of the pump ejection chamber decreases. The delivery plunger 50 completely covers the openings 76 in the guide sleeve 42 already after a short delivery stroke, so that no fuel contained in the pump ejection chamber 48 at that point in time can be displaced back in the direction of the inlet chamber 38 via the openings 76 . During a subsequent further minimization of the volume of the pump ejection chamber 48 , the fuel contained therein is displaced through an outlet opening 84 of the part 28 , so that the valve ball 32 will also lift off from its valve seat and the fuel being delivered can be released via the outlet pipe connection 30 while overcoming the valve arrangement 26 . Liquid fuel is also drawn at the same time into the inlet chamber 38 during this delivery cycle due to the increase in the volume of the inlet chamber 38 due to the fact that the delivery plunger 50 dips more deeply into the guide sleeve 42 .
If the excitation of the electromagnet arrangement 34 is terminated after the minimum volume of the pump ejection chamber 48 had been reached, the delivery plunger 50 returns under the pretension in the direction of increasing pump ejection chamber volume and a vacuum is generated during this phase in this pump ejection chamber 48 as long as the openings 76 are still being covered by the delivery plunger 50 . At the same time, overpressure is generated in the inlet chamber 38 by the delivery plunger 50 moving out of the guide sleeve 42 . A certain percentage of the liquid fuel can now escape through the inlet opening 40 . However, as the escape via the inlet opening 40 is becoming increasingly difficult and the connection between the pump ejection chamber 48 and the inlet chamber 38 is released, the fuel is then displaced via the channel arrangement 74 into the pump ejection chamber 48 , so that another quantity of fuel is then delivered in the direction of the outlet pipe connection 30 during a subsequent reduction of the volume of the pump ejection chamber 48 .
Due to the use of a guide sleeve made of a plastic material, which can be optimized in terms of its sliding properties, on the one hand, and concerning the resistance to the medium to be delivered, on the other hand, the wear due to the frictional contact between the delivery plunger 50 and the guide sleeve 42 can be markedly reduced. Due to the fact that the guide sleeve 42 is also supported in the length area in which it defines the channel arrangement 74 together with the carrier element 24 , it is ensured at the same time that very stable mounting is nevertheless achieved if plastic material is used for this guide sleeve 42 .
It shall be pointed out that the shape of the guide sleeve 42 may, of course, be different in its second length area 64 . For example, splitting at an angle ratio other than 180° is possible. It is, of course, also possible to provide the channel arrangement 74 by groove-like depressions of a different shape, which are open radially outwardly and extend along the guide sleeve 42 to one or more of the openings 76 . The variant that can be recognized in FIGS. 3 and 4 can ultimately also be interpreted such that an interruption of the outer surface 60 that otherwise corresponds to the shape in the first length area 58 is generated in certain circumferential areas in the second length area 64 , so that support of the guide sleeve 42 is achieved not only via the two support sections 78 , 80 , but the guide sleeve is also supported in relation to the carrier element 24 in the circumferential areas 82 , 84 located between the two surface areas 70 , 72 , which are flattened and thus provide the groove-like depressions. In case of corresponding stability of the guide sleeve 42 , it would optionally be possible to ensure support only via such circumferential areas 82 , 84 , which also act as support areas, and to do away with the support sections 78 , 80 .
While a specific embodiment of the invention has been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.
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A metering pump, especially for feeding fuel to a vehicle heater, comprising a delivery plunger ( 50 ), which can be moved to and fro for delivering liquid medium, a guide sleeve ( 42 ), which partially accommodates the delivery plunger ( 50 ) and guides same for the reciprocating movement, wherein the guide sleeve ( 42 ) with an inner surface ( 46 ) thereof defines a pump ejection chamber ( 48 ) and it defines with an outer surface ( 60 ) thereof a channel arrangement ( 74 ) leading to the pump ejection chamber ( 48 ), wherein the guide sleeve ( 42 ) is carried in a carrier element ( 24 ) and is in contact with the carrier element ( 24 ) by its outer surface ( 60 ) essentially over the entire circumference in a first length area ( 58 ) and is located with its outer surface at a spaced location from the carrier element ( 24 ) in a second length area ( 64 ), wherein the channel arrangement ( 74 ) is provided between the carrier element ( 24 ) and the guide sleeve ( 42 ) in its second length area ( 64 ), is characterized in that in its second length area ( 64 ), the guide sleeve ( 42 ) has at least one support area ( 78, 80, 82, 84 ), with which it is supported in relation to the carrier element ( 24 ).
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FIELD OF THE INVENTION
[0001] The invention relates to a safety access to a room, in particular a class room, The safety access shall protect people in the room, for example teachers and students from a homicidal attacker.
BACKGROUND OF THE INVENTION
[0002] Safety accesses that allow only authorized persons to enter are known in the art.
BRIEF SUMMARY OF THE INVENTION
[0003] The object is achieved by a safety access to a room in particular a class room with a safety lock, an entry from outside and an exit to the room, comprising a first door in the exit and a locking door which renders the locking chamber lockable.
[0004] The safety access includes a safety lock with a locking chamber and an entrance from an outside and an exit towards the room. The safety lock is a hallway, an ante chamber or similar which can also be arranged in the room and which can only be entered through the entrance and can only be exited through the exit. A person who wants to enter the room from outside has to move through the safety lock. The safety lock is advantageously closed above so that nobody can climb over it. The designations entry and exit have been selected for unambiguous identification, both are openings of the safety lock through which the safety lock can be entered and exited. Through the entrance the safety lock can be entered from outside and can be exited towards the outside and through the exit the safety lock can be exited towards the room and entered from the room. “Outside” is to be viewed relative to the room, it relates for example to a hallway in a building for reaching the room.
[0005] The locking chamber can be a portion of the safety lock or a room adjacent to the safety lock wherein the room is accessible from the safety lock and is advantageously not discernible as a proprietary separable room. The locking chamber is configured for locking up an unauthorized person, in particular a homicidal attacker which wants to penetrate the room.
[0006] The safety lock includes a first door in an exit from the safety lock towards the room by which the exit and thus the access to the room is closable. Furthermore the safety lock includes a locking door by which the locking chamber is lockable. An unauthorized person can be locked in the locking chamber by closing the locking door.
[0007] Advantageously the locking chamber is arranged opposite to the entrance, so that a nervous person with therefore reduced attention for his or her environment and who runs through the entrance into the safety lock with the intention to enter the room accidentally runs into the locking chamber of the safety lock where the person is lockable by closing the locking door. The exit from the safety lock into the room is advantageously arranged laterally relative to the entrance and to the locking chamber so that a nervous and inattentive person does not unintentionally enter the room from the safety lock through the exit.
[0008] The locking chamber and the room can respectively have proprietary doors. One configuration provides a common door which forms the first door in the exit from the safety lock to the room, as well as the locking door by which the locking chamber is lockable. Opening the first door which simultaneously forms the locking door simultaneously facilitates locking the locking chamber so that a person is lockable in the locking chamber and the room can be exited.
[0009] Advantageously the locking chamber is transparent towards the room so that an impression is conveyed to a nervous and inattentive person, in particular a homicidal attacker that he or she can enter the room through the locking chamber. Thus, the locking chamber does not have to be transparent in its entirety. A transparent portion suffices which conveys the impression of a pass through. In particular the locking chamber includes a glass pane or a transparent plastic pane through which the room with the people in the room is visible from the locking chamber and at least upon first glance the impression of an access to the room is conveyed. Advantageously the glass or transparent plastic pane is bullet resistant.
[0010] An alternative to transparency is a dummy door in the locking chamber which cannot be opened or cannot be opened from the locking chamber and behind which a homicidal attacker anticipates the room into which he wishes to enter.
[0011] Advantageously the first door in the exit from the safety lock to the room cannot be opened by hand from the safety lock. From the safety lock the first door can for example only be opened with a key. Otherwise the first door can be opened from the room by hand or with a key or via remote control from the room or from another location outside of the safety lock. An unauthorized person without a key does not get into the room through the safety lock when the first door is closed.
[0012] An embodiment of the invention provides a quick drive for the locking door for locking the locking chamber, The quick drive is a drive which closes the locking door quickly enough so that escaping the locking chamber during locking the locking door is impossible. The quick drive can operate mechanically for example with one or plural springs. It can operate electro mechanically with an electro magnet or an electric motor, pneumatically or hydraulically. The enumeration is exemplary but not final.
[0013] Advantageously the locking door locks the locking chamber self-acting when a person enters the locking chamber, This is for example provided with a light barrier, a motion detector or by depressing a door handle of a dummy door which cannot be opened by depressing the door handle. Triggering the locking door by a person which is in particular in the room is also possible.
[0014] An embodiment of the invention provides a constriction device for fixating a person in the locked locking chamber. The fixation does not have to be complete, however it restricts the movement of the person to use a weapon or to exercise force to relieve himself or herself from the locking chamber significantly. The restraining device can include a moving wall or another device which moves into the locking chamber and presses a person in the locking chamber against an opposite wall.
[0015] A configuration of the invention provides one or plural bags that are inflatable by a pressure medium like an air bag as a constriction device which can be inflated or filled in order to constrict the locking chamber and to fixate a person in the locking chamber, Differently from an air bag the bag or the bags of the restraining device according to the invention retain their interior pressure until the interior pressure is released. The pressure medium can be a liquid or a gas, a pyrotechnic unfolding of the bag or bags is also possible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The invention is subsequently described in more detail based on an embodiment described in more detail with reference to drawing figures, wherein:
[0017] FIG. 1 illustrates a class room with a safety access according to the invention; and
[0018] FIG. 2 illustrates the safety access according to the invention with a locked locking chamber.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The class room 1 illustrated in FIG. 1 which generally represents a chamber or a room in a building includes a safety access 2 according to the invention with a safety lock 3 which protects students and teachers in the class room or generally people in the room against a homicidal attacker 4 . The safety lock 3 is a short hall way or a small ante chamber in the class room 1 through which the class room 1 is entered or exited. The safety lock 3 connects to a wail opening 5 like a door opening in a wall 6 of the class room 1 . The wall opening 5 is also designated as an entrance 7 of the safety lock 3 through which the safety lock 3 can be entered from an outside and exited towards the outside, Viewed from above the safety lock 3 in the embodiment is U-shaped with a flat side wall 8 and a semi cylindrical face wall 9 which is arranged opposite to the entrance 7 . The side wall 8 and the face wall 9 in the embodiment are made from bullet resistant glass or bullet resistant plastic material so that a homicidal attacker which runs quickly and nervously and therefore with low attention for his environment through the entrance 7 into the safety lock has the impression that he can walk straight into the class room 1 since he sees people in the room through the transparent wall 8 and the face wall 9 of the safety lock 3 .
[0020] The safety lock includes an opening opposite to the flat wall 8 wherein the opening is designated as an exit 10 and through which the class room 1 is entered from the safety lock 3 or vice versa. The class room 1 is exited through the safety lock 3 . In the exit 10 the safety lock 3 includes a first door 11 which is closed in FIG. 1 , this means it closes the exit 10 . The first door 11 can be opened by hand by depressing a door handle 12 only from the class room 1 , however not from the safety lock 3 . The first door 11 can be opened from the safety lock 3 with a key or for example by typing in a code. Also a remotely controlled opening of the first door 11 can be possible, however, as stated supra there is no option to open the first door 11 by hand from the safety lock 3 . To a person like the homicidal attacker 4 who runs into the safety lock 3 quickly and with a low level of attention for his environment the first closed door 11 on its one side looks like an open door of the entrance 7 through which the safety lock 3 can be entered from an outside. The safety lock 3 is closed on all sides and covered on top so that there is no option to enter the class room 1 when the first door 11 is closed like illustrated in FIG. 1 , this means it closes the exit 10 of the safety lock 3 which leads into the class room 1 . Therefore the homicidal attacker 4 runs through the entrance 7 straight into and through the safety lock 3 until he hits the transparent face wail 9 that is semi cylindrical in the embodiment which would typically subdue him already. As soon as the homicidal attacker 4 or another unauthorized person is in the semi cylindrical face wail 9 of the safety lock 3 the first door 11 which is simultaneously a locking door 13 is opened, wherein the first door 11 is pivoted into the safety lock 3 . The first door 11 is pivoted by 90° into the safety lock 3 so that it locks the attacker 4 in the semi cylindrical face wall 9 of the safety lock 3 whose interior forms a locking chamber 14 . In this locking position in which the first door 11 locks the homicidal attacker 4 in the locking chamber 14 the first door 11 which simultaneously forms the locking door 13 cannot be opened from the locking chamber 14 . The homicidal attacker is caught in the locking chamber 14 until security opens the locking door 13 and arrests the attacker.
[0021] Opening the first door 11 which simultaneously forms the locking door 13 and pivoting it by 90° into the locking position in which the first door and thus the locking door 13 locks the locking chamber 14 is performed self-acting with a non illustrated quick drive which includes for example a spring for example a spiral spring or pneumatically. The quick drive can be triggered by remote control from the class room 1 and/or automatically for example by a light switch or a motion detector which determines when the locking chamber 9 is entered by the attacker 4 .
[0022] In the entrance 7 a conventional room door can be provided which opens in outward direction or away from the first door 11 In the embodiment no door is provided in the entrance 7 . The safety lock 3 can have another shape than the drawn shape and the described shape and transparent bullet resistant walls 8 and 9 are not mandatory but are advantageous.
[0023] Two gas tight bags 15 are arranged at inner corners between the locking door 13 and the semi cylindrical face wall 9 wherein the bags are inflatable like air bags with compressed gas or pyrotechnically, however, differently from an air bag they maintain an interior pressure until the interior pressure is released, In the embodiment the bags 15 inflate into cylinders as illustrated in FIG. 2 which illustrates the inflated bags 15 . The bags 15 form a constriction device 16 which fixates the homicidal attacker 4 in the locking chamber 14 or at least significantly reduce his mobility.
[0024] Since the first door 11 which simultaneously forms the locking door 13 is opened when locking the locking chamber 14 , this means the first door 11 opens the exit 10 , an escape path 17 opens when the locking chamber 14 is locked wherein the escape path leads from the class room 1 through the exit 10 and the safety lock 3 in outward direction.
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A safety access to a room in particular a class room with a safety lock, an entry from outside and an exit to the room, comprising a first door in the exit and a locking door which renders the locking chamber lockable.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.
BACKGROUND
[0002] 1. Field of the Invention
[0003] This invention relates to dry stretched polyolefin (PP, PE, and PP/PE/PP) microporous membranes as battery separators, specifically to the continuous method of making the membrane separators.
[0004] 2. Discussion of Prior Art
[0005] In batteries, the anode and cathode are separated from one another by a separator. Today, “lithium batteries” are very popular because they are able to generate high-energy outputs. The lithium battery market can be divided into two groups, the “primary” lithium battery and the “secondary” lithium battery. The primary lithium battery is a disposable battery, while the secondary lithium battery is a rechargeable battery.
[0006] The rechargeable lithium battery technology was first commercialized by Sony in 1992. Since then, this new type of high-energy rechargeable batteries has been widely used in consumer markets, such as computer, camcorder and cellular phone. More applications are being developed. One of them is the Electric Vehicle (EV) and the Hybrid Electric Vehicle (HEV) applications.
[0007] However, the rechargeable lithium batteries for EV and HEV applications are significantly larger than the consumer rechargeable lithium batteries. The separator used in the batteries needs much more square footage than that in the consumer batteries. In the EV and HEV batteries, the unit cost of the separator needs to be much lower to make the EV and HEV batteries commercially possible. In addition, the cost of the separator in non-rechargeable lithium battery remains relatively high in comparison to that of the separators in other types of batteries.
[0008] In summary, there is a strong need for low-cost separators for lithium batteries, especially for rechargeable lithium battery.
[0009] The separators for lithium batteries can be made from polyolefin basically with two types of processes in the prior art: dry-stretch process and solvent-stretch process. The solvent-stretch process (such as U.S. Pat. Nos. 4,539,256; 4,726,989) usually costs more than the dry-stretch process, and it creates environmental issues. It is not our interest. Our focus is on the clean dry-stretch process for the micro-porous membranes as separators for the lithium batteries.
[0010] Polyolefin, as used herein, refers to a class or group name for thermoplastic polymers derived from simple olefins. Exemplary polyolefins include polyethylene and polypropylene. Polyethylene refers to, for example, polymers and copolymer substantially consisting of ethylene monomers. Polypropylene refers to, for example, polymers and copolymers substantially consisting of propylene monomers.
[0011] Developed in the prior art are single-ply and multiply of dry-stretch microporous membrane from polyolefin resins, including polypropylene (PP) and polyethylene (PE), with at least three separate steps: (a) film extrusion (blown film or slit film), (b) annealing, and (c) stretching, as described in U.S. Pat. Nos. 3,426,754; 3,558,764; 3,679,538; 3,801,404; 3,801,692; 3,843,761; 4,138,459; 4,994,335 and 5,173,235.
[0012] The term, multiply, herein is defined as more than one ply of film or membrane stacked together and then rolled up into a big roll. The adhesion between plies is minimum, and the multiply films or membranes can be easily deplied into multiple single-ply film or membrane. So, multiply can be two-ply, four-ply, or eight-ply. In contrast, the term, multi-layer, herein is defined as more than one layer of film adhered together with a reasonably good adhesion. The multi-layer film (or membrane) can be handled as a single-ply film (or membrane). So, multi-layer can be bilayer, tilayer, penta-layer. For example, PP/PE/PP trilayer membrane means that the two layers of PP membrane sandwich one layer of PE membrane with a reasonably good adhesion, and that the trilayer can be handled as a single-ply membrane without losing its integrity.
[0013] The terms, microporous membrane and membrane, herein imply the open-cell microporous membrane.
[0014] In the prior art, U.S. Pat. No. 3,801,692, a cold stretching was applied right before hot stretching, and the stretched membrane gave a higher porosity.
[0015] In the prior art, U.S. Pat. No. 3,843,761, right after cold stretching, the precursor film was hot stretched in a plurality of discrete hot stretching increments. The obtained stretched microporous membrane had greater gas flux.
[0016] In the prior art, U.S. Pat. No. 4,058,582, more than two plies of precursor film were simultaneously stretched for the first time. The surface properties of microporous membranes were significantly improved.
[0017] In the prior art, U.S. Pat. No. 4,138,459, an additional heat relaxing step was added to the end of the hot stretching process, and the dimensional stability of the final membrane was improved with a significantly lower shrinkage.
[0018] In the recent multi-layer products (PP/PE/PP trilayer and PP/PE bilayer separators) as described in U.S. Pat. Nos. 5,565,281; 5,691,077; 5,952,120, the process also includes three separate steps: film extrusion, annealing and stretching. The extruded films are rolled up first into big film rolls, and the film rolls are then unrolled and fed to an oven for annealing. The annealed films are rolled up into multiply big rolls, and the annealed rolls are then unrolled and fed to another oven for stretching into membranes. The stretched membranes from the oven are rolled up into rolls with desired length and filter sent for deplying and slitting separately.
[0019] The disadvantages of the conventional process with separate steps are the following:
[0020] 1. Yield loss due to many more start-ups and endings of the film rolls.
[0021] 2. Potentially less stable product quality due to the start-up and ending of each step
[0022] 3. More oven idle time during the change of film rolls
[0023] 4. More space and film-roll/inventory management is needed for the intermediate products. It adds extra operation cost.
[0024] 5. Need more manpower for more separate steps of operation. It adds extra operation cost.
[0025] 6. Potentially more maintenance needed due to much more frequently machine on and off, especially with the ovens for annealing and stretching.
[0026] As described in U.S. Pat. Nos. 3,426,754; 3,558,764; 3,679,538; 3,801,404; 3,801,692; 3,843,761; 4,138,459; 4,994,335 and 5,173,235, the films (either blown film extrusion or slit film extrusion) was extruded with the state-of-the-art film extrusion machine technology for packaging films, which require as fast as possible. However, in the process for the dry stretch membranes, the fast film extrusion speed is not compatible with rest of the processes in ovens. It made the overall process break into three separate steps, which are undesirable. Even though the state-of-the-art film extrusion line can be run faster for multi-rolls for the followed separate processes in the oven, the obtained precursor film and membranes lost some products during start-up and ending in the separate oven processes. It lost the production efficiency.
[0027] Accordingly, there is a strong need to reinvent a process for low-cost membrane separators.
SUMMARY OF THE INVENTION
[0028] A continuous method for making microporous polyolefin (PP, PE or PP/PE/PP trilayer) membrane for use in battery separator having a thickness ranging from about 0.2 mil to about 4.0 mil comprising the sequential connected steps of: extruding multiple parison with multiple smaller film extrusion lines; collapsing the parison onto itself to form a flat sheet comprising multiple plies; annealing the multiply flat-sheet precursor films; stretching the multiply flat-sheet precursor films; and winding up the multiply flat-sheet membranes.
[0029] The novelty of this invention is to use multiple small film extrusion lines and to run at a line speed compatible with the speed of the following annealing step and then the following cold stretching step and then the following hot stretching step and then the following relaxing step. And, the sequential steps of making the dry-stretch membrane as described above are run continuously from film extrusion to film annealing and to film stretching without stop. In contrast, in the conventional process with separate steps, a single large film extrusion line is used to extrude the multiple rolls at a much faster speed. Then the multiple collected rolls of film are unrolled and fed to an annealing oven and collected as annealed rolls. The rolls of the collected annealed film are unrolled and fed to a stretching oven (cold and hot stretch) for the membrane rolls.
[0030] In this invention of the continuous process, the yield of the product is much higher; the operation cost is lower; the machine usage time is much higher; the more stable process is potentially for more stable quality product.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] [0031]FIG. 1 schematically illustrates the continuous process of making multiply PP membranes or multiply PE membranes, in which each ply has a thickness ranging from 0.2 mil to 2 mil.
[0032] [0032]FIG. 2 schematically illustrates the film-extrusion set-up for making multiply PP/PE/PP trilayer precursor films. The combined multiply PP/PE/PP precursor films are continuously fed to annealing oven for annealing and bonding between PP and PE layers.
REFERENCE NUMERALS IN DRAWINGS
[0033] [0033] 1 . Extruder
[0034] [0034] 2 . Die
[0035] [0035] 3 . Air Ring
[0036] [0036] 4 . Collapsing frames and collapsing rolls
[0037] [0037] 5 . Annealing Oven
[0038] [0038] 6 . Quenching Rolls
[0039] [0039] 7 . Cold-stretching rolls
[0040] [0040] 8 . Stretching Oven
[0041] [0041] 9 . Quenching Rolls
[0042] [0042] 10 . Winder Roll
[0043] [0043] 11 . Two-ply collapsed PP precursor films with two edges trimmed
[0044] [0044] 12 . one of the two-ply PP film 11 .
[0045] [0045] 13 . one of the two-ply PP film 11 .
[0046] [0046] 14 . Two-ply collapsed PE precursor films with two edges trimmed
[0047] [0047] 15 . non-bonded PE/PP bilayer
[0048] [0048] 16 . one-ply PE from 14 .
[0049] [0049] 17 . two-ply PP film
[0050] [0050] 18 . non-bonded PP/PE bilayer
[0051] [0051] 19 . two-ply non-bonded PP/PE/PP trilayer films
[0052] [0052] 20 . four-ply non-bonded PP/PE/PP trilayer films
DESCRIPTION OF THE INVENTION
[0053] The present invention shall be described in further detail below by way of the following detailed description and the non-limiting examples.
[0054] The battery separators according to the instant invention of continuous process comprises singly-ply polyolefin (preferably PP or PE) microporous membranes, the thickness of which ranges from 0.2 mil to 2.0 mil. One mil is equal to 0.001 inch. The instant invention uses one or multiple small film-extrusion lines, preferably four blown-film extrusion lines, placed directly before annealing oven at a line speed compatible with the line speed of the annealing process in the annealing oven. So, the extruded multiple-ply films from multiple film-extrusion lines can be continuously and directly fed to the annealing oven. Following that, the exit of the annealing oven is aligned with the entrance of stretching oven, which is composed of cold stretching section, then hot stretching section, and then relaxing/heat-set section. At the end of the stretching oven, a winder collects the stretched membrane cut at the desired length for further separate deplying and slitting process. The process of the instant invention produces the dry-stretch microporous membrane separator continuously and directly from extrusion to annealing and to stretching. The process of the instant invention provides the advantages of (1) higher yield, (2) more stable quality products, (3) more machine time usage, (4) no need to handle and manage the intermediate product rolls, (5) less manpower needed and (6) less maintenance with this continuous process.
[0055] In summary, the inventive continuous process provides a big jump in production efficiency by converting a single large fast film extrusion line into multiple smaller film extrusion lines. The latter runs continuously at a compatible speed with the followed annealing and stretching operations.
[0056] [0056]FIG. 1 shows an example of the set-up for the continuous production line for multiply PP or PE membranes, in which each ply has a thickness ranging from 0.2 mil to 2 mil. Extruder 1 is hooked up with a rotational circular die 2 . The die 2 extrudes a tubular film going through an air ring 3 to form a bubble. The bubble is collapsed by a pair of collapsing frames 4 and by a pair of collapsing rolls 4 to form two-ply films. Four two-ply films are continuously fed to an annealing oven 5 . At the exit of the annealing oven 5 , the total eight-ply annealed films are quenched with a pair of quenching rolls 6 . The eight-ply quenched, annealed films are continuously fed through two pair of cold-stretching rolls 7 , and then through an oven 8 for stretching. At the exit of the stretching oven 8 , the eight-ply stretched membranes are quenched with a pair of quenching rolls 9 before the eight-ply membranes are collected on a winder roll 10 .
[0057] [0057]FIG. 2 shows an example of the film-extrusion set-up for making multiply PP/PE/PP trilayer precursor films, in which each ply has a thickness ranging from 0.6 mil to 4 mil. Two-ply collapsed PP precursor films 11 with two edges trimmed are separated into two separate plies of films, 12 and 13 . Two-ply collapsed PE precursor films 14 with two edges trimmed are separated into two separate plies of films, part of 15 and 16 . One ply of PP film 12 and one ply of PE film from trimmed PE film 14 form PP/PE non-bonded bilayer 15 . Below the extrusion lines, a non-bonded PP/PE bilayer 18 is continuously fed to combine with two-ply PP film 17 and with PE/PP non-bonded bilayer 15 to form two-ply non-bonded PP/PE/PP trilayer films 19 . The two-ply non-bonded PP/PE/PP trilayer films 19 are combined with another stream of two-ply non-bonded PP/PE/PP trilayer films to form four-ply non-bonded PP/PE/PP trilayer films 20 . The combined four-ply PP/PE/PP precursor films are continuously fed to annealing oven for annealing and bonding between PP and PE layers. Then, the annealed films are continuously fed through the cold stretching unit and through the hot-stretching oven to form PP/PE/PP trilayer membrane as described in FIG. 1. In this invention, the process is continuous while in the prior art U.S. Pat. No. 5,952,120, the process is comprised of separate steps.
[0058] The detailed running conditions in the annealing and stretching ovens are mostly described in the prior art for dry-stretch polyolefin microporous membranes. For example, annealing temperature, stretching temperature, line speeds in the oven, cold stretching ratio, hot stretching ratio and heat-set/relaxing ratio can be the same as or different from those described in the prior art, U.S. Pat. No. 4,138,459 for multiply (PP or PE) single-layer separator, U.S. Pat. No. 5,952,120 for multiply PP/PE/PP trilayer separator, U.S. Pat. No. 6,057,060 for multiply ultra-thin (PP or PE) separator. They need to be adjusted based on different grades of PP or PE raw materials used.
[0059] The following lists an example of production efficiency advantage with the continuous method described herein. Taking the example shown in FIG. 1, Table 1 list the comparison of production efficiency between the continuous process and the process comprised of separate steps.
TABLE 1 Comparison of production efficiency between the separate process and the continuous process Product Yield Runnable Machine Operation Cost Productivity Index PY Usage, RMU OC PY * RMU/OC Separate Processes 68% 80% 100% 54.4% Continuous Process 92% 100% 80% 115.0% Of this Invention
[0060] The separate processes are comprised of three separate steps: film extrusion, annealing and stretching. The estimate yields are 90% for film extrusion, 90% for annealing and 85% for stretching. The yield of stretching is expected to be lower because of losing the film during starting-up and ending under high tension. Runnable machine usage is estimated to be 80% because of idle time during roll change, starting up, and ending. The operation cost is assumed to be 100% as a comparison basis. So, the total productivity index is estimated to be 54.4%.
[0061] In contrast, the continuous process of this invention is a single step. The yield of film extrusion is estimated to be 95%, slightly higher than that in the separate processes because of no roll-collection operation. Membrane collection yield at the end of the process is expected to be 98%. So, the product yield would be 92%. Runnable machine usage is expected to be 100% because of no idle time for roll change, roll starting up and roll ending. The operation cost is estimated to be 80% of that in the separate processes because of no need for operation, management and storage for intermediate products. So, the total productivity index is estimated to be 115.0%.
[0062] The production efficiency of the continuous process in this invention is much greater than that of the conventional separate processes.
[0063] The extrusion conditions are mainly dominated by the process conditions in the ovens, especially to the film-extrusion line speed. It needs to be compatible with the planned line speed in the annealing oven so that it can be run continuously. For the PP/PE/PP trilayer membrane, the PP film extrusion and the PE film extrusion need to be run at the same speed. The preferred annealing line speed ranges from 15 ft/min and 35 ft/min. The film extrusion speed is preferably in the range of 15 ft/min and 35 ft/min. In the conventional processes of separate steps, the higher line extrusion speed is preferred. In the prior art, with the conventional separate processes, the film extrusion line speed is preferably in the range of 30 ft/min and 700 ft/min for blown film extrusion and preferably in the range of 50 ft/min and 500 ft/min for slit film extrusion as described in the prior art, U.S. Pat. Nos. 3,426,754; 3,558,764; 3,679,538; 3,679,540; 3,801,404; 3,801,692; 3,843,761; 3,932,682. For the line speed of blown film extrusion for the precursor in another prior art U.S. Pat. Nos. 4,994,335; 5,173,235, the line speed of extrusion was in the range of 100 ft/min and 120 ft/min (30 meter/min and 36 meter/min). In this invention, the line extrusion speed is preferred at a compatible speed with the line speed in the annealing oven. Film extrusion line speeds can be higher than 35 ft/min, but it needs longer ovens to accommodate the need of the optimized residence time of the film in the ovens. In this case, the investment of oven capital is required more, but it certainly produces even more products,
[0064] The overall process speeds of this invention need to be considered from technical point of view and from business point of view.
[0065] The following examples demonstrate the quality precursor produced at a preferable speed described above, and the precursor can be made into the quality membrane.
EXAMPLE 1
[0066] PP(Fina PP 3271) produced by Fina Oil & Chemical has a density of 0.905 g/cc and a melt index of 1.5 g/10 min. PE(Hizex 5202B) produced by Mitsui Chemical has a density of 0.964 g/min and a melt index of 0.3 g/10 min. Either PP or PE are blended with 2500 ppm sodium benzoate as a nucleating agent to promote the crystal formation during film formation at a lower speed. A blown-film extrusion line made by Lung-Meng Plastics Machinery is equipped with a ˜1.6 inch diameter of screw with a L/D ratio of 36. The line is equipped with a 300-cm circular die with a die gap of ˜100 mil. The air ring height is adjusted to a level around 1.0 inch above the die.
[0067] The PP and PE precursor films have been annealed in a batch convention oven, respectively, at 150° C. and 120° C. for ˜12 min. The annealed precursors are further stretched on an Instron Machine equipped with an environment control chamber. PP films are stretched, respectively, at 150° C., 20% cold stretch, 140% hot stretch, 40% relax; PE films, at 120° C., 40% cold stretch, 140% hot stretch, and 40% relax.
TABLE 2 Resin Extrusion Line Speed Membrane Thickness Gurley Fina PP 3271 30 ft/min 1.03 mil 26 sec 25 ft/min 1.04 mil 32 sec 20 ft/min 1.02 mil 40 sec Hizex 5202B 35 ft/min 1.02 mil 28 sec 30 ft/min 1.01 mil 33 sec 25 ft/min 1.00 mil 40 sec
[0068] From the above example, the film precursors from lower extrusion speed can yield quality membranes. There are no prior art found that this preferred slower line speed of film extrusion in this invention can result in quality membranes. In the same way, ultra-thin PP and ultra-thin PE precursor films (0.2˜0.5 mil) can be extruded at the preferred line speed for making PP/PE/PP trilayer separator, continuously. The intention of the lower extrusion speed is to lower down the line speed in the ovens, which will need smaller size of ovens for the same residence time.
[0069] The detailed running conditions in the annealing and stretching ovens are mostly described in the prior art for dry-stretch polyolefin microporous membranes. For example, annealing temperature, stretching temperature, line speeds in the oven, cold stretching ratio, hot stretching ratio and heat-set/relaxing ratio can be the same as or different from those described in the prior art, U.S. Pat. No. 4,138,459 for multiply (PP or PE) single-layer separator; U.S. Pat. No. 5,952,120 for multiply PP/PE/PP trilayer separator, U.S. Pat. No. 6,057,060 for multiply ultra-thin (PP or PE) separator. They need to be slightly adjusted based on different grades of PP or PE raw materials used.
[0070] According to the above information, one can estimate the needed length of film path in the annealing oven to be equal to Extrusion Line Speed multiplying 12 min. According to the stretch ratios, one can estimate the needed length of film path in the stretching oven. The slower line speed of extrusion requires shorter length of film path in the ovens. One of the major advantages with it is that the shorter length of film path in the annealing oven and then in the stretching oven allows the smaller needed size of the ovens and then the less investment. Another advantage with the preferred line speed of the film extrusion is to allow an excellent control on the overall operation of the continuous process in this invention.
[0071] The continuous method of this invention will benefit the process at both fast and slow film extrusion speeds.
[0072] Test Methods:
[0073] Gurley ASTM-D726(B)
[0074] Gurley is a resistance to air flow measured by the Gurley densometer. Gurley is the time in seconds required to pass 10 cc of air through one square inch of product under a pressure of 12.2 inches of water pressure.
[0075] Porosity ASTM D-2873
[0076] Density ASTM D-792
[0077] Melt Index ASTM D 1238; PE: 190° C./2.16 Kg; PP: 230° C./2.16 Kg.
CONCLUSION, RAMIFICATIONS, AND SCOPE OF INVENTION
[0078] Thus the reader will see that the continuous process of this invention can produce dry-stretch PP, PE, and PP/PE/PP trilayer membrane separators in a highly efficiency. The preferred extrusion line speed with multiple blown film extrusion (or slit film extrusion) can be a line speed compatible with the line speed in the annealing oven. The membrane thickness can be in the range of 0.2 mil and 4.0 mil. The annealing conditions and stretching conditions can be the conditions described herein or the conditions in the prior art.
[0079] The raw material used is polyolefin as defined early. In PP/PE/PP trilayer membrane separators, the PE layer is served as potential shutdown layer as described in U.S. Pat. No. 5,691,077. In this invention, the PE layer can be a pure PE resin, PE containing particles, as described in U.S. Pat. No. 6,080,507, and PE containing other additives or minor polymeric components (less than 30%). All the membranes obtained from the invented continuous process will not be involved in solvent.
[0080] The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification as indicating the scope of the invention.
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A continuous method of making dry-stretch microporous membrane battery separators from polypropylene (PP) or polyethylene (PE) or both benefits to the manufacturers in the production efficiency. The precursor-film extrusion in this invention is accomplished by multiple small film-extrusion lines at a compatible line speed with the followed oven processes (annealing and stretching). The overall production process starts continuously from film extrusion to annealing and to stretching. The benefits of the inventive continuous process includes a higher product yield, more effective oven-time usage, no need to handle and manage the intermediate products, less need in labor and machine maintenance, and potentially more stable product quality.
The dry-stretch membrane separators made with this inventive continuous method include (1) single-ply PP or PE separators having a thickness ranging from 0.2 mil to 2.0 mil; (2) PP/PE/PP trilayer microporous membrane separators having a thickness ranging from 0.6 mil to 4.0 mil. The PP/PE/PP trilayer can be accomplished in the early extrusion via either co-extrusion or extruding separately and then interposing PE layer between two PP layers, continuously, right before annealing/bonding and stretching process.
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BACKGROUND OF THE INVENTION
This invention relates to a method and apparatus for controlling the flow of bakery and other items in a manufacturing process. More particularly, this invention relates to a method and apparatus that can be utilized to transfer bakery and other items from one conveyor to another and to align bakery and other items on conveyors in order to facilitate faster processing or the packaging of such items.
In many instances before an item can undergo further processing or be packaged, it must be brought into a particular alignment. This is the case with regard to many different items. This is particularly the case with regard to bakery items, and more particularly with regard to fragile bakery items. Various fragile bakery goods which will include various types of cookies, must be carefully handled and packaged so that the cookies will not be damaged and will be maintained in a separated condition. Such items need this type of packaging since if packaged in a random fashion the cookies would either become broken, marred in some manner, or if they contain a delicate or multiple coating, could become bonded one to the other. There is therefore a continuing need in the bakery art for specialized handling equipment for various types of products.
The present invention is directed to a method and apparatus for controlling the flow of items, and in particular bakery items, which are being fed to a packaging or some other operating point. The items could be aligned prior to being fed to an enrobing operation, or prior to being fed to a packaging operation. In any regards, one objective is to put the various items into an alignment so that they can be fed in an orderly and controlled manner. This is necessary in many operating sequences.
The present invention also provides a convenient technique for transferring items from one conveyor belt to another conveyor belt. Further, the conveyor belts need not be in the same plane. The technique is also gentle with regard to the item being transferred to thereby minimize damage to any of the items.
Various techniques have been utilized for the alignment of items, including bakery items. In some cases the apparatus consists of a gate mechanism which is controlled by either a mechanical switch means or a photo-electric switch means. In such cases, when there are a number of items on a conveyor and adjacent to the gate mechanism the gate mechanism is opened and permits a row of such items to move forward along a conveyor belt. In such equipment and methods, the various items will move forward on the same conveyor belt or will be allowed to move onto another conveyor belt which is adjacent to the gate mechanism. There are yet other types of apparatus that have been utilized for similar purposes. For instance, in U.S. Pat. No. 3,556,280 there is disclosed an apparatus for placing articles in rows on a conveyor. The conveyor belt receives the articles at one end and delivers them to the other end. At the other end a number of the articles are removed from the conveyor belt and are dropped downwardly onto a further transporting medium. This second transporting medium is transverse to the conveyor. However, there is not disclosed in this patent a technique of utilizing a rotatable wheel mechanism as a means to align a particular number of items.
In U.S. Pat. No. 3,786,617 there is disclosed a device for the automatic filling of biscuits into packaging containers. In this patent there is disclosed a chute which contains a plurality of cookies which move downwardly through the chute. A given number of the cookies are released from the chute and moved downwardly onto a supporting surface. Once on the supporting surface, the given number of cookies are moved transversely over to a tray where the cookies are slid into the tray. As the trays are filled they move downwardly and complete the packaging sequence.
U.S. Pat. No. 3,812,647 discloses an apparatus for stacking and packaging food products. This apparatus is particularly adapted for round disc-shaped articles such as cookies. In this apparatus the cookies move in a single file along a series of conveyor belts. The cookies at the end of the conveyor belt are stacked to a given number. They are then moved forwardly onto a rotating table which moves the cookies around to a point where they will be slid onto a packaging tray.
U.S. Pat. No. 4,413,462 discloses an accumulator and stacker for sandwich cookies, biscuits and similar articles In this mechanism cookies are accumulated and stacked one on top of the other. These individual two-high stacks can then be further stacked to increase the size of the stack prior to packaging. This patent discloses an interesting conveyor arrangement, however there is no disclosure in this patent, or in the other above-cited patents, with regard to the use of a rotatable wheel having longitudinal slots in order to move articles from one conveyor to another, or to arrange items, including cookies, biscuits and the like, for further processing or packaging by putting them in a particular alignment.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to a method and apparatus for controlling the flow of items along a conveyor belt system. In particular, the present method and apparatus is directed to transferring articles from one conveyor belt to another or to aligning articles that are in a number of rows so that the articles will move transversely in a row along a conveyor belt mechanism. The apparatus consists of two conveyor belts. In between the conveyor belts is a rotating wheel having a plurality of longitudinal slots. Also, in a preferred embodiment, the conveyor belts have multiple lanes and at the end of the conveyor belt which delivers the items to the rotatable wheel, there may be a gate mechanism which opens when there is an item in each lane of the conveyor belt. That is, at the gate mechanism, it is sensed when there is an item in the area of the gate in each lane whereby when the gate opens one item from each lane passes onto the rotatable wheel and via the rotatable wheel is deposited downwardly onto the second conveyor belt mechanism. The articles will under the influence of gravity slide off the rotating wheel and advance along the second conveyor belt in a transverse alignment. Such an alignment is important with regard to packaging operations. A gate mechanism at the end of the conveyor which delivers the items to the rotatable wheel can be operated by means of an electro-mechanical mechanism or a photo electric mechanism.
The method of the present invention in its preferred embodiment consists of flowing items from an oven, an enrobing machine or some other device into individual lanes of a first conveyor. This first conveyor moves the items along in a disparate arrangement from the entry end to the exit end which is in the region of the rotatable wheel. At the exit end the items are deposited onto a longitudinal slot of a rotating wheel. The rotating wheel takes the items and under the influence of gravity permits the items to slide from the rotatable wheel onto a second conveyor mechanism. On the second conveyor mechanism the items will now be in a transverse alignment to the conveyor belt. These items are then moved along at a desired rate for further processing or to a packaging station.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of the present apparatus showing the conveyor belt delivering items to the rotatable wheel and a second conveyor belt transporting items from the rotatable wheel.
FIG. 2 is an elevational view of the apparatus of FIG. 1.
FIG. 3 shows a mechanical sensing mechanism for sensing when an item is in a lane of the first conveyor and adjacent to the gate.
FIG. 4 shows a photo-electric controlled mechanism which senses when an item is adjacent to the gate at the end of the first conveyor belt and adjacent to the rotatable wheel.
FIG. 5 is a sectional view of the rotatable wheel showing it in addition as a heating or cooling means.
DETAILED DESCRIPTION OF THE INVENTION
There is a need in many processes to transfer items in a careful manner from one conveyor belt to another conveyor belt. There is also a need in many operations, and particularly in packaging operations, to align a number of articles traveling along a conveyor belt so that these items can be packaged in an orderly manner. The technique that has been devised in order to meet these objectives, as well as other objectives, consists of utilizing a rotating wheel having longitudinal slots therein for carrying the particular items and for receiving the items from one conveyor belt mechanism and to deposit the items onto the second conveyor belt mechanism. In this way, there is a positive flow of the items from one conveyor belt to another conveyor belt.
The present mechanism is particularly advantageous when used in combination with a gate mechanism just prior to the rotating wheel. In this way the gate mechanism will fill each longitudinal slot of the rotating wheel with the items to be conveyed to the second conveyor belt. These items are then deposited onto the second conveyor belt in an aligned row. The items can then be sent to further processing such as coating or enrobing, or they can be forwarded to packaging. Regardless of the situation in which it is used, the rotating wheel mechanism will deposit the items in a manner in which the items undergo a minimum amount of potential damage.
The present invention will be described for particular use with bakery products. However, it is to be recognized that it can be utilized with essentially any situation where a plurality of articles are being conveyed.
In more detail and with specific reference to FIG. 1, the various articles 20 exit an oven 9 or a device which has conducted some other operation on the various bakery items 20. These bakery items 20 are deposited onto conveyor belt 10 which consists of lanes 10a separated by vertical separators 10b. In this embodiment it is shown that the conveyor belt 10 delivers the items 20 to the area of gate 11. At gate 11 when there is an item 20 in each lane adjacent to the gate, the gate opens and permits a row of items 20 to be deposited onto a drum or rotating wheel 12 which rotates on axis 17. Rotating wheel 12 has a plurality of peripheral grooves or longitudinal slots designated 12a, 12b, 12c, 12d, and so on. The number of longitudinal slots will range from 2 to about 24. However, it is to be recognized that there is no limitation on the number of longitudinal slots. The number of longitudinal slots will be governed by the circumference of the wheel and the size of the items 20 that are being conveyed. As wheel 12 rotates, the items 20 fall or slide from the peripheral grooves and are deposited down onto the conveyor belt mechanism 13. As seen in FIG. 2, the items 20 slide down and bridge the distance or gap between the rotating drum 12 and the conveyor 13. Conveyor belt 13 consists of a plurality of lanes 13a separated by vertical projections 13b. The items move along conveyor belt 13 in an aligned row. These items are delivered by conveyor 13 to a further processing step or to packaging.
FIG. 2 is an elevational view of the device of FIG. 1. This view shows the rotating wheel in more detail. In this view there is shown a wheel which has 12 peripheral steps These peripheral steps each have a bottom portion 14 and a ledge or raised portion 15. Bottom portion 14 supports the item as it is rotated by the wheel and raised portion 15 catches and maintains the item in that particular peripheral step. An item exiting end of the conveyor belt 10 is positioned adjacent to the side of the drum 12 rotating upwardly. As shown in FIG. 2, the exiting end of the conveyor belt is positioned just below the highest point of rotation of the drum 12. An item receiving end of the belt conveyor 13 is positioned adjacent to the side of the drum 12 rotating downwardly. As also shown in FIG. 2, the receiving end of the conveyor is positioned approximately at the center of rotation of the drum 12.
When a gate 11 is incorporated into a system it converts the conveyor 10 into an accumulator mechanism. The function of an accumulator mechanism is to accumulate an item in each lane of the conveyor prior to the gate's opening. The gate then opens and permits one or more of the items in each row to proceed forwardly. In the present case when the gate 11 opens it permits one item to go forward and to fall into a longitudinal slot on wheel 12. In such an instance the gate 11 must have some manner of detecting when there is an item in each lane adjacent to the gate. In this regard this gate can be actuated either electro-mechanically or photo-electrically.
In FIG. 3, there is illustrated an electro-mechanical arrangement for the operation of gate 11. In this Figure, gate 11 is supported on rods 21 on which it can pivot. It will pivot by means of an actuating motor connected to either rod 21. The mechanism for sensing whether there is an item in a row consists of electro-mechanical switch 18 which has depending therefrom a spring loaded arm 19. When an item in a lane contacts a spring loaded arm 19, it closes the switch 18. When the switches 18 are connected in series, there will not be a continuous circuit from the individual switches lB through to a motor to actuate the rod 21 until there is an item in each lane pressing against the arms 19. Once this occurs, each of the switches is closed to thereby close the circuit. That is, when each switch 18 is closed, power can be actuated to flow to motor 22 and open the gate 11. In FIG. 4, there is shown a similar arrangement but wherein there is utilized a diode and photocell arrangement 25 in place of the electro-mechanical arrangement for sensing when an item is within a particular lane and adjacent the gate. Here diode 24 provides light that is reflected and sensed by photo-electric unit 23. The photo-electric units 23 can be connected in a series arrangement, and when there is an item in each lane, this is sensed photo-electrically and the motor 22 actuates the gate 11 to permit a row of articles to proceed.
When a photo-electric mechanism is used, it will sense the reflectivity of the base conveyor mechanism and the reflectivity of the items supported on the conveyor belt. The reflectivity will be different for each. Thus, when the reflectivity is in the range of that for a conveyed item, the particular switch closes to indicate an item in that lane. When all of the photo-electric switches are closed, this permits a current to flow and to actuate motor 22 to operate gate 11. In construction the diode 24 is surrounded by photo-electric cell 23 to determine the reflectivity of the light emitted from diode 24.
Besides electro-mechanical and photo-electric techniques for operating such a gate, there are various other ways that a gate can be operated if one is to be used. As a for instance, the accumulator and the gate mechanisms which are disclosed in U.S. Pat. No. 4,662,152 could be utilized in the present instance In this regard that part of U.S. Pat. No. 4,662,152 is hereby incorporated by reference.
It is not necessary that there be a gate 11 in the conveyor system. In such an instance the wheel 12 will be utilized as a means for transferring items from one conveyor belt mechanism to another conveyor belt mechanism. This provides a convenient technique for carefully moving items, and in particular baked items, from one conveyor belt to another conveyor belt. This assures that the items that are being transported on the conveyor belt will not be damaged by the roller at the end of the first conveyor belt or by the roller at the beginning of the second conveyor belt.
Further, the wheel can be cooled or heated on the interior by means of water or some other fluid or by a gas so as to cool or heat the bottom surface of the item while it is transferring it from one conveyor belt to another conveyor belt. In this way, if it were cooling the item, it would be making the item, such as a cookie, more stable for transport through successive operations. In order to utilize the wheel 12 as a cooling or heating mechanism, all that is necessary is that cold or hot water or other fluid, including cold or hot gases, be flowed in one support rod 17, allowed to permeate throughout the interior of the wheel, and then exit the other support rod 17. In such an instance, each end of the rod 17 would be bored through this center as shown in FIG. 5. In FIG. 5 the rods 17 are shown as 17a and 17b. These rods are centered and support the wheel as it rotates. Each rod has a bore 18 which is open to the hollow center 19 of the wheel. In use a heating or cooling fluid can be flowed in either rod I7a or 17b. It will then exit the opposite end. Inside wheel 19 there can be baffles or other means to control the flow of the heating or cooling fluid. Other adaptations could also be made to increase the effectiveness of the wheel as a heating or cooling device.
There are yet other uses to which this wheel transferring mechanism can be utilized. However, such uses based on the present disclosure would be within the skill of one in the art.
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There is set forth a rotating wheel transfer mechanism for transferring items, but in particular bakery items, from one conveyor belt to another conveyor belt. Combined with the conveyor belt mechanism there can be a gate arrangement to assist in aligning the conveyed items. In addition, the wheel transfer mechanism can be heated or cooled in order to respectively heat or cool the items being conveyed. The net result is that the items can be transferred from one conveyor belt to another conveyor belt with less damage to the particular items.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application of U.S. Ser. No. 15/329,380, filed on Jan. 26, 2017, which is a US national phase application based upon an International Application No. PCT/CN2016/077014, filed on Mar. 22, 2016, which claims priority to Chinese Application No. 201510220531.6, filed Apr. 30, 2015. The entire disclosures of each of the above applications are incorporated herein by reference.
BACKGROUND OF THE DISCLOSURE
1. Field of the Disclosure
[0002] The present disclosure relates to the field of mobile communication technology, and more particularly, to a method of accessing to networks and a mobile communication terminal.
2. Description of the Related Art
[0003] Public land mobile network (PLMN) is a network built and operated by the government or operators approved by the government for the purpose of providing land-bound mobile communication services for the public. The network is usually connected to public switched telephone network (PSTN), forming a communication network that covers a whole region or country.
[0004] A network identity of the PLMN is usually just a string of numbers. For example, the network identity of PLMN of China Mobile is 46000, and the network identity of PLMN of China Unicom is 46001. Through the mobile networks provided by each operator, users can enjoy rapid and convenient communication. The number of users carrying communication terminals has been on the rise as people's living standard elevates. When a user inserts a new user identification card into a mobile communication terminal for the first time, the mobile communication terminal (e.g. a cell phone) must search a network to acquire the network identity of the PLMN. However, when the user inserts the new user identification card into the mobile communication terminal for the first time, it usually takes the terminal a long time (sometimes even as long as ten to twenty minutes) to search the network. And, only when the terminal successfully found the network can it connect to the PLMN of the location. It significantly influences users' communication experience.
SUMMARY
[0005] The embodiment of the present disclosure provides a method and mobile communication terminal for accessing to a network and reducing the time needed to connect to a PLMN, thus greatly improves users' communication experience.
[0006] The present disclosure proposes a method for accessing to a network. The method includes follows.
[0007] A location of a mobile communication terminal is determined.
[0008] a Bluetooth low energy (BLE) protocol broadcast channel is scanned if a network identity of a public land mobile network (PLMN) corresponding to the location have not been added to a first equivalent public land mobile network (EPLMN) list.
[0009] a second EPLMN list is extracted when the second EPLMN list released on the BLE protocol broadcast channel is scanned.
[0010] The network is accessed based on the second EPLMN list if the second EPLMN is added with the network identity of the PLMN corresponding to the location.
[0011] The present disclosure also proposes a mobile communication terminal. The mobile communication terminal includes a determining unit, a scanning unit, an extracting unit, and an accessing unit.
[0012] The determining unit is configured to determine a location of the mobile communication terminal.
[0013] The scanning unit is configured to scan a Bluetooth low energy (BLE) protocol broadcast channel if a network identity of PLMN corresponding to the location determined by the determining unit has not been added into a first EPLMN list.
[0014] The extracting unit is configured to extract a second EPLMN list if the second EPLMN list released on the BLE protocol broadcast channel is scanned by the scanning unit.
[0015] The accessing unit is configured to connect to a network based on the second EPLMN list if the second EPLMN list extracted by the extracting unit is added with the network identity of the PLMN corresponding to the location.
[0016] The embodiment of the present disclosure determines a location of the mobile communication terminal. If the network identity of a PLMN corresponding to the location has not been added in a stored first EPLMN list, a Bluetooth low energy (BLE) protocol broadcast channel is scanned. When a second EPLMN list released on the BLE protocol broadcast channel is detected during scanning, the second EPLMN list is extracted. If the network identity of the PLMN corresponding to the location has already been added into the second EPLMN list, the network connection is conducted based on the second EPLMN list. The embodiment of the present disclosure connects to the network based on the second EPLMN list that has already been added with the network identity of the PLMN corresponding to the location. The network identities of PLMNs stored in the second EPLMN list are regarded as equivalent to a certain extent by the mobile communication terminal. Therefore, when the mobile communication terminal connects to a network based on the EPLMN list, which has stored network identities of PLMNs corresponding to the location, it significantly heightens the chance of finding a PLMN whose network identity matches a network identity that is already stored in the EPLMN list during the process of network searching. It also heightens the possibility of the mobile communication terminal accessing to a network at the location. It is instrumental in minimizing the waiting time when users are communicating (ideally, it only takes a few seconds for the mobile communication terminal to complete network connection), and thus is instrumental in greatly improve users' communication experience.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order to more clearly illustrate the embodiments of the present disclosure or related art, the following figures will be described in the embodiments are briefly introduced. It is obvious that the drawings are merely some embodiments of the present disclosure, those of ordinary skill in this field can obtain other figures according to these figures without paying the premise.
[0018] FIG. 1 is a flow chart of the method for accessing to a network according to an embodiment of the present disclosure.
[0019] FIG. 2 is a flow chart of the method for accessing to a network according to another embodiment of the present disclosure.
[0020] FIG. 3 is a block diagram of a mobile communication terminal according to a first embodiment of the present disclosure.
[0021] FIG. 4 is a block diagram of a mobile communication terminal according to a second embodiment of the present disclosure.
[0022] FIG. 5 is a block diagram of a mobile communication terminal according to a third embodiment of the present disclosure.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0023] For the purpose of description rather than limitation, the following provides such specific details as a specific system structure, interface, and technology for a thorough understanding of the application. However, it is understandable by persons skilled in the art that the application can also be implemented in other embodiments not providing such specific details. In other cases, details of a well-known apparatus, circuit and method are omitted to avoid hindering the description of the application by unnecessary details.
[0024] The embodiment of the present disclosure proposes a method and mobile communication terminal for accessing to a network to reduce the time needed for the mobile communication terminal to connect to a PLMN, thus greatly improves users' communication experience.
[0025] Please refer to FIG. 1 . FIG. 1 is a flow chart of the method for accessing to a network according to an embodiment of the present disclosure. It can be applied to mobile communication terminals such as smart phones (e.g. android phones, iOS phones, and so on). The method for accessing to a network includes following blocks:
[0026] S 101 : A location of the mobile communication terminal is determined.
[0027] As an optional method for implementation, when the user carrying the mobile communication terminal moves from a home location to a visited location, or from location A to location B, geographical the location data of the user carrying the terminal must be obtained so to extract the network identity of the PLMN corresponding to the visited location when the mobile communication terminal is shifting to another network or reactivated upon arriving the visited location. Extracting the current geographical location of the terminal can be achieved through various means of positioning, such a global positioning system (GPS) embedded in the terminal.
[0028] In the embodiment of the present disclosure, the mobile communication terminal can extract the location data based on the location's longitude and latitude, or on an iconic building that sits on the location. For example, if the mobile communication terminal currently locates in Beijing, an iconic building corresponding to the location can be Imperial Palaces.
[0029] S 102 : If the PLMN corresponding to the location has not been added to a first EPLMN list, a BLE protocol broadcast channel is scanned.
[0030] In the embodiment of the present disclosure, PLMN is a network built and operated by the government or operators approved by the government for the purpose of providing land-bound mobile communication services to the public. The network is usually connected to PSTN, forming a communication network that covers a whole region or country. For example, the network identity of PLMN of China Mobile is 46000, and the network identity of China Unicom is 46001. PLMN is a wireless communication system, inclined to be accessed by land-bound users riding on transportation tools or moving on foot. Such a system can be independent, but it is usually connected to a landline telephone system, such as PSTN. However, there are also more and more mobile and portable Internet users. An ideal PLMN system provides services to mobile and portable users equivalent to that provides to landline users. It can be especially challenging in areas with complicated terrains, because it is difficult to find and maintain a base station. There are also many obstacles in an urban environment, such as noises and interfering radiation that can be evoked by buildings and radio frequencies.
[0031] In the embodiment of the present disclosure, an EPLMN is a PLMN that has the same status and level of priority as the PLMN currently chosen by the user's terminal. The EPLMN mainly solves problems related to user retention and roaming strategy in shared networks and original networks. Operators can deploy equivalent PLMNs so to realize sharing of communication network resources. From a business perspective, the practice realizes sharing of communication network resources among different PLMNs defined by the same operator or PLMNs of different operators.
[0032] In the embodiment of the present disclosure, the network identity of the PLMN can include network codes. For example, the network code of China Mobile include: 46000, 46002, 46007, and 46008. The network codes of China Unicom includes: 46001, 46006 and 46009.
[0033] Specifically, when the mobile communication terminal determines the location, it will detect whether the network identity of the PLMN corresponding to the location has been added to the first ELPMN list.
[0034] S 103 : A second EPLMN list is extracted when the second EPLMN list released on the BLE protocol broadcast channel is scanned.
[0035] In the embodiment of the present disclosure, when the mobile communication terminal detects that the network identity of the PLMN corresponding to the location has not been added to the first EPLMN list, it activates a BLE scan, which is broadcasting a Bluetooth message through the BLE protocol broadcast channel. A scan done by BLE scan technique can lower the power consumed by the mobile communication terminal during the scan.
[0036] S 104 : If the second EPLMN list is added with the network identity of the PLMN corresponding to the location, connect to the network based on the second EPLMN list.
[0037] The embodiment of the present disclosure also needs to detect whether the network identity of the PLMN corresponding to the location is added into the second EPLMN list. When the network identity of the PLMN corresponding to the location is added into the second EPLMN list, connect to the network based on the second EPLMN list.
[0038] In FIG. 1 , the mobile communication terminal first determines the location of the mobile communication terminal. If the network identity of the PLMN corresponding to the location has not been added to the first EPLMN list, the BLE protocol broadcast channel is scanned; when the second EPLMN list released on the BLE protocol broadcast channel is scanned, extract the second EPLMN list. If the network identity of the PLMN corresponding to the location has been added to the second EPLMN list, the last block is to connect to the network based on the second EPLMN list. The embodiment of the present disclosure, when putting into practice, connects the network based on the second EPLMN list in which the network identity of the PLMN corresponding to the location is added. The PLMNs whose network identities have been stored in the second EPLMN list are, to an extent, regarded as equivalent by the mobile communication terminal. Therefore, if the mobile communication terminal connects the network based on the EPLMN list, which has stored the network identity of the PLMN corresponding to the location, the chance of finding a network identity of a PLMN that has already been stored in the EPLMN list when the mobile communication terminal searches a network at the location is greatly elevated. Therefore, the chance of the mobile communication terminal accessing to the network at the location is greatly elevated, which is instrumental in minimizing the waiting time when users are communicating (ideally, it only takes a few seconds for the mobile communication terminal to complete network connection), and thus is instrumental in greatly improve users' communication experience.
[0039] Please refer to FIG. 2 . FIG. 2 is a flow chart of the method for accessing to a network according to another embodiment of the present disclosure. The method for accessing to a network includes following blocks:
[0040] S 201 : A location of the mobile communication terminal is determined.
[0041] In the embodiment of the present disclosure, the location can be a home location of the user identification card inserted in to the terminal, or a visited location of the user identification card inserted into the terminal.
[0042] S 202 : If a network identity of a Public Land Mobile Network (PLMN) corresponding to the location has not been added into a first equivalent public land mobile network (EPLMN) list, a Bluetooth low energy (BLE) protocol broadcast channel is scanned.
[0043] In the embodiment of the present disclosure, PLMN is a network built and operated by the government or operator approved by the government for the purpose of providing land-bound mobile communication services for the public. The network is usually connected to PSTN, forming a communication network that covers a whole region or country. For example, the network identity of PLMN of China Mobile is 46000, and the network identity of China Unicom is 46001. PLMN is a wireless communication system, inclined to be accessed by land-bound users riding on transportation tools or moving on foot. Such a system can be independent, but it is usually connected to a landline telephone system, such as PSTN. However, there are also more and more mobile and portable Internet users. An ideal PLMN system provides services to mobile and portable users equivalent to that provides to landline users. It can be especially challenging in areas with complicated terrains, because it is difficult to find and maintain a base station. There are also many obstacles in an urban environment, such as noises and interfering radiation that can be evoked by buildings and radio frequencies.
[0044] In the embodiment of the present disclosure, an EPLMN is a PLMN that has the same status and level of priority as the PLMN currently chosen by the user's terminal. The EPLMN mainly solves problems related to user retention and roaming strategy in shared networks and original networks. Operators can deploy equivalent PLMNs so to realize sharing of communication network resources. From a business perspective, the practice realizes sharing of communication network resources among different PLMNs defined by the same operator or PLMNs of different operators.
[0045] S 203 : A request is broadcasted to share the second EPLMN list through the BLE protocol broadcast channel.
[0046] In the embodiment of the present disclosure, a share request can be in text or voice. The present disclosure does not specify any limit on a format of the share request.
[0047] S 204 : A second EPLMN list is extracted when the second EPLMN list released on the BLE protocol broadcast channel by another mobile communication terminal in response to the share request is scanned.
[0048] In the embodiment of the present disclosure, when the mobile communication terminal scans a second EPLMN list released on the BLE protocol broadcast channel by another mobile communication terminal in response to the share request, it extracts the second EPLMN list.
[0049] S 205 : A network is connected based on the second EPLMN list if the network identity of the PLMN corresponding to the location has been added into the second EPLMN list.
[0050] S 206 : A reminder message is output to remind users of the time needed to connect to the network.
[0051] In the embodiment of the present disclosure, when the mobile communication terminal detects that the network identity of the PLMN corresponding to the location has been added into the second EPLMN list, it connects to the network based on the second EPLMN list. When the connection succeeds, it outputs a reminder message to remind users of the time needed to connect to the network this time. When the connection fails due to some other reasons, the mobile communication terminal detects reasons of this failure and outputs solutions to the user.
[0052] FIG. 2 illustrates in detail the procedure of the mobile communication terminal accessing to the network and outputting a reminder message to remind the user of the time needed for the connection this time when the connection succeeds. The embodiment of the present disclosure, when putting into practice, can accurately calculate the time needed for each network connection, and determine the efficiency of the network connection based on the time needed to connect to the network, so to take measures to elevate the efficiency of network connection.
[0053] Please refer to FIG. 3 . FIG. 3 is a block diagram of a mobile communication terminal according to a first embodiment of the present disclosure to implement the method for accessing to the network. The mobile communication terminal in FIG. 3 can include but is not limited to terminals that are capable of accessing to networks, such as smart phones (e.g. android phones, iOS phones, and so on), tablets, personal digital assistants (PDA), and mobile internet devices (MID). As shown in FIG. 3 , the mobile communication terminal can include a determining unit 301 , a scanning unit 302 , an extracting unit 303 , and an accessing unit 304 .
[0054] The determining unit 301 is used to determine the location of the mobile communication terminal.
[0055] As an optional method for implementation, when the user carrying the mobile communication terminal moves from a home location to a visited location, or from location A to location B, geographical the location data of the user carrying the terminal must be obtained so to extract the network identity of the PLMN corresponding to the visited location when the mobile communication terminal is shifting to another network or reactivated upon arriving the visited location. Extracting the current geographical location of the terminal can be achieved through various means of positioning, such a global positioning system (GPS) embedded in the terminal.
[0056] In the embodiment of the present disclosure, the determining unit 301 can determine the location data of the mobile communication terminal based on the location's longitude and latitude, or on an iconic building that sits on the location. For example, if the mobile communication terminal currently locates in Beijing, an iconic building corresponding to the location can be Imperial Palaces.
[0057] The scanning unit 302 is used to detect whether the network identity of a PLMN corresponding to the location determined by the determining unit has been added to the first EPLMN list, and is used to scan a Bluetooth low energy (BLE) protocol broadcast channel if a network identity of a public land mobile network (PLMN) corresponding to the location determined by the determining unit has not been added into a first equivalent public land mobile network (EPLMN) list.
[0058] In the embodiment of the present disclosure, Public Land Mobile Network (PLMN) is a network built and operated by the government or operators approved by the government for the purpose of providing land-bound mobile communication services to the public. The network is usually connected to PSTN, forming a communication network that covers a whole region or country. For example, the network identity of PLMN of China Mobile is 46000, and the network identity of China Unicom is 46001. PLMN is a wireless communication system, inclined to be accessed by land-bound users riding on transportation tools or moving on foot. Such a system can be independent, but it is usually connected to a landline telephone system, such as PSTN. However, there are also more and more mobile and portable Internet users. An ideal PLMN system provides services to mobile and portable users equivalent to that provides to landline users. It can be especially challenging in areas with complicated terrains, because it is difficult to find and maintain a base station. There are also many obstacles in an urban environment, such as noises and interfering radiation that can be evoked by buildings and radio frequencies.
[0059] In the embodiment of the present disclosure, an equivalent public land mobile network (EPLMN) is a PLMN that has the same status and level of priority as the PLMN currently chosen by the user's terminal. The EPLMN mainly solves problems related to user retention and roaming strategy in shared networks and original networks. Operators can deploy equivalent PLMNs so to realize sharing of communication network resources. From a business perspective, the practice realizes sharing of communication network resources among different PLMNs defined by the same operator or PLMNs of different operators.
[0060] In the embodiment of the present disclosure, the network identity of the PLMN can include network codes. For example, the network codes of China Mobile include: 46000, 46002, 46007, and 46008. The network codes of China Unicorn include: 46001, 46006 and 46009.
[0061] Specifically, when the determining unit 301 determines the location, it will detect whether the network identity of the PLMN corresponding to the location has been added to the first ELPMN list.
[0062] The extracting unit 303 is used to extract a second EPLMN list when the second EPLMN list released on the BLE protocol broadcast channel is scanned.
[0063] In the embodiment of the present disclosure, upon detecting that the network identity of the PLMN corresponding to the location has not been added to the first EPLMN list, the scanning unit 302 activates a BLE scan, which is broadcasting a Bluetooth message through the BLE protocol broadcast channel. A scan done by BLE scan technique can lower the power consumed by the mobile communication terminal during the scan.
[0064] The accessing unit 304 is used to connect to a network based on the second EPLMN list if the second EPLMN list extracted by the extracting unit is added with the network identity of the PLMN corresponding to the location.
[0065] The embodiment of the present disclosure also needs to detect whether the network identity of the PLMN corresponding to the location is added into the second EPLMN list. When the network identity of the PLMN corresponding to the location is added into the second EPLMN list, the accessing unit 304 connects to the network based on the second EPLMN list.
[0066] In FIG. 3 , the determining unit 301 determines the location of the mobile communication terminal. If the network identity of the PLMN corresponding to the location has not been added to the first EPLMN list, the BLE protocol broadcast channel is scanned by the scanning unit 302 ; when the second EPLMN list released on the BLE protocol broadcast channel is scanned, the extracting unit 303 extracts the second EPLMN list. If the network identity of the PLMN corresponding to the location has been added to the second EPLMN list, the accessing unit 304 connects to the network based on the second EPLMN list. The embodiment of the present disclosure, when putting into practice, connects the network based on the second EPLMN list in which the network identity of the PLMN corresponding to the location is added. The PLMNs whose network identities have been stored in the second EPLMN list are, to an extent, regarded as equivalent by the mobile communication terminal. Therefore, if the mobile communication terminal connects the network based on the EPLMN list, which has stored the network identity of the PLMN corresponding to the location, the chance of finding a network identity of a PLMN that has already been stored in the EPLMN list when the mobile communication terminal searches a network at the location is greatly elevated. Therefore, the chance of the mobile communication terminal accessing to the network at the location is greatly elevated, which is instrumental in minimizing the waiting time when users are communicating (ideally, it only takes a few seconds for the mobile communication terminal to complete network connection), and thus is instrumental in greatly improve users' communication experience.
[0067] Please refer to FIG. 4 . FIG. 4 is a block diagram of a mobile communication terminal according to a second embodiment of the present disclosure to implement the method for accessing to the network. As shown in FIG. 4 , in addition to the units illustrated in FIG. 3 , the mobile communication terminal can further include a broadcasting unit 305 and an outputting unit 306 .
[0068] The broadcasting unit 305 is used to broadcast a request to share the second EPLMN list through the BLE protocol broadcast channel.
[0069] In the embodiment of the present disclosure, the extracting unit 303 is used, specifically, to extract a second EPLMN list when the second EPLMN list released on the BLE protocol broadcast channel by another mobile communication terminal in response to the share request is scanned.
[0070] In the embodiment of the present disclosure, a share request can be in text or voice. The present disclosure does not specify any limit on a format of the share request.
[0071] The outputting unit 306 is used to output a reminder message reminding the user of the time needed to connect to the network this time.
[0072] In the embodiment of the present disclosure, when the mobile communication terminal detects that the network identity of the PLMN corresponding to the location has been added into the second EPLMN list, it connects to the network based on the second EPLMN list. When the connection succeeds, it outputs a reminder message to remind users of the time needed to connect to the network this time. When the connection fails due to some other reasons, the outputting unit 306 detects reasons of this failure and outputs solutions to the user.
[0073] FIG. 4 illustrates in detail the procedure of the mobile communication terminal accessing to the network and outputting a reminder message to remind the user of the time needed for the connection this time when the connection succeeds. The embodiment of the present disclosure, when putting into practice, can accurately calculate the time needed for each network connection, and determine the efficiency of the network connection based on the time needed to connect to the network, so to take measures to elevate the efficiency of network connection.
[0074] FIG. 5 is a block diagram of a mobile communication terminal according to a third embodiment of the present disclosure. The mobile communication terminal is configured to perform the above network access methods. A mobile communication terminal 500 may include: elements such as at least one processor 501 , at least one input device 502 , at least one output device 503 , and a memory 505 . These elements are communicatively connected through one or a plurality of buses 504 . Those of ordinary skill in the art would understand that the embodiment of the present disclosure is not limited to the structure of the mobile communication terminal shown in FIG. 5 . It may be either a bus-type structure or a star-type structure, or may include more or fewer elements than illustrated, or some elements may be combined, or the elements may be arranged differently.
[0075] The processor 501 is a control center of the mobile communication terminal 500 . The processor 501 is connected to various parts of the mobile communication terminal 500 by utilizing various interfaces and circuits. Through running or executing program instructions and/or modules stored in the memory 505 , and using data stored in the memory 505 , the processor 501 performs a variety of functions of the mobile communication terminal and processes data. The processor 501 may be constituted by an integrated circuit (IC), for example, it may be formed by a single packaged IC, or may be formed by connecting a plurality of packaged ICs having a same function or different functions. For example, the processor 501 may only include a central processing unit (CPU), or may be a combination of a CPU, a digital signal processor (DSP), a graphic processing unit (GPU), and various types of control chips. In the embodiment of the present disclosure, the CPU may be a single-core CPU or may include a multi-core CPU.
[0076] The input device 502 includes a standard touch panel, a standard keyboard, etc.
[0077] The output device 503 includes a display panel, a speaker, etc.
[0078] The memory 505 may be configured to store a software program and the module. The processor 501 , the input device 502 , and the output device 503 performs a variety of functional applications of the mobile communication terminal and achieve data processing through using the software program and the module stored in the memory 505 . The memory 505 mainly includes a program storage area and a data storage area. The program storage area may store an operating system, an application program required by at least one function, or the like. The data storage area may store data or the like created according to uses of the mobile communication terminal. In the embodiment of the present disclosure, the operating system may be an Android system, an iOS system, a Windows operating system, or the like.
[0079] Specifically, the processor 501 executes the program instructions stored in the memory 505 to perform the following steps:
[0080] determining a location of a mobile communication terminal by using the processor 501 controlling the input device 502 ;
[0081] scanning a Bluetooth low energy (BLE) protocol broadcast channel if a network identity of a public land mobile network (PLMNs) corresponding to the location have not been added to a first equivalent public land mobile network (EPLMN) list;
[0082] extracting a second EPLMN list when the second EPLMN list released on the BLE protocol broadcast channel is scanned;
[0083] accessing to the network based on the second EPLMN list if the second EPLMN is added with the network identity of the PLMN corresponding to the location.
[0084] In the embodiment of the present disclosure, the network identity includes network code.
[0085] In the embodiment of the present disclosure, the processor 501 executes the program instructions stored in the memory 505 to perform a following step:
[0086] broadcasting a request to share the second EPLMN list on the BLE protocol broadcast channel.
[0087] In the embodiment of the present disclosure, when the processor 501 executes the program instructions to extract a second EPLMN list when the second EPLMN list released on the BLE protocol broadcast channel is scanned, the processor 501 executes the program instructions stored in the memory 505 to perform a following step:
[0088] extracting the second EPLMN list when the second EPLMN list released on the BLE protocol broadcast channel by another mobile communication terminal in response to the share request is scanned.
[0089] In the embodiment of the present disclosure, the processor 501 executes the program instructions to perform a following step:
[0090] outputting a reminder message by the output device 503 controlled by the processor 501 to remind the user of a time needed to connect to the network this time.
[0091] Specifically, the embodiment of the present disclosure introduces a terminal that can implement part or all of the procedure of the method for accessing to a network introduced by the present disclosure in combined with FIGS. 1 and 2 .
[0092] All the modules or submodules of the embodiments of the present disclosure can be realized by general integrated circuits, such as central processing unit (CPU) or application specific integrated circuit (ASIC).
[0093] The blocks of the embodiments of the present disclosure can be adjusted, combined or deleted based on real needs.
[0094] The units of the terminal in the embodiments of the present disclosure can be combined, divided or deleted based on real needs.
[0095] An ordinary technician of this field understands that part or all of the procedure of the embodiments can be completed by commanding relevant hardware through computer programs. The program can be stored in a computer readable storage medium. Procedures of the embodiments of the methods can be included when the program is operating. Wherein the storage medium can be a disk, CD, read-only memory (ROM), or random access memory (RAM).
[0096] While the present invention has been described in connection with what is considered the most practical and preferred embodiments, it is understood that this invention is not limited to the disclosed embodiments but is intended to cover various arrangements made without departing from the scope of the broadest interpretation of the appended claims.
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Disclosed in the embodiments of the present invention are a network access method and a mobile communications terminal, comprising: first determining the current position of a mobile communications terminal; if the network identifier of the public land mobile network (PLMN) corresponding to said position has not been added to a pre-stored first equivalent public land mobile network (EPLMN) list, then scanning a Bluetooth low energy protocol broadcast channel; when a second EPLMN list published to said Bluetooth low energy protocol broadcast channel is detected by scanning, obtaining said second EPLMN list; if the network identifier of the PLMN corresponding to said position is added to said second EPLMN list, then lastly, accessing the network according to said second EPLMN list.
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This is a continuation of application Ser. No. 08/131,767 filed Oct. 4, 1993, now abandoned.
FIELD OF THE INVENTION
This invention is in the area of general-purpose computers, and pertains more specifically to power supplies for general-purpose computers.
BACKGROUND OF THE INVENTION
State-of-the-art power supplies in general-purpose computers typically use pulse-width modulation to digitally regulate power generation. A typical power supply first converts the incoming 60-Hz utility power frequency to a much higher frequency range, such as 20,000 cycles per second. The duration of each power pulse is varied in response to the needs of the computer circuitry being supplied. The width of the pulses is controlled by electronically switching the current flow on and off. The pulses are reduced in voltage by a step-down transformer and turned into direct current by rectification and filtering. Switching the current off and on reduces losses in power from heat dissipation and makes power supplies relatively efficient.
Power supplies used by general-purpose computers produce different distinct voltages that are used by powered devices and circuits within each machine. Nearly all circuitry in state-of-the-art computers, from microprocessors to memory, requires either 5 or 3.3 volts. The motors of most disk drives use either 12 or 5 volts. Serial ports and some other input/output (I/O) devices often require both a positive and negative 12 volt supply. A few components and peripherals also require a negative 5 volt direct current supply.
Typically, a single power supply supplies all required voltages and varying amperage requirements to the different components that comprise a general-purpose computer system. The power supply's maximum power output must be rated close to the sum of all the power needs of installed components and expected addition of peripherals. It is a common practice, therefore, to provide a power supply rated considerably higher than the average usage of a system.
To work at optimum efficiency, the ratio of minimum to maximum load, or minimum to maximum power requirement, should not exceed a ratio of approximately 1:6. When a much larger power supply than is needed is initially installed, power efficiency is decreased for low power modes of operation. Efficiency may also be affected negatively when personal general-purpose computers incorporate advanced power (APM) management systems that have low-power modes, such as a standby mode.
Typically, these power-saving computers have four operating modes, with greatly varying power consumption. As an example, power modes in a typical portable general purpose computer may be as follows: a peak mode at approximately 90 watts for power-on surge; a normal mode at about 50 watts for operation with full expansion capabilities; a suspend mode at about 10-15 watts for no processing activity, but data is retained in random access memory (RAM); and a standby mode at about 1-2 watts for power only to wake-up circuits. Control for these power management modes is typically incorporated into the basic input/output system (BIOS) and works independently of state-of-the-art installed power supplies.
In this example, a power-saving system consumes as little as 1-2 watts in standby mode and as much as 90 watts in the power-on peak mode as described above. This design reduces power efficiency in trade for a power management system with low-power standby modes. In an additional effort to save power, manufacturers of general-purpose computers are reducing voltage levels to 3.3 volts for system microprocessors, integrated circuits and memory. This decreases power efficiency further when only system board functions are activated.
Designing and producing power-saving computers can significantly reduce the use of valuable natural resources. The Environmental Protection Agency (EPA) estimates that the annual energy consumption of office equipment has risen 400 percent between 1983 and 1993, and computers represent a large portion of this growth. That is a compound annual growth rate of about 17 percent, exceeding most estimates of workplace productivity improvements for the same period. Considering very low efficiencies associated with electric air-conditioning required to cool computerized equipment, every watt that goes into a general-use computer may actually represents as much as 3.3 watts of total demand. It is estimated by the EPA that the power to operate a personal computer and cool the space around it may cost as much as a personal computer costs on an annualized depreciation basis. These considerations have prompted the EPA to establish an Energy Star Computer Program to affix a government Energy Star seal on desk-top and workstation computers that can maintain a suspend mode of less than 30 watts. The federal government has even expressed that in the future they will but only such machines.
What is needed now is a power supply system for general-purpose computers that can be efficient at low power modes but can still have sufficient peak power for expanded configurations, with even larger power demands at varying time intervals. The present invention optimizes the use of an APM system with a power supply that can deliver optimized efficiency over different load requirements.
SUMMARY OF THE INVENTION
In an embodiment of the invention, a plural-mode power supply system for powering elements of general-purpose computers is provided. The computer has system circuitry comprising computing elements and non volatile memory, a keyboard having a keyboard controller, and electrically powered elements peripheral to the system circuitry and the keyboard, including but not limited to, one or more hard disk drives, one or more floppy disk drives, and system video display elements. The plural-mode power supply system comprises a first power supply for powering the electrically powered peripheral elements; a second power supply for powering the system circuitry, the keyboard, and the keyboard controller; a first electrically operable, normally open switching means with the operating element connected to the output of, and operable by, the output of the first power supply, and the output from the second power supply for the system circuitry connected through the normally open contacts of the electrically operable switch; and a second electrically operable switching means configured to turn the primary power on and off to the first power supply in response to the presence or absence respectively of an input signal at the voltage level of the second power supply.
In another embodiment there is a third power supply powering another group of peripheral devices, and other embodiments may employ even more power supplies. The use of separate power supplies for separate groups of circuitry provides enhanced efficiency by allowing the computer to operate in reduced power modes with a power supply more closely matched to the powered circuitry than would be the case if all the computer were powered by a single power supply.
In further embodiments, pushbutton switches or toggle switches may be employed to initiate reduced power operating modes for the computer, and also to cause the computer to resume full power operation.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a general-purpose computer with a power supply unit according to an embodiment of the present invention.
FIG. 2 is a block diagram of a general-purpose computer in an embodiment of the present invention comprising a Fax/modem ring indicator circuit.
FIG. 3 is a block diagram of a general-purpose computer according to another embodiment of the present invention and comprising multiple power supplies.
FIG. 4 is a block diagram of a general-purpose computer in an embodiment of the present invention comprising multiple power supplies incorporated on individually driven peripherals.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention addresses the inefficiencies that state-of-the-art power supplies in general-purpose computers exhibit while operating in reduced-power-consumption modes. FIG. 1 is a block diagram of a general-purpose computer in an embodiment of the invention. Power supply unit 11 comprises two power supplies A and B. In this embodiment supply A is a Command Supply and supply B is a Main Supply. Command Supply A supplies regulated voltages of -5, +12 and -12 volts on line 13 to system peripherals 19 at a nominal load of 30 watts and a peak load of 45 watts.
System peripherals comprise any electronic device compatible with one of these voltages for operation. Typically, in a portable, general-purpose computer such devices would be the hard drive, modem, local area network card, cooling fan and/or other serial port I/O devices. The video display and its driving circuitry also fall into this class for purposes of the present invention.
Main supply B supplies a regulated voltage of +5 volts on line 15 at a nominal load of 30 watts and a peak load of 45 watts. Supply B powers the computer's system board to operate all related bus, memory and microprocessor power requirements. Main Supply B also allows for optional power connections at a connection point 38 to run low voltage peripherals, and optionally +3.3 volts at connection point 37 to provide power to CMOS and other low voltage integrated circuits. In an alternative embodiment the system board could be a board powered at 3.3 V, and the output of supply B shown as 5 V could be 3.3 V.
In this arrangement, the system's power requirements are balanced between the two supplies A and B. The fixed and equal split of 90 watts between the two power supplies A and B is exemplary. Power supplies of different nominal and peak capacities may be used where load requirements dictate. The split configuration allows each power supply to operate at improved efficiency by inherently maintaining a higher ratio of minimum to maximum load requirements. The two power units A and B in this embodiments are turned on synchronously by a solid-state switch, such as a Metal Oxide Semiconductor Field Effect Transistor (MOSFET) switch, not shown.
In this embodiment, a user can select to go into a standby mode by inputting to keyboard 25 a keystroke or keystroke combination that sends a signal to keyboard controller on path 12. Keyboard controller 23 in turn sends a shutdown signal on line 40 to Command supply A, turning it off. This removes power from fan 29 and peripherals 19, and by opening switch 27 removes power to system board 21. Main supply B remains on, and powers keyboard controller 23 and keyboard 25. Standby mode represents the lowest power consumption mode for the computer. To the user, standby mode is synonymous with turning the computer off. That is, the user should save work in progress, close applications, exit to the system prompt, and then press a predetermined key or key combination.
In the standby mode, only the keyboard and controller keyboard are active in this embodiment and powered by a single power supply B. From standby, when a user again uses the keyboard, the first keystroke causes a signal on line 40 from keyboard controller 23 to turn power supply A on again, returning power to peripherals 19 and switch 27. Switch 27 closes, and power is restored to system board 21. There are a number of equivalent ways that a signal on line 40 may turn power supply A on and off. For example, output on line 40 may operate a solid-state switch (not shown) which controls primary power to power supply A.
In the embodiment shown in FIG. 1 a user may initiate a suspend mode by a different combination of keystrokes to keyboard 25. In this case a +5 V output from keyboard controller 23 on line 14 powers system board 21, maintaining volatile memory on the board, while power supply A is shut down by a signal in line 40.
FIG. 2 shows an alternative embodiment that incorporates a ring indicator 31, which may be powered by supply B on line 42. The ring indicator signal from any conventional fax/modem or other transmission device is directed to keyboard controller 23 on line 32. While in standby or suspend mode the keyboard controller is active and receives a signal from the ring indicator. Keyboard controller 23 then signals power supply A for power-up as described above, to receive any electronic data from an outside transmission line. This configuration permits a system to be always ready to receive incoming communications via a fax/modem, but to consume significant quantities of power only when the fax/modem is actually in use. A termination signal may also may be received by the keyboard controller from the transmission device to initiate power-down to either standby or suspend mode shortly after receiving the communication.
In yet another alternative embodiment push button inputs or switches may be used to activate standby and/or suspend mode. For example, a push button labeled Standby may be provided to turn power off to power supply A and another labeled Suspend to turn power supply A off while maintaining power to system board 21. Another push button labeled Resume could return power to power supply A. There are many equivalent ways that such inputs might be arranged, which will be apparent to one with skill in the art.
In another aspect of the invention separate power supplies may replace single power supplies in desk-top and workstation computers. Any number of separate power supplies at different peak ratings may be incorporated into a design to best reflect individual system power consumption and production costs. For example, in yet another embodiment according to the invention a power module concept may be practiced where a computer grows with the addition of peripherals by also adding power supply modules.
FIG. 3 is a block diagram comprising a modular unit 11A and comprising an additional power supply C connected directly to keyboard controller 23 and to a number of dedicated peripherals 43A, 43B, and 43C. It also has an additional unused power connection 44. In this embodiment, each power connection may have a different voltage output to match the requirements of the installed peripherals.
The additional peripherals, in this example, may be devices dedicated to expansion slots 22 in a general-purpose computer and represent peripherals above and beyond the standard installed power consumption devices, such as floppy disk drives, hard disk drives and internal modems. In this embodiment, Command power supply A supplies the standard power devices and is connected to switch 27, which disconnects the system board from Main supply B to initiate a standby mode. In the event of a standby or suspend signal, the modular power supply C is signaled on line 46 to shut down power. In this aspect there may be standardized bays, either externally or internally, where additional power supplies such as power supply C are inserted as required. Through other dedicated keystrokes modular power supply C may also be powered up by a signal on a separate line 46. This enables a user to select which modular power supply to power up or down when more than one modular power supply is configured in the system. Custom-configured supplies employing sub-module construction offer flexibility in final design configuration and a means of controlling both initial equipment costs and power losses. Any number of modular power supplies may be dedicated to any number of peripheral banks through system BIOS utilizing machine control routines or a system board read only memory (ROM). In this arrangement each modular power supply may be powered up or down via line 40 and/or dedicated line 46, and system power losses due to the efficiency ratio are kept to a minimum. Less power loss means cooler operating temperatures that may lead to the elimination of some or all power supply cooling fans, thus further saving power and saving on ambient air-conditioning expenses as well.
In yet another aspect of the invention, separate power supplies may be solid-state, single-chip power supply ICs. In FIG. 4, IC power supplies are shown dedicated, sized and mounted on individual peripheral printed circuit boards for optimal power efficiency. Each peripheral carries its own power supply and system board 21 powers up each on-board-power-supply. In this example, on-board-power-peripheral devices 51A, 51B, 51C and 51D are connected by lines 46A 46B, 46C and 46D to keyboard controller 23. In this aspect of the invention, separate microprocessors 60A, 60B, 60C, 60D are dedicated to individual on board power supplies to switch their individual power on and off states directly by control from keyboard 25 though keyboard controller 23. In another configuration, each device's power status and individual proprietary advanced power management may be manipulated through user-friendly machine control routines interfaced to the BIOS. Each on board power peripheral may have different operational voltages. Their respective power requirements are supported through standard expansion bus slots 22A in system board 21, as illustrated in the line connections 45A, 45B, 45C and 45D.
In this arrangement, the on board power peripherals are powered down in the event that the system board's Main supply B is disconnected by switch 27. Further enhanced power modes may be controlled as described above. Each on board power peripheral in FIG. 4 is illustrated in block form as containing a power-supply and peripheral circuitry. In this embodiment, a general-purpose computer maintains near-constant load demands in relation to maximum power levels, therefore delivering optimum efficiency.
An additional embodiment may incorporate the use of multiple power supplies in an external power supply, where the external power supply may be upgraded with power modules as necessary to drive more complex and device-intensive computers. This would be an advantage by first, reducing audio interferences associated with internally installed power supply cooling fans, and secondly by providing a significant reduction in the computer's size. It is possible to implement the invention into existing computer packaging constraints, as well as other electronic devices, and use the electrical connections from existing system boards. There are a number of equivalent ways that several alternatives may be implemented in order to provide improved power efficiencies to present and future generations of general-purpose computers. The embodiments of split and multiple power supplies will further reduce power consumption and help to conserve natural resources.
It will be apparent to one skilled in the art that there are a relatively large number of changes that can be made in the embodiments described without departing from the spirit and scope of the present invention. Some of these alternatives have already been described, such as installing multiple module power supplies into desk-top general-purpose computers, and the different ways to signal a power-up mode to sleeping computers. In particular there are many equivalent ways that circuitry may be arranged and implemented in the many embodiments described.
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A power supply system for a general purpose computer has plural power supplies for powering selected groups of components. One of the power supplies serves the keyboard and its controller, and the keyboard controller is configured to turn the other power supply or supplies on and off in response to user input at the keyboard. The use of separate power supplies increases the efficiency of the computer when operating in reduced power modes.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is the U.S. National Phase of PCT/DK2013/050373 filed Nov. 12, 2013, which claims priority of Danish Patent Application PA 2012 70694 filed Nov. 12, 2012, and Danish Patent Application PA 2012 70742 filed Nov. 29, 2012.
FIELD OF INVENTION
The invention relates to a plug and a system of plugs enabling connection of multiple electronic circuits.
BACKGROUND OF THE INVENTION
When decorating and furnishing shops, hotels etc. numerous electrical installations are made including spots and other lighting devices. This requires connection of multiple cables as well as the use of cables providing different power e.g. 12V, 230V and/or 400V rendering the installation slow and often troublesome. In some cases installations are made above the sealing whereby work must often be performed in hard to reach areas with reduced or no visibility of the work site.
Thus there is a need for plugs and plugs systems which can assist simple and fast installation of multiple devices.
SUMMARY OF THE INVENTION
In a first aspect of the present invention is provided a compact system which is capable of providing more than one electric circuit.
In a second aspect of the present invention is provided a system which facilitates correct alignment of plugs when connected.
In a third aspect of the present invention is provided a system which enables connection of several different power circuits.
In a fourth aspect of the present invention is provided a plug which can form part of plug system.
System
These and other advantages can be achieved by means of a system comprising a housing, a plurality of connectors and a selector outlet, wherein
the plurality of connectors allows for connection of two or more electrical circuits, and the selector outlet has at least a part of the connectors in at least one selector part, and said at least one selector part is movably arranged, whereby a configuration of the connectors is changed when said at least one selector part is moved.
The housing may attain any suitable geometry, such as rectangular, triangular or circular. In particularly, if the housing is rectangular parts of the housing may have a triangular shape, such as the selector outlet may have a triangular shape, whereby the advantages described below in relation to triangular shapes are obtained.
In particularly the part of the housing comprising the selector outlet may have a triangular cross section defined by a first side A, a second side B and a third side C and the number of connectors allows for connection of two or more electrical circuits whereby a compact plug able to provide connection of several electric circuits is provided.
The system according to the present invention may in one embodiment be a plug.
Selector Outlet
The system comprises at least one selector outlet having at least a part of the connectors in at least one selector part, wherein said at least one selector part is movably arranged whereby the configuration of the connectors is changed when said at least one selector part is moved. In particularly, the movement may be a rotation, wherein the configuration of the connectors is changed when said at least one selector part is rotated. I.e. a selector output makes it possible for a user to choose the configuration of the connectors simply by moving, such as rotating the selector part.
The system may comprise one or more selector outlets, each being as defined above.
If e.g. a small plug (as a truncated plug) with five pins (a dali pair, a 230V pair and a ground) is mounted to a spot or other installation it is possible by means of the selector output to choose which of a number of connectors in a distributor plug will match the five pin connectors of the small plug.
Such a selector outlet can advantageously be arranged in e.g. a distributor plug with numerous electric circuits as described above and herein as it allows a user to choose which one or more of the many circuits inside the distributor plug will be connected to a device attached to the selector outlet.
A selector output as here described can however be arranged in various plug types not described herein where there is a need to change the configuration of all of or a part of the connectors.
Often the connector parts can be circular parts which are arranged to be rotatable between two, three, four or more different positions, wherein three different positions are preferred.
If the connectors of the distributor plug are connected to the internal connections by wires inside the plug preferably rotation above 360 deg is prevented by a lock or stop.
Connector parts which are arranged to be moved in e.g. a sliding motion are also imagined.
Thus, according to the present invention is provided a plug and a system of plugs which enable coupling of numerous and different electrical circuits in a manner where the plugs intuitively are correctly aligned by the user due to the shape of the plugs. This means that the present plugs advantageously can be used where many and/or different electrical installations and connections must be made. It also means the present plugs can be handled in hard to reach places as well as in places with limited or no view of the work site. This is achieved by the shape of the present plug together with the way the connectors can be arranged in the plugs and assisted by the guiding parts, sleeves, collars, and coding all in all limiting the possible errors when handling, choosing and connecting the present plugs.
Triangular Cross Section
In the present system the connectors for the two or more electrical circuits can be stacked in a compact formation where the nature of each connector or connector set (e.g. dali+ and dali− or L1 and N1) may be easily recognizable. The triangular cross section makes it possible to stack the connectors in a compact but yet simple pattern.
A triangular plug according to the present invention with connectors for two or more electric circuits also makes it possible that the plug is fed through a conduit, holes etc. which would not be possible with e.g. a rectangular plug where the connectors would have to be arranged side by side. This is due to the special triangular arrangement providing the possibility for a highly compact plug.
In some embodiments the number of connectors is eleven whereby the triangular plugs capability of containing numerous connectors in an easily overviewed arrangement is used highly efficiently. In other embodiments depending on the intended use the number of connectors can be more or less.
Preferably the lengths of the sides A, B, C are chosen to ensure that two plugs according to the present invention can be oriented correctly with respect to each other even when light or working conditions are not optimal. If for example the length of side A=the length of side B and both A and B are different from the length of side C (or if all three sides A,B,C are of a different length) a triangular plug according to the present invention is achieved, where said plug can be oriented correctly with respect to another plug without the need to fully see the plugs. This is due to the fat that it is not possible to connect two such triangular plugs if they are not oriented correctly with respect to each other. This is in contrast to e.g. circular or rectangular plugs.
Connectors
In some embodiments the connectors belong to dali+−, L1+N, L2+N, L3+N (e.g. 230V), and PE (ground) respectively, i.e. where 9 connectors are used. In this configuration the connectors for four circuits are arranged with a common ground. Here the four circuits are one 12 v and three 230V.
In some embodiments the connectors belongs to dali1+−, dali2+−, L1+N, L2+N, L3+N, and PE respectively, i.e. where 11 connectors are used. In this configuration the connectors for 5 circuits are arranged with a common ground. Here the five circuits are two 12 v and three 230V.
In some large embodiments the connectors belongs to dali1+−, dali2+−, dali3+−, L1+N, L2+N, L3+N, and PE respectively, i.e. where thirteen connectors are used. In this configuration the connectors for six circuits are arranged with a common ground. Here the six circuits are three 12 v and three 230V.
In smaller embodiments the connectors belongs to dali1+−, dali2+−, L1+N, and PE respectively, i.e. where seven connectors are used. In this configuration the connectors for 5 circuits are arranged with a common ground. Here the three circuits are two 12 v and one 230V.
In smaller embodiments the connectors belongs to dali1+−, L1+N, and PE respectively, i.e. where five connectors are used. Here the three circuits are one 12 v and one 230V.
The present plug can combine electrical circuits of 12V, 230V and 400V alone or in combination.
Plugs
A plug enabling connection of several and even different types electric circuits can be advantageous as it can minimize the number of parallel cables which may have to be installed. For example a plug with nine connectors limits the need for four different cables/installations to one. However, traditional e.g. rectangular or circular plugs becomes bulgy, long and/or complicated making identification of each connector hard.
A plug according to the present invention can be arranged so that the connectors forms a male (with connectors in form of pins) or a female plug (with connectors in form of holes) in order to achieve plugs which are connectable to each other.
In some embodiments the plug comprises a first end for receiving a cable and a second end arranged with the male or female connectors.
In various embodiments the plug comprises a first end having a first set of connectors (e.g. nine or eleven) and a second end arranged with a second set of connectors (e.g. nine or eleven). I.e. the plug comprises a first end arranged with male or female connectors and a second end arranged with male or female connectors.
In further embodiments one or more plugs according to the present invention are connected to another plug with a cable thus forming an extension.
Also plugs according to the present invention can comprise at least one further outlet thus forming a distributor plug. This further outlet is preferably also a triangular plug with connectors arranged according to the present invention.
Thus the plugs according to the present invention can be used in many different configurations providing a plug to different needs and situations.
If the plug comprises first and/or second lock parts for releasably locking two plugs together it is possible to avoid that the plugs are separated by accident. The lock formed by the first and second lock parts can be of different types. For example a first plug can have a hole and a corresponding second plug for connecting to the first plug can have a biased protrusion which can click into the hole of the first plug to lock the two plugs together. The biased protrusion can be pressed by a user thereby allowing the two plugs to be separated again. Plugs with first and/or second lock means may advantageously be used for example in permanent installations or in installations where there is a need for or a risk that one or more parts may be moved, pulled or otherwise handled after installation i.e. where there is a risk that two plugs may accidentally be separated.
In different embodiments the first side A is e.g. 1.5-4.5 cm depending on the intended use of the plug. A short side length provides a small, compact plug. A longer side length provides a larger plug where more connectors/electronic circuits can be arranged. Side lengths shorter or longer than 1.5-4.5 cm can be chosen to provide even smaller or larger plugs for example where very delicate connections must be made in little space or where a large number of electrical circuits must be connected by one plug.
The depth, i.e. the distance between first and second end can be chosen to make space for any internal connections to e.g. distributor plugs or to connections between wires from a cable and the connectors of the plug. Thus the depth can span from less than 1 cm to 20 cm or more depending on the intended use and number and type of cables and/or devices to be connected.
The corners and different sides of the plug can be sharp, rounded, truncated etc. to provide plugs with no or few sharp edges.
Plugs according to the present invention can be provided as closed units i.e. where the user cannot open or change the configuration of the internal parts and/or the connectors. Alternative embodiments where the user can open the plugs can be provided if it is advantageous to be able to change e.g. the configuration of the connectors.
The plug according to the present invention can be waterproof thus providing a plug which can be used with enhanced safety in moist conditions. Waterproofing can be provided by internal and/or external seals sealing openings in the plugs and/or preventing that moisture enters between two connected plugs.
The present invention also relates to a system comprising triangular female plugs, male plugs, distributor and/or extension plugs whereby a versatile system is achieved allowing use of the plugs in numerous configurations and for a variety of large and small installations.
A system may also comprise additional truncated plugs which fit into the triangular shape and the dimensions of the male, female, distributors and/or extensions of the system. Said truncated plugs comprising a subset of the connectors of the male, female, distributor and/or extension plugs of the system. For example truncated plugs can be used to engage in part of the output of a distributor plug. Truncated plugs can be used to mount on e.g. lamps or devices which are to be connected to an electrical installation comprising the present plugs but which lamp or device only require connection to a subset of the connectors in a male, female, distributors and/or extensions of the system. Truncated plugs may e.g. comprise from two connectors. In some embodiments systems comprising truncated male/female/distributor/extension plugs can be imagined e.g. where large systems of spots are to be mounted.
Rail
Preferably the system further comprises a rail which can hold one or more distributors and/or extensions according to the present invention.
Said rail can advantageously have means for receiving one or more distributors and/or extensions. These means can be arranged to fit with the different plugs, preferably distributor plugs, by sliding, twisting, pressing etc. the plug to be fastened on the means for receiving. Preferably the plug e.g. distributor and/or extensions are releasable attached in the rail.
In some embodiments the extensions are dimensioned to connect two distributors received in a rail. Several different types and lengths of extensions can be used but often preferably standard connector lengths are used. The length of the extensions can be adapted to correspond to the distance between two distributors arranged in a rail.
Type of Electrical Circuit
In some embodiments a plug is prepared for e.g. 7, 9, 10 or 11 connectors but only a subset of these are in use.
The type of electrical circuits relating to the connectors can be indicated by colour cording or other markings on the plug. It is also possible that codes are used to indicate which connectors are connected inside the plug. For example it can be imagined that a plug e.g. only has “active” dali+/− and L2, N2 which can be indicated on the plug by e.g. a colour code.
The different type of plugs according to the present invention can be hollow with internal connections (wires, cables, metal plates etc.) between connectors in the first side and corresponding connectors in the second side or between connectors in the first side and corresponding wires in a cable attached at second side or vice versa.
In other embodiments the plug is solid or at least partly solid with internal connections between connectors in the first side and corresponding connectors in the second side or between connectors in the first side and corresponding wires in a cable attached at second side or vice versa. The internal connections can advantageously be formed by metal conductors cast into the plug during manufacturing of the plug. In such solid or at least partly solid embodiments of different plugs according to the present invention, the internal connections can be protected to avoid short circuits by an electrical insulating material and/or the material from which the plug or part of the plug may be cast can be electrically insulating itself.
During manufacturing the internal connections can be arranged and fixated relatively to each other where after the plug is cast in one or more steps around the internal connections.
It is also possible that the ends of the connectors are fixated where after the ends and possibly other parts of the plug are cast. When the plug is cast around connectors fixated at their ends, the internal connections are preferably made of insulated conductors. The resulting plug, extension, distributor is preferably at least partly hollow.
A hollow plug, extension, distributor can be lighter and cheaper to produce as it contains less material. A solid plug, extension, distributor can be more sturdy and/or provide a fixed protection of the internal connections.
The pin connectors can be of various dimensions i.e. have a width and/or length adapted to the use of the plug.
The size and shape of the connectors can thus be chosen based on the intended use. The male connectors can e.g. be simple relatively thin pins, rounded pins with a larger diameter, flat pins and/or pins with a semi-circular cross section. The corresponding female connectors are arranged to match the shape of the male plugs and vice versa.
The female connectors can be holes adapted to receive the pin connectors. In several embodiments the female connectors are arranged with contact elements which are biased to press against the pin connectors to ensure a good electrical connection.
Plugs according to the present invention can be made of one or more materials for example from the group of plastics, rubber, resins, with electrical connectors and internal connections of various suitable conducting structures.
The present plugs can be arranged to comply with various international, regional or national safety protocols and requirements.
A plug can have one or more selector outlets having a number of connectors wherein at least a part of the connectors are arranged in one more selector parts, and wherein
said one or more selector part is moveably arranged, and the configuration of the connectors are changed when one or more selector parts is moved. I.e. a selector output makes it possible for a user to choose the configuration of the connectors.
If e.g. a small plug (as a truncated plug) with five pins (a dali pair, a 230V pair and a ground) is mounted to a spot or other installation it is possible by means of the selector output to choose which of a number of connectors in a distributor plug will match the five pin connectors of the small plug.
Such a selector outlet can advantageously be arranged in e.g. a distributor plug with numerous electric circuits as described above and herein as it allows a user to choose which one or more of the many circuits inside the distributor plug will be connected to a device attached to the selector outlet.
A selector output as here described can however be arranged in various plug types not described herein where there is a need to change the configuration of all of or a part of the connectors.
Often the connector parts can be circular parts which are arranged to be rotatable between two, three, four or more different positions, preferably it is rotatable between three different positions.
In one embodiment the selector has a pairs of connectors for each position. It is preferred each of the pair would be bipolar and have their own phase.
If the connectors of the distributor plug are connected to the internal connections by wires inside the plug preferably rotation above 360 deg is prevented by a lock or stop.
Connector parts which are arranged to be moved in e.g. a sliding motion are also imagined.
Thus, according to the present invention is provided a plug and a system of plugs which enable coupling of numerous and different electrical circuits in a manner where the plugs intuitively are correctly aligned by the user due to the shape of the plugs. This means that the present plugs advantageously can be used where many and/or different electrical installations and connections must be made. It also means the present plugs can be handled in hard to reach places as well as in places with limited or no view of the work site. This is achieved by the shape of the present plug together with the way the connectors can be arranged in the plugs and assisted by the guiding parts, sleeves, collars, and coding all in all limiting the possible errors when handling, choosing and connecting the present plugs.
DESCRIPTION OF THE DRAWINGS
The invention will in the following be described in greater detail with reference to the accompanying drawings. The drawings are exemplary and are not to be construed as limiting to the invention.
FIG. 1 shows a triangular female plug according to the present invention
FIG. 2 shows a triangular male plug according to the present invention
FIG. 3 shows an extension according to the present invention
FIG. 4 shows a distributor according to the present invention
FIG. 5 shows a rail according to the present invention
FIG. 6 shows a rail with distributors and extensions according to the present invention
FIG. 7 shows a coded triangular plug according to the present invention
FIG. 8 shows a triangular plug according to the present invention with a sleeve
FIGS. 9 and 10 show plugs according to the present invention with corresponding guiding means
FIGS. 11 and 12 show plugs according to the present invention with corresponding lock means
FIG. 13 a , 13 b , 13 c show exemplary different embodiments of plugs according to the present invention,
FIGS. 14 a and 14 b show truncated plugs matching a triangular plug
FIG. 15 shows a distributor plug with two selector outlets
FIG. 16 shows a distributor plug with a single selector outlet
FIG. 17 shows a selector output with two separate circular selector parts
FIG. 18 shows a selector output with two concentric selector parts
FIG. 19 shows two embodiments of plugs matching a selector outlet, and
FIGS. 20 and 21 shows two further embodiments of plugs matching a selector outlet.
FIGS. 22 a and 22 d show an assembled system of two triangular plugs
FIGS. 22 b and 22 c show two triangular plugs used to form an assembled system
FIG. 23 a shows a triangular housing for a plug
FIGS. 23 b and 23 c show a selector outlet for a plug
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a triangular plug 1 according to the present invention. The plug comprises a housing 2 having three sides A, B and C and side surfaces 2 a , 2 b , 2 c . In the present embodiment the sides A and B have the same length and are longer than the side C.
The housing has a first end 5 wherein eleven connectors 3 are arranged. Opposing the first end 5 is second end 6 wherein a cable 7 is attached. The cable 7 connects to the connectors inside the housing. The first, second and third surface extend between the first 5 and second end 6 . In the present the example the plug is a she plug where each of the connectors 3 are holes for receiving pins from a corresponding male plug.
The connectors are stacked in a pattern following the triangular shape of the first end 5 i.e. follow the triangular cross section of the plug. Hereby is provided a quite compact plug where the space of the first end is fully utilized to provide several electric circuits arranged in a pattern which is simple and which makes it easy to determine which connector belongs to which electric circuit.
In this shown embodiment the connectors are: a,b=L1,N; c,d=L2,N; e,g L3,N; f=ground; h,i=dali1+, dali1−; j,k dali2+, dali2−.
FIG. 2 shows a male plug with pin connectors 8 . This plug is shown without a connected cable 7 .
FIG. 3 shows two plugs 1 connected by a cable 7 thus forming a connector 9 . Depending on the intended use the plugs can be female and/or male plugs as well as the length of the cable can vary.
FIG. 4 shows a distributor plug 10 . In this embodiment the distance between the first 5 and second end 6 are long enough to allow eleven connectors 3 to be arranged on the first surface 2 a forming an outlet 11 thereby allowing a device or a plug to be attached not only at each of the first 5 and second end 6 but also at each of the surfaces 2 a and/or 2 b (not shown).
FIG. 5 shows a rail 12 . The rail is formed as an elongated element with a simple U shape formed by two side walls 12 a and a bottom 12 b . Along the middle of the bottom attachment means 13 a, b, c, d are distributed spaced apart by a distance d. 13 a is in the form of a partly circular protrusion. 13 b is in form of a rectangular protrusion. 13 c is in the form of a circular indentation and 13 d is in the form of a protruding hook shape for slideably receiving e.g. a distributor (not shown).
In FIG. 6 two distributors 10 have been attached to attachment means 13 in a rail 12 . The distributors are attached by engaging the attachment means 13 with corresponding means (not shown) in the distributors 10 . The distributors are connected by connectors 9 thereby forming and array of connected distributors to which different installations such as spots, speakers, ventilations etc can be connected.
The setup of FIG. 6 can for example advantageously be used where numerous devices are to be installed across a loft or panel where each device requires electrical connection and even requires different current which can be provided by the novel present plug.
FIG. 7 shows a plug which is coded e.g. colour coded by mark 14 . Coding of the plugs can advantageously be used where not all connectors (a-f) are connected to e.g. the cable 7 inside the housing of the plug.
FIG. 8 shows a plug where a circumferential collar 15 is arranged around the first end 5 . This collar 15 can e.g. be used to guide the engagement with another plug. If the collar is made of a e.g. rubber or silicone the collar may help avoid moisture entering the area between two plugs.
FIGS. 9 and 10 shows plugs with corresponding guiding parts here in the form of an elongated protrusion 16 on one for sliding into groove 17 on another plug. In the present embodiments the elongated protrusion 16 is on the female plug and the groove 17 is in the male plug however this can also be the other way around.
The guiding parts 16 , 17 are used to assist the connection of the two plugs even further than what is achieved by the triangular structure alone. I.e. it may help that the two plugs are inserted in a way which may further prevent bending of the connectors.
In FIG. 9 the plug has sides extending further than the first end 5 thus forming a circumferential sleeve 18 . This sleeve can have a function the same or similar to the collar 15 of FIG. 8 . However the sleeve here is an integrated part of the plug whereas the collar 15 can be a detachable part of the plug.
FIGS. 11 and 12 shows plugs with corresponding first 19 and second 20 lock means for locking the two plugs releasably together to avoid accidental disconnection. The first lock part is 19 a hole in the sleeve 18 which will be engaged by a knob 21 on the second lock means 20 when the two plugs are connected. The second lock means has the shape of a flap 22 which can be pressed inwards to allow engagement and disengagement of the two lock parts.
The plug in FIG. 12 is a distributor plug with two outlets 11 on one side (the side not shown can have similar or other outlets). In this embodiment the outputs 11 has eleven and five female connectors. The connectors 8 in the first end 5 are eleven male connectors 8 .
FIG. 13 a , 13 b , 13 c show different embodiments of female plugs according to the present invention. In FIG. 13 a the third side C is significantly longer than sides A and B and the connectors 3 are here flat and elongated holes for receiving corresponding male pins in matching plugs. In FIG. 13 b the sides A and B are significantly longer than side C. In FIG. 13 c the sides A; B; C have the same length and the corners 23 are truncated.
FIGS. 14 a and 14 b show different types of truncated plugs matching other types of plugs according to the present invention (indicated by dotted lines). A truncated plug as 24 a and 24 b can clearly be arranged to fit in one position only of another plug (dotted line). However, this can also be the case for 24 c where the width of the plug can be chosen to allow precise positioning.
FIG. 15 shows a distributor plug with two selector outlets 25 a . The selector outlets each comprise a first selector part 26 (having two pairs of dali connectors) and a second selector part 27 having (three pairs of 230V connectors). In the present arrangement the first and second selector part are discs which can be moved more specifically rotated to change the configuration of the outlet 25 a . A matching plug 24 d has five pin connectors 8 which in the present configuration of first and second selector part of the left outlet in distributor plug will connect to Dali2+− and to L1, N1, PE. If the first selector part is rotated 90 deg counter clockwise the plug 24 d will engage Dali1+− and L1, N1, PE. Similarly if second selector part is rotated 50 deg the plug 24 d will engage Dali2+− and L2, N2, PE.
This way the selector outlets 25 a allows the user to configure the connectors, by turning the first and second selector part, to select which connectors 3 will engage with the matching plug 24 d . I.e. this way the special selector output enables a user to choose which of the several circuits in the distributor plug will be connected to a device attached to the plug 24 d.
FIG. 16 shows a distributor plug with an alternative selector outlet 25 b wherein the first 26 and second 27 selector part are arranged as two concentric circles.
FIG. 17 shows an alternative outlet with a first 26 and second 27 selector part arranged to allow a user to select which five of the eleven connectors 3 will engage with matching connectors 8 in male plug 24 e.
As in FIG. 15 the first and second selector part are a small circular rotatable part with two dali connector pairs and a larger circular rotatable part with three 230V/400V connector pairs and a common ground PE respectively.
In FIG. 17 the matching male plug is a rectangular narrow plug with a row of five pin connectors 8 . Dx+ and Dx− are for connecting to one of the two dali pairs of the first selector part 26 and Lx, PE, Nx is for connecting to PE and one of the 230V/400V connector pairs of the second selector part 27 .
Depending on the position of the first selector part 26 Dx will be either D1 or D2 (i.e. dali 1 or dali 2). Depending on the position of the second selector part 27 Lx,Nx will be either L1,N1 or L2,N2 or L3,N3.
FIG. 18 shows another embodiment of a selector outlet wherein the first and second selector part are arranged as two concentric rotatable parts. In this embodiment the second selector part 27 has four pairs of 230V/400V connectors L1,N1 L2,N2 L3,N3 L4,N4. A common ground PE is arranged in the centre. The first selector part 26 has two pairs of dali connectors dali1+− and dali2+−. I.e. this sector outlet comprises thirteen connectors.
The selector outlets of FIG. 17 and FIG. 18 can be arranged in triangular plugs as described herein or in other types of plugs 28 with another geometry. Generally the selector outlet can advantageously be used in plugs with several circuits wherein only one or a subset of the total electrical circuits needs to be connected to a device or other plug.
FIG. 19 shows a triangular and a truncated triangular embodiment of plugs with five pin connectors for engaging in a selector outlet as e.g. in FIG. 15 or FIG. 17 .
FIG. 20 shows a circular male plug 24 h with five pins 8 connectors. FIG. 21 shows a circular male plug 24 i with three pin connectors 8 . Both plugs can engage with e.g. selector outlets with concentric selector parts as in FIG. 16 and FIG. 18 .
FIGS. 22 a and 22 d show an assembled system of two triangular plugs consisting of two triangular plugs as shown in FIGS. 22 b and 22 c . FIG. 22 c shows a configuration wherein the different connectors are female and rotationally arranged. The connectors are rotatable between three different positions, such that the selector has three pairs of connectors, i.e. a pair of L1+1, a pair of L2+1 and pair of L3+1. FIG. 22 b shows a male plug, however the pins are not shown. The housing is an equilateral triangle but it could be scalene.
FIG. 23 a shows a triangular housing for a plug, wherein a selector output with one selector part as shown in cross section in FIG. 23 c and in perspective in 23 b can be inserted. The selector part is rotationally arranged and is shown with female connectors. The housing is an equilateral triangle but it could be scalene.
The above figures each show different features of the present invention which features can be combined in various ways. E.g. the sleeve 18 or collar 15 can form part of male plugs, distributors and/or extensions. Similarly guides, locks, connectors of different shape/size and truncated corners can form part of the various embodiments.
Thus according to the present invention is provided a plug which can be arranged in numerous ways, male and/or female, as an extension and a distributor providing a new type of plugs enabling the connection of a multitude of electric circuits by one compact plug. The plugs can be arranged to connect different types and numbers of electric circuits as well as they can be arranged to provide a very intuitive orientation of the plugs ensuring correct and fast connection of two plugs.
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The invention regards a plug comprising a housing, a number of connectors and a selector outlet having a movable selector part whereby the configuration of the connectors may be changed when the selector part is moved. The housing may have a triangular cross section defined by a first side A, a second side B and a third side C and where the number of connectors allows for connection of two or more electrical circuits. The invention also relates to a system of plugs and a method of producing the same.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This present application claims priority to U.S. Provisional Patent Application Ser. No. 60/848,091, to Bala, filed Sep. 29, 2006, entitled “INFERCLUSTER: A PRIVACY PRESERVING DISTRIBUTED CLUSTERING ALGORITHM.” The present application is also a continuation-in-part of U.S. application Ser. No. 10/616,718, filed Jul. 10, 2003, entitled “DISTRIBUTED DATA MINING AND COMPRESSION METHOD AND SYSTEM.”
FIELD OF THE INVENTION
[0002] This invention relates generally to methods for classifying data, and in more particular applications, to data clustering methods.
BACKGROUND
[0003] Data clustering methods generally relate to data classifying methods whereby common data types are grouped together to form one or more data clusters. Generally, there are two main types of clustering techniques—partitional clustering and hierarchical clustering. Partitional clustering involves determining a partitioning of data records into “k” groups or clusters such that the data records in a specific cluster are more similar or nearer to one another than the data records in different clusters. Hierarchical clustering involves a nested sequence of partitions such that it keeps merging the closest (or splitting the farthest) groups of data records to form clusters.
[0004] Clustering from non-distributed data has been studied extensively and reported. For example, clustering and statistics has been described in P. Arabie and L. J. Hubert. “An overview of combinatorial data analysis.” In P. Arabie, L. Hubert, and G. D. Soets, editors, Clustering and Classification, pages 5-63, 1996. Clustering and pattern recognition has been discussed in K. Fukunaga. Introduction to statistical pattern recognition, Academic Press, 1990. Clustering and machine learning has been discussed in D. Fisher. “Knowledge acquisition via incremental conceptual clustering.” Machine Learning, 2:139-172, 1987.
[0005] Most of the existing distributed data clustering techniques assume that all data can be collected on a single host machine and represented by a homogeneous and relational structure. This assumption is not very realistic in today's distributed data collection computing systems. Thus, there have been a number of efforts in the research community directed towards distributed data clustering. Unfortunately, the problem with most of these efforts is that although they allow the databases to be distributed over a network, they assume that the data in all of the databases is defined over the same set of features. In other words they assume that the data is partitioned horizontally. In order to fully take advantage of all the available data, the distributed data clustering algorithms must have a mechanism for integrating data from a wide variety of data sources and should be able to handle data characterized by: spatial (or logical) distribution, complexity and multi feature representations, and vertical partitioning/distribution of feature sets.
SUMMARY
[0006] In one form, a method for distributed data clustering is provided. The method includes the steps of providing data points each having at least one attribute, determining a two class set of data including data to be clustered and non-cluster data or synthetic, determining an overall best attribute selection from each of a plurality of clustering agents whereby the overall best attribute selection has the highest overall information gain containing data to be clustered, creating a rule based on the overall best attribute, splitting the data points into at least two groups, creating a plurality of subsets wherein each subset contains data from only one class and outputting complete rules whereby the data points are all located in the subsets.
[0007] According to one form, a method for distributed data clustering is provided. The method includes the steps of invoking a plurality of clustering agents at different data locales by a mediator, beginning attribute selection by the plurality of clustering agents, wherein each of the agents determines a best attribute selection that has the highest local information gain value among all attributes to differentiate cluster data from non-cluster data, passing the best attribute from each of the plurality of clustering agents to the mediator, selecting a winning clustering agent from said plurality of agents by said mediator, the winning clustering agent having the best attribute having the highest global information gain, initiating data splitting by the winning agent, forwarding split data index information resulting from the data splitting by the winning agent to the mediator, forwarding the split data index information from the mediator to each of the plurality of clustering agents, initiating data splitting by each of the plurality of clustering agents other than the winning clustering agent, generating and saving partial rules and outputting complete rules to the plurality of clustering agents.
[0008] In one form, the rules are created by a decision tree classification.
[0009] According to one form, the steps of determining an overall best attribute, creating a rule and splitting the data points are performed in an iterative manner such that each subset contains data from only one class.
[0010] In one form, the data to be clustered is in data dense regions and the non-cluster data are in empty or sparse regions.
[0011] According to one form, the non-cluster data is synthetic data.
[0012] In one form, a system for distributed data clustering is provided. The system includes at least one memory unit having a plurality of data points and a plurality of processing units. The plurality of processing units are used for determining a two class set of data including data to be clustered and non-cluster data, determining an overall best attribute selection from each of a plurality of clustering agents whereby the overall best attribute selection has the highest overall information gain containing data to be clustered, creating a rule based on the overall best attribute, splitting the data points into at least two groups, creating a plurality of subsets wherein each subset contains data from only one class and outputting complete rules whereby the data points are all located in the subsets.
[0013] Other forms are also contemplated as understood by those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] For the purpose of facilitating an understanding of the subject matter sought to be protected, there are illustrated in the accompanying drawings embodiments thereof, from an inspection of which, when considered in connection with the following description, the subject matter sought to be protected, its constructions and operation, and many of its advantages should be readily understood and appreciated.
[0015] FIG. 1 is a diagrammatic representation of one form of method for data clustering;
[0016] FIG. 2 is a diagrammatic representation of communication between an agent and a mediator regarding the discovery of data clusters;
[0017] FIG. 3 is a diagrammatic representation of one form of a distributed data mining method and system; and
[0018] FIG. 4 is a diagrammatic representation of an agent-mediator communication mechanism.
DETAILED DESCRIPTION
[0019] Clustering refers to the partitioning of a set of objects in groups (clusters) such that objects within the same group are more similar to each other than objects in different groups. The data in each cluster (ideally) share some common trait, often proximity according to some defined distance measure. Clustering is often called unsupervised learning because no classes denoting an a priori partition of the objects are known.
[0020] In one form, the method is concerned with scenarios where data to be clustered is collected at distributed databases and cannot be directly centralized or unified as a single file or database due to a variety of constraints (e.g., bandwidth limitations, ownership and privacy issues, limited central storage, etc).
[0021] FIG. 1 depicts one form of the distributed clustering method. There are two distributed data locales (x and y coordinates of the distributed representation space). As illustrated in FIG. 1 , the data locales each contain one or more agents 20 , 22 and contain data to be clustered 24 (shown as darker shaded circles) and synthetic data 26 (shown as lighter shaded circles). It should be understood that in one form, the synthetic data 26 is non-cluster data. Additionally, in one form, the synthetic data 26 are uniformly distributed in the representation space to differentiate the synthetic data 26 from the data to be clustered 24 .
[0022] The method starts by generating the synthetic data points 26 representing empty (sparse) regions by uniformly distributing them in the representation space. Clustering agents 20 , 22 on each site of the data locales (x and y coordinates), use their accessible data definitions (x and y coordinates) and find the first best partition separating data to be clustered 24 from the synthetic data 26 . The quality measures on the best local partitions are computed using information gain parameters and are sent to a mediator component. This mediator component compares all quality measures and decides which one is globally the most optimal one. Following this determination, the mediation component instructs the agent 20 , 22 with the best partition quality measure to split the data. For example, in FIG. 1 ( a ) the agent 20 at a first data locale splits the data 24 , 26 . After the data is partitioned, the data partitioning agent broadcasts indices on the data split to other agents (i.e., in FIG. 1 ( a ), agent 20 sends indices to agent 22 at another data locale). This step results in generation of two partitions, denoted “ 1 ” and “ 2 ” in FIG. 1 ( a ).
[0023] In the next step, the agents 20 , 22 collaborate on further splitting of the “ 2 ” partition. In FIG. 1 ( b ), two additional partitions, “ 2 . 1 ” and “ 2 . 2 ”, are generated by the contributing agent, in this case, agent 22 . This process is repeated/iterated until all data points to be clustered 24 are consistently and completely “enclosed” inside partitions (i.e., in FIG. 1 ( d ), the cluster partitions are “ 1 . 2 ” and “ 2 . 2 . 1 ”).
[0024] FIG. 2 represents another form of the clustering method. In one form, the method executes the following steps:
[0025] Step 1. Agent B contributes the “best” split measure and partitions the data. Data indices are broadcast to Agent A which generates partitions: “ 1 ” and “ 2 ”.
[0026] Step 2. Agent A contributes the “best” split measure and partitions the data within the partition “ 2 ”. Data indices are broadcast to Agent B which generates partitions: “ 2 . 1 ” and “ 2 . 2 ”.
[0027] Step 3. Agent A contributes the “best” split measure and partitions the data within partition “ 2 . 2 ”. Data indices are broadcast to Agent B which generates partitions: “ 2 . 21 ” and “ 2 . 22 ”. Partition “ 2 . 2 . 2 ” is a cluster partition.
[0028] Step 4. Agent B contributes the “best” split measure and partitions the data within partition “ 1 ”. Data indices are broadcast to Agent A which generates partitions: “ 1 . 1 ” and “ 1 . 2 ”. Partition “ 1 . 2 ” is a cluster partition.
[0029] Distributed Data Mining
[0030] In one form, distributed data mining is utilized as part of the clustering method. FIG. 3 illustrates one basic form of distributed data mining. Distributed mining is accomplished via a synchronized collaboration of agents 10 as well as a mediator component 12 . (see Hadjarian A., Baik, S., Bala J., Manthorne C. (2001) “InferAgent—A Decision Tree Induction From Distributed Data Algorithm,” 5th World Multiconference on Systemics, Cybernetics and Informatics (SCI 2001) and 7th International Conference on Information Systems Analysis and Synthesis (ISAS 2001), Orlando, Fla.). The mediator component 12 facilitates the communication among agents 10 . In one form, each agent 10 has access to its own local database 14 and is responsible for mining the data contained by the database 14 .
[0031] Distributed data mining results in a set of rules generated through a tree induction algorithm. The tree induction algorithm, in an iterative fashion, determines the feature which is most discriminatory and then it dichotomizes (splits) the data into a two class set, a class representing data to be clustered and a class representing synthetic data. The next significant feature of each of the subsets is then used to further partition them and the process is repeated recursively until each of the subsets contain only one kind of labeled data (cluster or non-cluster data). The resulting structure is called a decision tree, where nodes stand for feature discrimination tests, while their exit branches stand for those subclasses of labeled examples satisfying the test. A tree is rewritten to a collection of rules, one for each leaf in the tree. Every path from the root of a tree to a leaf gives one initial rule. The left-hand side of the rule contains all the conditions established by the path and thus describe the cluster. In one form, the rules are extracted from a decision tree.
[0032] In the distributed framework, tree induction is accomplished through a partial tree generation process and an Agent-Mediator communication mechanism, such as shown in FIG. 4 that executes the following steps:
[0033] 1. Clustering starts with the mediator 12 issuing a call to all the agents 10 to start the mining process.
[0034] 2. Each agent 10 then starts the process of mining its own local data by finding the feature (or attribute) that can best split the data into cluster and non-cluster classes (i.e. the attribute with the highest information gain).
[0035] 3. The selected attribute is then sent as a candidate attribute to the mediator 12 for overall evaluation.
[0036] 4. Once the mediator 12 has collected the candidate attributes of all the agents 10 , it can then select the attribute with the highest information gain as the winner.
[0037] 5. The winner agent 10 (i.e. the agent whose database includes the attribute with the highest information gain) will then continue the mining process by splitting the data using the winning attribute and its associated split value. This split results in the formation of two separate clusters of data (i.e. those satisfying the split criteria and those not satisfying it).
[0038] 6. The associated indices of the data in each cluster are passed to the mediator 12 to be used by all the other agents 10 .
[0039] 7. The other (i.e. non-winner) agents 10 access the index information passed to the mediator 12 by the winner agent 10 and split their data accordingly. The mining process then continues by repeating the process of candidate feature selection by each of the agents 10 .
[0040] 8. Meanwhile, the mediator 12 is generating the classification rules by tracking the attribute/split information coming from the various mining agents 10 . The generated rules can then be passed on to the various agents 10 for the purpose of presenting them to the user through advanced 3D visualization techniques.
[0041] Clustering has become an increasingly essential Business Intelligence task in domains such as marketing and purchasing assistance, multimedia as well as many others. In many of these areas, the data are originally collected at distributed databases. In order to extract clusters out of these databases the expensive and time-consuming data warehousing step is required, where data are brought together and then clustered.
[0042] One exemplary application of one form of the method for clustering data is for marketing products to customers. Different divisions of a company maintain various databases on customers. The databases are owned by multiple parties that guard confidential information contained in each database. For example, the marketing division of a company won't share its data as it contains important strategic information like the customer segments who responded most frequently to high-profile campaigns. The product design division maintains its own database and would like to see the marketing data as they target certain demographics for new product features.
[0043] The goal is to cluster the entire distributed data, without actually first pooling this data from the two divisions.
[0044] One form of the clustering method can be used to generate cluster descriptions of customer segments across these data sources that will help to answer questions such as: What will customers buy?; What products sell together?; What are the characteristics of customers that are at risk for churning?; What are the characteristics of marketing campaigns that are successful? These questions can be answered by analyzing the rule based descriptions of the clustered data.
[0045] The customer databases may also represent different web portals. Users of a web application on a specific portal can follow a variety of paths through the portal. The method and system can analyze distributed data and can find patterns that represent a sequence of pages through the site. Such distributed data represents one or more sequences of visited pages and clock stream elements. These patterns can be analyzed to determine if some paths are more profitable than others.
[0046] It should be appreciated that the above example is an application of one form of the present method and system. It should be understood that variations of the method are also contemplated as understood by those skilled in the art. Furthermore, it should be understood that the methods described herein may be embodied in a system, such as a computer, network and the like as understood by those skilled in the art. The system may include one or more processing units, hard drives, RAM, ROM, other forms of memory and other associated structure and features as understood by those skilled in the art. It should be understood that multiple processing units may be used in the system such that one processing units performs certain functions at one data locale, a second processing unit performs certain functions at a second data locale and a third processing unit acts as a mediator.
[0047] The matter set forth in the foregoing description and accompanying drawings is offered by way of illustration only and not as a limitation. While particular embodiments have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the broader aspects of applicants' contribution. The actual scope of the protection sought is intended to be defined in the following claims when viewed in their proper perspective based on the prior art.
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A method for distributed data clustering is provided. The method includes the steps of providing data points each having at least one attribute, determining a two class set of data including data to be clustered and non-cluster data, determining an overall best attribute selection from each of a plurality of clustering agents whereby the overall best attribute selection has the highest overall information gain containing data to be clustered, creating a rule based on the overall best attribute, splitting the data points into at least two groups, creating a plurality of subsets wherein each subset contains data from only one class and outputting complete rules whereby the data points are all located in the subsets.
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This is a continuation of Ser. No. 07/101,569, filed 9/25/87, now U.S. Pat. No. 4,826,334.
TECHNICAL FIELD
This invention relates generally to printing ribbon holders and particularly to an endless loop-type ribbon cassette
BACKGROUND OF THE INVENTION
It is common practice today to employ a ribbon cassette carrying an endless ribbon as an ink source for typewriters and computer driven printers, the latter typically being of either the dot matrix or printwheel type. One method of storing such a ribbon has been by randomly stuffing it into a chamber of a cassette. This often results in an extremely high number of bends or creases in the ribbon, this occurring at repeated distances on the order of one-quarter inch or less. Thus, with a typical 360-inch length ribbon, there may be on the order of 1,440 bends or creases. It is to be appreciated that this has two distinct disadvantages. One is that an impact of a print head through a crinkled ribbon will produce uneven print. The second disadvantage is that each bend or crease in a ribbon consumes extra storage space and thus the storage capacity for ribbon is diminished.
Another method of storing such ribbon in a cassette is by directing the ribbon into a storage cavity where it is stored in orderly arranged folds. Typically, the ribbon is routed through adjacent feed rollers or drive wheels which grip the ribbon therebetween and direct the ribbon into a storage compartment in the cassette where it is stored in folded relation.
In addition to the employment of devices for directing a ribbon into a storage compartment of a cassette, certain cassettes are configured to direct ribbon across the print head of the printer along a line which is at a small angle, for example, 2°, with the base line of printing of a print head. The reason for this is that there is less tendency for repetitive striking of an area of a ribbon by a print head and thus less wear on the ribbon. This in turn enables a greater number of cycles of use of a given length of ribbon. In the patent to David W. Bell et al., U.S. Pat. No. 4,209,261, issued June 24, 1980, this offset has been accomplished by an intentional angular misalignment between a drive shaft of the host printer and the drive roller assembly of the cassette. In order to accomplish this intentional offset and still allow the ribbon to pass through adjacent drive wheels of &he angled roller assembly, the storage compartment is angled between the extreme sides or edges of the cassette body. The storage compartment and ribbon path are disposed in generally parallel relation. While the difference in elevation of the ribbon path at the entrance and exit of the storage compartment has been achieved so that the ribbon is directed across the print head of the printer at an oblique angle with the base line of the print head, the resulting intentional misalignment between the drive roller assembly of the cassette and the drive shaft of the printer may result in undue binding and thus undue wear on both the printer and cassette.
It is the object of this invention to overcome the aforesaid disadvantages and to provide a ribbon cassette which effects an ordered storing of the ribbon with substantially fewer number of bends while eliminating the problem of misalignment between the drive member of the printer and a drive roller of the cassette.
SUMMARY OF THE INVENTION
In accordance with this invention, the ribbon is fed into the storage cavity of the cassette by a drive mechanism which is mounted in the body of the cassette and which includes a drive shaft in axial alignment with the drive shaft of the printer. The cassette includes a pair of spaced horizontal side sections. One horizontal section supports guide members for the ribbon, and the other horizontal section supports the cassette's drive shaft in axial alignment with the output drive shaft of the printer. Such axial alignment assures that there is no binding between the mating drive shafts. A desired angular offset along the print line is accomplished in the printing region by an offset path between a pair of end guides arranged at the different elevations. Such an offset does not adversely affect the travel of the ribbon and, the ribbon being flexible, has no effect on the mechanism.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view, partially broken away to show the interior of a ribbon cassette as contemplated by this invention.
FIG. 2 is a front view, partially broken away, of the ribbon cassette of FIG. 1.
FIG. 3 is a sectional view as seen along line 3--3 of FIG. 1.
FIG. 4 is a side view as seen from the left side of FIG. 1.
FIG. 5 is an enlarged pictorial fragmentary view as seen along line 5--5 of FIG. 1.
FIG. 6 is an enlarged pictorial fragmentary view as seen along line 6--13 of FIG. 1.
FIGS. 7 and 8 are sectional views taken along lines 7--7 and 8--8 of FIG. 1. FIG. 7 illustrates the sectional view of the top cover of the cassette body, and FIG. 8 illustrates the sectional view of the base of the cassette body.
FIG. 9 is a top plan view of the body of another cassette employing the principles of the present invention.
FIGS. 10 and 11 are views similar to FIGS. 7 and 8 taken along lines 10--10 and 11--11 of FIG. 2 and illustrate the top and bottom portions of the cassette.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, ribbon cassette 10 is formed, with a molded plastic came 12 in turn formed of a base enclosure 14 comprised of front and rear portions 8 and 9 and an enclosure cover 16, the two being frictionally fit together in a conventional fashion. Cover 16 fits over and encloses the rear portion 9 of the base 14 as shown in FIG. 1, principally enclosing a ribbon storage cavity 18, ribbon entrance region 20, and ribbon exit region 22.
The rear portion 9 of base 14 (FIGS. 8 and 11) includes a pair of spaced horizontal surfaces 11 and 13 disposed at different elevations adjacent to, opposite sides of the casing. An intermediate angled surface 15 is disposed between surfaces 11 and 18. In similar manner, cover 16 (FIGS. 7 and 10) includes a pair of spaced inner horizontal surfaces 17 and 19 disposed at different elevations adjacent to opposite sides of the casing and connected by an intermediate angled surface 21. The planes of intersection of the angled and horizontal surfaces are indicated by the numerals 28 and 25 of FIGS. and 9-11.
Printing ribbon 24 (FIG. 1) is a continuously inked ribbon, and in operation it extends between guides 26 and 28. The printing process occurs between guides 26 and 28; thereafter, the ribbon passes between guide 28 and cavity entrance 30, through cavity 18 to cavity exit 32. From this point it extends through exit region 22 to exit opening 34. Intermediately, the ribbon extends through guide posts 31 and 33 (FIG. 1) to sloped guide 35 (FIG. 4) which is at a 45° slope, it thus rotating the ribbon 45°. From guide 35 the ribbon extends under horizontal guide 37 (dotted line position in FIG. 1), which is mounted on and extends downward from enclosure cover 16. In this manner, the ribbon is rotated 45°. From guide 87 it is rotated 90° as it is received by exit opening 34 which, as shown, is a vertical slot. Thus, in all, ribbon 24 is rotated 180°, reversed, between cavity exit 82 and exit opening 84. This thus enables the ribbon to be turned over after each pass through the cassette. As a result, it has been found that an approximately 40% longer effective usage can be obtained from a ribbon.
From exit opening 84 the ribbon extends back to and by guide 26 which is at the same elevation as exit opening 34 and at a lower elevation than guide 28. This difference in elevation enables the gradual rise of ribbon 24 from guide 26 to guide 28, being at an oblique angle of approximately 2° with respect to the axis 36 of a line of print, and as best illustrated in FIG. 2.
Guide 26 is shown in detail in FIG. 5 and, as shown, ribbon 24 passes over a guide surface 88 and is retained by upper hook 40 and lower hook 42.
Guide 28, shown in FIG. 6, is similar to guide 26, ribbon 24 passing over surface 44 and being retained by upper hook 46 and lower hook 48.
From guide 28 the ribbon is drawn through entrance opening 80, then into cavity 18 by ribbon drive 50. In the embodiment shown in FIGS. 1, 3, and 8, the drive consists of belt drive assembly 52 and spring bias assembly 54. Belt drive assembly 52 consists of rollers 55 and 56 mounted on horizontal surface 11 and tubular-shaped belt members 58 and 60 which fit over mating grooves (not shown) in the rollers. Roller 56, which is a drive roller, is supported in an opening (not shown) in top cover 16 and an opening 64 in a lower support member 66 of enclosure 14. Roller is supported by an opening (not shown) in top cover 16 and an opening 70 in support 66. As shown in FIG. 3, a hollow collar 68 of roller 55 extends above cover 16; and, as shown in FIG. 1, the interior 72 of collar 68 has serrations which enable a male drive member from a printer to effect a drive coupling with collar 68 and thus drive roller 56 in the indicated, clockwise, direction.
Ribbon 24 is frictionally driven as it passes across a portion of belts 58 and 60 where belts 58 and 60 rest on roller 55, ribbon 24 being urged against the belts by leaf spring 74 of bias assembly 54. Leaf spring 74 is biased against belts 58 and 60 by a coil spring 76 extending between wall 78 of enclosure 14 and leaf spring 74.
The particular function of ribbon drive 50 is to effect the long folds of ribbon illustrated in FIG. 1 instead of quite short ones typically resulting from conventional random stuffing of a ribbon in a storage cavity. Ribbon 24 has a length of approximately 45 feet which is to be substantially encased in cavity 18, the cavity having a rectangular area of approximately 52 square inches (approximately 2"×2.6"), or approximately nine feet of ribbon per square inch of cavity 18.
Openings 75a, 75b, 75c, and 75d are receptacles which receive locking pins (not shown) of cover 16 to effect locking of enclosure cover 16 to enclosure 18. Square members 75 and 76 are employed as structural stiffeners for arms 77 and 78 upon which guides 26 and 28 are mounted.
Initially, a short length of ribbon 24 is placed in the cassette through entrance opening 30, being pulled between leaf spring 74 and belts 58 and 60 and then through openings 82 and 84. Roller 56 is rotated clockwise, stuffing the ribbon randomly in cavity 18 until filled. Once cavity 18 is full, the randomly stuffed ribbon applies pressure against belts 58 and 60, and as additional ribbon is drawn into cavity 18, loops of ribbon are formed which are pressed between the previously stuffed ribbon and belts 58 and 60. This pressing causes the loops formed by new ribbon to be drawn along the length of belts 58 and 60, resulting in the elongated folds shown in FIG. 1. By continuing the process, the earlier formed random folds are allowed to exit until they are exhausted from cavity 18, leaving the long folds of ribbon 24 totally filling cavity 18 and continuing to bias incoming ribbon against the length of belts 58 and 60 as described above. At this point, the ribbon will be maintained as shown as it is cycled through cavity 18 and between guide posts 26 and 28 when in use.
It is to be understood that the cassette may be driven by other drive mechanisms than that discussed above. For example, the drive mechanism may be similar to that disclosed in U.S. Pat. No. 4,209,261 to David W. Bell et al., and which is further shown in FIGS. 9 and 10. In such drive mechanism, it is necessary that the drive wheels be supported on a flat surface in the manner set forth above so that the drive shafts of the printer and cassette be in axial alignment. The drive apparatus 50 consists of a pair of identical roller assemblies 80 and 82 which are positioned adjacent to cavity entrance region 20 (FIGS. 1 and 9) Roller assemblies 80 and 82 cooperate to drive the ribbon through cavity entrance 30 and into the storage cavity. Assemblies 80 and 82 are identical and are positioned adjacent to one another in inverted relation with ribbon 24 passing between them. Roller assembly 80 is the driver mechanism and assembly 82 is the driven mechanism which is driven by the printer.
To provide for the angular movement of the ribbon through the printing region and to provide for the vertical mounting of assemblies 80 and 82 in the casing to assure alignment of the output shaft of the printer with the drive shaft of the cassette, the casing cover 16 includes the pair of spaced horizontal surfaces 17 and 19 which are respective)y positioned adjacent to opposite sides of the casing. Angled section 21 is disposed between surfaces 17 and 19. Angled section 21 angles downwardly from surface 17 to surface 19 at an angle of approximately 2°. Surfaces 17 and 19 are horizontally disposed with section 17 being in normal relation with the axis of the output shaft of the printer. Base 14 is similarly provided with spaced horizontal surfaces 11 and 13 and intermediate angled surface 15. Surfaces 17, 19, and 21 of upper cover 16 are disposed in substantially parallel relation respectively with surfaces 11, 13 and 15 of base 14. As shown in FIG. 10, assemblies 80 and 82 are mounted to surface 17 of cover 16 with the drive shaft coaxially aligned with printer drive shaft 84.
It is to be understood that while the drawing shows and the description describes the drive shafts of the printer and cassette to be incoaxial alignment, such description is not limiting. For example, the axes of the drive shafts of the cassette and printer may be disposed in parallel spaced relation and each drive shaft provided with intermeshing gears or friction wheels on the ends thereof. Of course, either construction requires that the drive shaft of the cassette be mounted normally to the horizontal surface of the cassette body so that no binding can occur between the drive shafts.
It is to be also understood that while guides 35 and 37 (FIG. 1) are shown and described as rotating the ribbon 180°, such angled guides may be omitted and straight guides provided so that the ribbon may be guided out of cavity 18 without the 180° rotation.
From the foregoing, it is to be appreciated that the ribbon cassette of this invention enables optimum storage of a ribbon from the point of view of feet of ribbon stored in a given cavity size.
Further, this invention enables the provision of an obliquely presented ribbon without distortion of drive assembly linkage, enabling smooth transmission of power between printer and cassette, preventing mechanical binding and reducing wear on the drive components.
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An endless loop ribbon cassette wherein the storage of a ribbon in a ribbon cassette is effected by a belt assembly which causes the ribbon to move along a generally linear path substantially corresponding to one dimension of a storage cavity. This effects an ordered, rather than a random, storage of a ribbon. In addition, a ribbon is obliquely positioned with respect to a line of print of a printer with which a cassette is to be used.
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TECHNICAL FIELD
The present invention relates generally to thermal fuses, and more particularly, to a thermal fuse having a pair of electrical contacts that are retained in contact by a thermally deformable element.
BACKGROUND ART
Electrical appliances often include mechanisms that terminate operation of the motor in response to thermal overload conditions that could result in permanent damage to the motor or associated equipment. A thermal overload, such as an excessively high winding or rotor temperature, may occur as a result of a locked rotor, a high mechanical load, a supply overvoltage, a high ambient temperature, or some combination of these conditions.
Conventional thermal cut-outs (TCOs) are based on a thermally responsive element that fuses in response to a thermal overload condition, and which thereby interrupts the flow of electrical power to the protected apparatus, One typical approach uses a spring loaded contact pin or lead that is held in electrical connection with an opposing contact by a fusible material such as solder. Another typical approach uses one or more springs, which are independent from the electrical contacts, that drive the contacts apart into a displaceable fusible stop material. These known approaches have several significant drawbacks. In the first approach, the electrical power flows directly through the fusible material. Thus, self-heating in the fusible material itself, particularly in high power applications, can seriously impair the ability of the TCO to be responsive only to the temperature of the protected apparatus. In both described approaches, the TCO typically comprises a complex arrangement of springs and contact elements that are mounted in a housing. Thus, these approaches are costly, and do not allow for the direct inspection of the TCO because the fusible material and contact conditions are not usually visible through the housing.
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention, a first electrical contact extends through and is engaged with a second contact. A spring is disposed between the first and second contacts. A thermally deformable pin retains the first contact against the second contact. The pin is responsive to a high temperature condition such that the pin deforms, thereby allowing the spring to disengage the first and second contacts.
Preferably, the thermally deformable pin is made of a plastic material. Also preferably, the spring is a helical compression spring.
In accordance with another aspect of the present invention, a spring is compressed between a first electrical contact and a second electrical contact. A thermally deformable pin extends through the contacts and the spring. The pin is engaged with the first and second contacts, and is responsive to a high temperature condition such that the pin deforms and breaks under the expansive force of the spring to interrupt an electrical path between the first and second contacts.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevational view of an embodiment of the present invention;
FIG. 2 is a bottom view of the embodiment of FIG. 1;
FIG. 3 is a side elevational view of the embodiment of FIG. 1;
FIG. 4 is a plan view of one of the electrical contacts of FIG. 1;
FIG. 5 is a plan view of the other electrical contact of FIG.1;
FIG. 6 is a bottom elevational view of another embodiment of the present invention;
FIG. 7 is a plan view of one of the electrical contacts of FIG. 6;
FIG. 8 is a front elevational view of one of the electrical contacts of FIG. 6;
FIG. 9 is a plan view of one of the electrical contacts of FIG. 6;
FIG. 10 is a plan view of a Belleville washer that may be utilized in the embodiment of FIG. 6; and
FIG. 11 is a front elevational view of the Belleville washer of FIG. 10.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Illustrated in FIGS. 1 and 2 is a thermal fuse 10 that embodies aspects of the present invention. The thermal fuse 10 includes a first electrical contact 12, a second electrical contact 14, a helical compression spring 16, and a thermally deformable pin 18, all preferably arranged as shown. The first contact 12 extends through a slot 13 (shown most clearly in FIG. 5) in the second contact 14 and makes electrical contact with the second contact 14. The spring 16 is retained in a compressed state between a first face 17 of the second contact 14 and a shouldered portion 26 of the first contact 12. The spring 16 is preferably made of metal, but may alternatively be made from a non-metallic, non-electrically conductive material without impairing the operation of the fuse 10. The thermally deformable pin 18 extends through a first opening 24 in the first contact 12 and the spring 16 urges a second face 19 of the second contact 14 into contact with the pin 18. The first contact 12 may additionally include mounting ears or tabs 20, 22 that facilitate mounting of the fuse 10 to a structural member (not shown) of a protected electrical apparatus (also not shown).
Illustrated in FIG. 4 is a more detailed view of the first contact 12. As shown in FIG. 4, the first contact 12 has a spring guide portion 28 disposed at a first terminal end 29, and a second terminal end 30. The second terminal end 30 is preferably configured to accept a standard female spade connector. The spring guide 28 is an elongate tab that extends from the shouldered portion 26 of the contact 12. The spring guide 28 has a width that is smaller than the inner diameter of the spring 16 and a length that is substantially less than the free length of the spring 16. The first opening 24 is disposed at one end of the spring guide 28 and is dimensioned to easily accommodate the diameter or width of the thermally deformable pin 18.
Referring now to FIG. 5, the second contact 14 has a first terminal end 32 that is preferably configured to accept a standard female spade connector. The slot 13 is disposed near a second terminal end 34 and is sized to accept the width and thickness of the spring guide 28 of the first contact 12. Thus, the spring guide 28 of the first contact 12 may easily extend through the second contact 14 via the slot 13. Although a rectangular geometry for the slot 13 is depicted, a variety of geometries could accomplish the desired result without departing from the spirit of the invention. For example, the opening may have a rounded rectangle geometry and/or may be unbounded (i.e., open) on one or more sides.
The first contact 12 and the second contact 14 are preferably made of metallic contact materials that are well known in the art. A particular material composition may be selected to optimize contact performance under the specific application conditions for current, voltage, environmental conditions, etc. The contacts 12, 14 are preferably fabricated using a stamping operation to keep costs low. For example, the mounting tabs 20, 22 may be semi-perforations that are formed directly from the metallic blank used to make the first contact 12.
The thermally deformable pin 18 is preferably cylindrical (although not necessarily) and is made of a thermoplastic material having a melting point above the normal operating temperature of the protected apparatus, but at or below an operating temperature encountered during, for example, an overload condition. For example, the fuse 10 may be mounted to an electric motor, and the pin material may be selected to soften in response to the elevated winding temperatures caused by a locked rotor condition.
Those of ordinary skill in the art will immediately recognize that a variety of other configurations and materials may be used for the pin 18 without departing from the spirit of the invention. For example, the pin 18 may have a rectangular profile, or may be a plastic rivet or plug. Alternatively, the pin 18 may be a threaded screw or bolt that threads into or passes through the first opening 24, or a Christmas tree-shaped plug. In addition, the pin 18 may be made from a variety of materials other than a thermoplastic. For example, metals having a low melting point such as lead or lead alloys could be used to achieve similar results.
In operation, the fuse 10 is mounted to or adjacent to the protected apparatus (not shown). For example, the fuse 10 may be mounted to the housing of an electric motor (not shown) via the mounting tabs 20, 22. A power leadwire for the motor is connected to the second terminal end 30 of the first contact 12, and a magnet wire from the motor winding is connected to the first terminal end 32 of the second contact 14. Thus, the fuse 10 is serially interposed in the power supplied to the motor. In an overload condition, the motor and surrounding ambient temperature increases. Accordingly, because the contacts 12, 14 of the fuse are thermally conductive and are in thermal connection to the motor and the surrounding ambient environment they heat the thermally deformable pin 18. The pin 18 softens in response to the overload temperatures, and if the elevated temperature is high enough and persists for a sufficient time the expansive force of the spring 16 will shear the pin 18 where it contacts the walls defining the first opening 24. Once the pin 18 has sheared, the spring 16 extends to its free length and disengages the second contact 14 from the first contact 12. Additionally, the wire attached to the first terminal end 32 of the second contact 14 tends to pull the second contact away from the free end of the spring 16 and the spring guide portion 28 of the first contact 12, thereby guaranteeing a break in the electrical path through the fuse 10.
Illustrated in FIG. 6 is another thermal fuse 60 that embodies aspects of the present invention. The thermal fuse 60 includes a first electrical contact 62, a second electrical contact 65, a thermally deformable pin 70, a first electrically conductive Belleville washer 72, and a second electrically conductive Belleville washer 74, all preferably arranged as shown. The Belleville washers 72, 74 are in a compressed state between the first and second contacts 62, 65. The pin 70 extends through the washers 72, 74 and the contacts 62, 65. The pin 70 is engaged with the contacts 62, 65, thereby retaining the washers 72, 74 in a compressed state and completing an electrical path between the first and second contacts 62, 65. The first contact 62 may additionally include the mounting tabs 20, 22.
Illustrated in FIG. 7 is a more detailed view of the first contact 62. As shown in FIG. 7, the first contact 62 has a first terminal end 63 and a second terminal end 76. The first terminal end 63 is preferably configured to accept a standard female spade connector. To ensure adequate electrical contact and uniform compression of the first Belleville washer 72, the second terminal end 76 is preferably dimensioned so that it completely engages the footprint of the first Belleville washer 72 in its compressed state. Thus, the length and width of the second terminal end 76 preferably equal or exceed the length and width or diameter of the first washer 72. The second terminal end 76 further includes a first opening 70 that is surrounded by a first extruded collar 68 (see also FIG. 8).
Illustrated in FIG. 9 is a more detailed view of the second contact 65. The second contact 65 has a first terminal end 82 that is preferably configured to accept a standard female spade connector. The second contact has a second terminal end 64 that is preferably dimensioned identically to the second terminal end 76 of the first contact 62. Thus, the second Belleville washer 74 is engaged with the second terminal end 64 of the second contact 65 in a manner identical to that of the first washer's 72 engagement with the second terminal end 76 of the first contact 62. The second contact 65 includes a second opening 80 that is surrounded by a second extruded collar 66.
Illustrated in FIGS. 10 and 11 are top and side views respectively of the first and second Belleville washers 72, 74. Each of the washers 72, 74 includes an opening 84 having a diameter substantially greater than the largest cross sectional dimension of the thermally deformable pin 70. The Belleville washers 72, 74 are preferably made from an electrically conductive material so that when they are compressed between the first and second contacts 62, 65 an electrical path is formed between the contacts 62, 65.
As shown in FIG. 6, the thermally deformable pin 70 extends through the first and second openings 70, 80, and through the openings 84 of the first and second washers 72, 74. The pin 70 is dimensioned so that it is frictionally engaged with or pressed into the first and second collars 68, 66, thereby retaining the washers 72, 74 in a compressed state and providing an electrical path between the first and second contacts 62, 65 through the conductive washers 72, 74. The specific materials and geometry of the contacts 62, 65 and the thermally deformable pin 70 may be similar to those used in connection with the first embodiment discussed above and shown in FIGS. 1 through 5.
In operation, the fuse 60 is mounted to or adjacent to the protected apparatus (not shown) in a manner similar to that used with first described embodiment. In an overload condition, the expansive force of the washers 72, 74 causes the pin 70 to extrude and break along its length. Once the pin 70 has broken, the first and second washers 72, 74 separate, thereby interrupting the electrical path between the first and second contacts 62, 65. Additionally, a lead wire attached to the third terminal end 82 of the second contact 65 tends to pull the second contact away from the first contact 62, thereby guaranteeing a break in the electrical path through the fuse 60.
Of course, it should be understood that a range of changes and modifications can be made to the preferred embodiment described above. For example, various types of springs may be substituted for the helical spring and Belleville washers shown in the preferred embodiments. It is therefore intended that the foregoing detailed description be regarded as illustrative rather than limiting and that it be understood that it is the following claims, including all equivalents, which are intended to define the scope of this invention.
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A thermal fuse includes a first electrical contact extending through and engaged in electrical contact with a second contact. A spring is compressed between the first and second contacts. A thermally deformable pin retains the second contact against the compressed spring. The pin is responsive to a high temperature condition such that the pin deforms, thereby allowing the spring to disengage the first and second contacts.
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This is a continuation of application Ser. No. 07/767,819, filed Sep. 30, 1991.
FIELD OF THE INVENTION
This invention relates to UCT-4B, which is a clerodane-type diterpene having antitumor and antibacterial activities, and a process for producing a compound having a clerodane-type diterpene structure using a microorganism belonging to the genus Streptomyces.
BACKGROUND OF THE INVENTION
Known examples of antibiotics having a clerodane-type diterpene structure include terpentecin (MF730-N6) produced by a microorganism belonging to the genus Kitasatosporia [refer to EP 205981A; The Journal of Antibiotics, 38, 1664 (1985); and ibid. 38, 1819 (1985)] and clerocidin (PR-1350) produced by a microorganism belonging to the genus Oidiodendron [refer to U.S. Pat. No. 4,576,961; The Journal of Antibiotics, 36, 753 (1983); and Tetrahedron Letters, 25, 465 (1984)].
Both of clerodane-type diterpene antibiotics usually occur as an equilibrium mixture of tautomers which are chemically equivalent with each other. For example, it is known that clerocidin is present in the form of an equilibrium mixture of monomers such as hydroxyaldehyde (compound A) and hemiacetal (compound B) or a dimer (compound C), as shown by the following formulae. ##STR1##
SUMMARY OF THE INVENTION
It is an object of the present invention to provide UCT4-B having antitumor and antibacterial activities as well as a process for producing a clerodane-type diterpene derivative using a microorganism belonging to the genus Streptomyces.
The present invention relates to a process for producing a clerodane-type diterpene derivative represented by formula (I): ##STR2## wherein R represents a --CH 3 (terpentecin) or --CH 2 OH (UCT4-B); which comprises culturing a microorganism belonging to the genus Streptomyces and capable of producing said clerodane-type diterpene derivative in a medium so as to accumulate said clerodane-type diterpene derivative in the culture and recovering the clerodane-type diterpene derivative from said culture; and UCT4-B represented by formula (II): ##STR3## as well as chemically equivalent tautomers thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the 1 H-NMR spectrum of UCT4-B.
FIG. 2 shows the 13 C-NMR spectrum of UCT4-B.
DETAILED DESCRIPTION OF THE INVENTION
Now a process for producing UCT4-B and terpentecin will be described.
UCT4-B and terpentecin can be obtained by culturing a microorganism belonging to the genus Streptomyces and capable of producing UCT4-B and terpentecin so as to accumulate UCT4-B and terpentecin in the culture and recovering the UCT4-B and terpentecin from said culture.
As the UCT4-B and terpentecin-producing strain, any strain may be used so long as it belongs to the genus Streptomyces and can produce UCT4-B and terpentecin. A typical example thereof is strain S-464 which is newly isolated by the present inventors.
The mycological properties of the strain S-464, which will be given hereinbelow, are determined in accordance with a method for determining the properties of Streptomyces strains recommended by the International Streptomyces Project (ISP) [refer to E. B. Shirling and D. Gottlib, Int. J. Syst. Bacteriol., 16, 313 (1966)]. Diaminopimelic acid isomers in the hydrolysate of the whole cells are identified in accordance with the method reported by B. Becker et al. [refer to Appl. Microbiol., 12, 421 (1964)]. An optical microscope is used for morphological studies, while a scanning electron microscope is used, in particular, for observing the morphology of the surface of a spore. Colors are expressed in accordance with Color Harmony Manual, Container Co. of America, 4th ed. (1958).
The mycological properties of the strain S-464 are as follows.
(1) Morphology
Aerial hypha: branched.
Submerged hypha: branched but not fragmented.
Spore: attached to hyphae as a long refractile or loop chain consisting of 10 to 30 or more fragmented spores.
Surface of spore: smooth.
Motility of spore: no.
Shape and size of spore: ellipsoid (0.5×0.7 μm).
Neither any sclerotia nor any sporangiums are observed.
(2) Color
Aerial hypha: white.
Submerged hypha: pale yellow - yellowish brown.
Soluble pigment: pale yellow.
Melanin pigment: yes.
Chemical composition of cell wall
Stereostructure of diaminopimelic acid: LL-type.
(4) Physiological properties
Anabolism of carbon source:
Anabolized carbon source: glucose, xylose, inositol, mannitol, arabinose, rhamnose, raffinose, lactose, sucrose and galactose.
Unanabolized carbon source: salicin.
*Gelatin liquefaction: negative
Starch hydrolysis: positive.
*Skim milk solidification: negative.
*Skim milk peptonization: positive.
*Decomposition of cellulose: positive.
**Growth temperature range: 16°-37° C. (optimum temperature: 28°-32° C.).
Note: *The effects on gelatin, skim milk and cellulose are expressed in the results of a test performed after 1 month at 28° C., while **the growth temperature range is determined based on the results observed 2 days.
(5) Growth in various agar media
The S-464 strain was cultured in various agar media at 28° C. for 28 days. Table 1 shows the results.
In Table 1, G represents the growth level, AM represents the attachment and color of aerial hyphae, SM represents the color of submerged hyphae and P represents the color of a soluble pigment.
TABLE 1______________________________________Medium Growth______________________________________Sucrose/nitrate agar G: moderate.medium AM: poor, white. SM: light ivory (2ca). P: no.Glucose/asparagine G: good.agar medium AM: rich, light ivory (2ca). SM: light ivory (2ca). P: no.Glycerol/asparagine G: good.agar medium AM: rich pearl - shell pink (3ba - 5ba). SM: nude tan (4gc). P: yes, pale yellow.Starch agar G: good.medium AM: rich, natural - white (3dc). SM: apricot (4ge). P: yes, a little.Tyrosine agar G: good.medium AM: rich, white. SM: nude tan (4gc). P: yes, brown.Nutrient agar G: good.medium AM: rich, natural (3dc). SM: toast tan - nude tan (41g - 4gc). P: yes, pale yellow.Yeast/malt agar G: good.medium AM: rich, sand (3cb). SM: light brown (4ng). P: yes, pale yellow.Oatmeal agar G: good.medium AM: no. SM: dark brown (4pn). P: yes, brown.Peptone/yeast extract/ G: moderate.iron agar medium AM: no. SM: beaver (4li). P: yes, brown.______________________________________
(6) Identification of strain S-464
Since LL-form diaminopimelic acid is detected from the strain S-464, it falls within Actinomycetes of the cell wall I type [refer to Int. J. Syst. Bacteriol., 20, 435 (1970)]. Further, the above-mentioned morphological characteristics of this strain suggest that it reasonably belongs to the genus Streptomyces.
The species of this strain S-464 has been identified, from among those belonging to the genus Streptomyces, by detecting species whose characteristics are similar to those of this strain (namely, white hyphae, refractile or loop spore chain, smooth spore surface, production of the melanin-like pigment, production of the soluble pigment and metabolism pattern of carbon sources) from species recited in Approved Lists of Bacterial Names in view of the description of ISP [Int. J. Syst. Bacteriol., 18, 69 (1968); ibid., 18, 279 (1968); ibid., 19, 391 (1969); and ibid., 22, 265 (1972)] and Bergey's Manual of Determinative Bacteriology [ed. by R. E. Buchanan and N. E. Gibbons, 8th ed., Williams and Wilkins Co., (1974)].
Thus it has been identified that the strain S-464 belongs to a novel species of the genus Streptomyces. This strain was deposited with the Fermentation Research Institute (FRI), Agency of Industrial Science and Technology of 1-3, Higashi 1-chome, Tsukuba-shi, lbaraki, Japan as Streptomyces sp. S-464 No. FERM BP-3036 on Jul. 31, 1990 under the Budapest treaty.
The strain S-464 may be cultured in accordance with a method commonly employed for culturing Actinomycetes. Either a synthetic medium or a natural one may be used so long as it contains a carbon source, a nitrogen source and inorganic matters, which can be metabolized by this strain, substances required for the growth thereof and substances capable of promoting the production of the target compounds.
Examples of the carbon source include glucose, starch, dextrin, mannose, fructose, sucrose, lactose, xylose, arabinose, mannitol, molasses and mixtures thereof. Further, hydrocarbons, alcohols and organic acids may be used depending on the metabolism capability of the strain. Examples of the nitrogen source include ammonium chloride, ammonium sulfate, ammonium nitrate, sodium nitrate, urea, peptone, meat extract, yeast extract, dry yeast, corn steep liquor, soybean flour, casamino acids and mixtures thereof. Further, inorganic salts such as sodium chloride, potassium chloride, magnesium sulfate, calcium carbonate, potassium dihydrogen phosphate, dipbtassium hydrogen phosphate, ferrous sulfate, calcium chloride, manganese sulfate, zinc sulfate and copper sulfate may be added to the medium, if required. Furthermore, trace components capable of promoting the growth of the strain and the production of UCT4-B and terpentecin may be optionally added thereto.
It is preferable to culture this strain by the liquid culture method, in particular, the submerged agitation culture method. The culture temperature ranges from 16° to 37° C., preferably from 25° to 32° C., and the pH value of the medium is maintained at 4 to 10, preferably 6 to 8, during the culture period by adding, for example, sulfuric acid, aqueous ammonia or an ammonium carbonate solution.
When the strain is cultured by the liquid culture method for 1 to 7 days, UCT4-B and terpentecin are generally produced and accumulated in the culture medium and cells. When the production in the culture medium reaches the maximum level, the culture is ceased.
The UCT4-B and terpentecin may be isolated from the culture medium and purified by a method commonly employed for isolating and purifying metabolites of a microorganism from its culture.
For example, the culture medium is filtered and thus separated into a culture filtrate and cells. Next, the cells are extracted with, for example, chloroform or acetone. Then the extract is combined with the culture filtrate and passed through a column packed with a polystyrene adsorbent such as Diaion HP20 (product of Mitsubishi Kasei Corporation) to thereby adsorb the active components contained therein, followed by eluting with, for example, ethyl acetate or acetone. The obtained eluate is concentrated and purified by chromatography commonly employed in the art, for example, silica gel column chromatography or high-performance liquid chromatography. Thus UCT4-B and terpentecin can be obtained as a white powder.
The UCT4-B thus obtained may be in the form of, for example, an equilibrium mixture of chemically equivalent tautomers represented by the following formulae. All the isomers including these tautomers are involved in the present invention. ##STR4##
As the following reaction scheme shows, an equilibrium mixture of the compounds 2 and 3 each having a quinoxaline ring may be obtained by reacting UCT4-B with o-phenylenediamine. Then the equilibrium mixture is acetylated to thereby give a single compound 4 which is never contaminated with any equilibrium mixture of tautomers (refer to Reference Examples 1 and 2). ##STR5##
Thus the structure of UCT4-B has been more clearly confirmed.
Now the biological activities of UCT4-B will be illustrated by reference to the following Test Examples.
TEST EXAMPLE 1
Antibacterial Activity
The antibacterial activities of UCT4-B on four bacteria (i.e., Staphylococcus aureus, Enterococcus faecium, Bacillus subtilis, Klebsiella pneumoniae) were examined by the agar dilution method (pH 7.0) [refer to "Biseibutsu Jikken Manyuaru (Manual of The Microbial Experiments)" 80, Kodansha (1986)].
The results are shown in terms of the minimum growth inhibition concentration (MIC) in Table 2.
TABLE 2______________________________________Test strain MIC (μg/ml) of UCT4-B______________________________________Staphylococcus aureus ATCC 6538P 4.1Enterococcus faecium ATCC 10541 4.1Bacillus subtilis ATCC 10707 8.3Klebsiella pneumoniae ATCC 10031 2.1______________________________________
TEST EXAMPLE 2
Acute Toxicity
UCT4-B was intravenously administered once to ddy mice weighing about 20 g (each group having 5 animals) and then the survival state of the animals was monitored for 14 days following the administration. Then LD 50 of the compound was calculated based on the mortality of mice in each group in accordance with the Behrens-Karber method. As a result, it was found that the LD 50 of UCT4-B is 50 mg/kg or above.
TEST EXAMPLE 3
Effect on Lymphocytic Leukemia
1×10 6 lymphocytic leukemia p338 tumor cells were intraperitoneally transplanted into CDF male mice weighing 22 g (each group having 5 animals). 24 hours after the transplantation, 0.2 ml of a solution of UCT4-B in physiological saline or 0.2 ml of physiological saline (the control group) was intraperitoneally administered to the animals.
The results of the test are expressed in terms of T/C (%) calculated by dividing the average survival days of each test group (T) with that of the control group (C).
Table 3 shows the results.
TABLE 3______________________________________ Dose Life-prolonging effectTest compound (mg/kg) (T/C %)______________________________________UCT4-B 50 141 25 137 12 127 6 131 3 124______________________________________
To further illustrate the embodiments of the present invention, the following Examples and Reference Examples will be given.
EXAMPLE 1
Streptomyces sp. S-464 was inoculated into 300 ml of a seed medium (pH 7.2 before sterilization) comprising 5 g/l of Bacto Tripton (product of Difco), 5 gl of yeast extract, 3 g/l of meat extract, 10 g/l of soluble starch, 10 g/l of glucose and 5 g/l of calcium carbonate contained in a 2 l Erlenmeyer flask and cultured at 30° C. under shaking at 200 rpm for 48 hours.
The seed culture thus obtained was then transferred into 100 l of a fermentation medium of the following composition in a 200 l culture tank at a ratio of 10% by volume and cultured at 28° C. under aerating at a ratio of 15 /min. and agitating at 200 rpm.
Composition of the fermentation medium: 5% of soluble starch, 3% of KNO 3 , 0.5 g/l of KH 2 PO 4 , 0.5 g/l of MgSO 4 .7H 2 O and 5 g/l of calcium carbonate (the pH value of the above medium had been adjusted to 7.0 with NaOH prior to the sterilization).
Then the culture was continued for 67 hours while controlling the pH value of the medium to 7 with 4N H 2 SO 4 . Next, the cells and precipitate were removed from the culture medium by filtration and thus 100 l of a filtrate was obtained. The filtrate was concentrated, diluted with water and then passed through a column packed with a polystyrene adsorbent Diaion HP20 (10 l) to thereby adsorb the active substances.
After eluting impurities with deionized water and 50 methanol, UCT4-B was eluted with 60% methanol and then terpentecin was eluted with 80% methanol.
The 60% methanol fraction containing UCT4-B was concentrated and adjusted to pH 4. Then the active substance was extracted with ethyl acetate. The ethyl acetate layer was concentrated and passed through a column packed with silica gel (Lichroprepsi 60, product of Merck Inc.) so as to adsorb the active substance. Next, the adsorbed substance was eluted with chloroform, chloroform/methanol (100:1 by volume) and chloroform/methanol (50:1 by volume) under elevated pressure to approximately 10 kg/cm 2 . The obtained fraction was subjected to column chromatography with the use of Sephadex LH20 and eluted with methanol to thereby give an active fraction. This fraction was then purified with reverse-phase high performance liquid chromatography [column: YMC-Pack (YMC Ltd.), ODS SH363-5; development solvent: CH 3 OH 0.7 l+H 2 O 0.03 l; flow rate: 20 ml/min.; detection: UV absorption at 230 nm]. The active fraction thus obtained was concentrated to dryness to give 100 mg of UCT4-B as a white powder.
The physiochemical properties of the obtained UCT4-B are as follows.
As described above, it is assumed that UCT4-B is in the form of an equilibrium mixture of tautomers, similar to terpentecin and clerocidin. Therefore its physiochemical properties might vary depending on the determination conditions and the method for preparing the sample. Thus the physicochemical properties of the sample prepared by the method described in the above Example will are given below. The instruments employed for the determination are as follows.
m.p.: Micro Melting Point Meter produced by Yanagimoto Seisakusho, K.K.
Optical rotation: Polarimeter DIP-370 produced by Nippon Bunko Kogyo K.K.
Mass spectrum: M-80B produced by Hitachi, Ltd.
UV absorption spectrum: Spectrophotometer 200-20 produced by Hitachi, Ltd.
IR absorption spectrum: JIR-RFX 3001 produced by JEOL Ltd. or IR-810 produced by Nippon Bunko Kogyo K.K.
1 H and 13 C-NMR spectra: AM500 or AM400 produced by Bruker Co.
A) Form: colorless powder.
B) m.p.: within a range of from 160° to 172° C.
C) Optical rotation:
In a chloroform solution, [α] D 27 =+27.8° (c=0.53). When dissolved in a 50% aqueous acetonitrile solution, [α] D 27 =+23.2° (c=0.53) immediately after the dissolution. 195 minutes after the dissolution, [α] D 27 =+1.21° (c=0.53) and then this level was maintained.
D) EI mass spectrum: m/z 380, 365, 249, 219, 203, 165, 135, 125, 109, 107 and 105.
E) Secondary ion mass spectrum: (methanol solution, matrix: glycerol) m/z 743, 725, 491, 473, 455, 437, 381, 363, 345, 317, 259, 237, 225, 215 and 201.
F) UV absorption spectrum: (acetonitrile solution) nothing but the terminal absorption was observed.
G) IR absorption spectrum: (KBr method) 3431, 2966, 1707, 1385, 1016 and 999 cm -1 .
(H) Solubility: highly soluble in methanol, chloroform and ethyl acetate, soluble in water and acetonitrile and insoluble in hexane.
I) 1 H-NMR spectrum: (500 MHz, CD 3 OD solution) shown in FIG. 1.
J) 13 C-NMR spectrum: (125 MHz, CD 3 OD solution) shown in FIG. 2.
K) Coloration: positive in coloration reactions of anisaldehyde, sulfuric acid, iodine and phosphomolybdic acid and negative in Dragendorff's reaction.
On the other hand, the 80% methanol fraction containing terpentecin was concentrated and purified in the same manner as the one employed for purifying UCT4-B. Thus 90 mg of terpentecin was obtained.
The 1 H-NMR spectrum and IR spectrum of the terpentecin thus obtained agreed with the reported ones [refer to The Journal of Antibiotics, 38, 1819 (1985)].
REFERENCE EXAMPLE 1
Preparation of o-phenylenediamine Adducts of UCT4-B (compounds 2 and 3)
13.4 mg of UCT4-B was dissolved in 1 ml of 50% aqueous acetonitrile and 8.3 mg of o-phenylenediamine was added thereto. The mixture was stirred at room temperature for 1 hour. Then the reaction mixture was concentrated under reduced pressure. The crude product thus obtained was purified by preparative thin layer chromatography [product of Merck Inc., Kieselguhr 60F 254 Art 5744; development solvent: chloroform:methanol (9:1 by volume)]. Thus 5.2 mg of an equilibrium mixture of the compounds 2 and 3 (1:1) which could not be separated by TLC or HPLC was obtained. Physicochemical data of the equilibrium mixture of the compounds 2 and 3:
Rf: 0.70 [product of Merck Inc., Kieselguhr 60F 254 Art 5719; development solvent: chloroform:methanol (9:1 by volume)].
0.44 [product of Merck Inc., HPTLC CNF 254 S Art 16464; development solvent: acetonitrile:water (1:1 by volume)].
High resolution EI mass spectrum: m/z as C 26 H 32 O 5 N 2 : found: 452.2298 (M+). calculated: 452.2308.
EI mass spectrum: m/z 452 (M+), 434, 201, 185, 173, 157, 144, 129 and 102.
IR absorption spectrum: (KBr method) 3425, 2960, 2924, 1385, 1049, 1014 and 763 cm -1 .
1 H-NMR spectrum: (500 MHz, CDCl 3 solution) δppm.
Compound 2
8.81 (1H, s), 8.15 (1H, m), 8.01 (1H, m), 7.81 (2H, m), 5.73 (1H, m), 4.48 (1H, m), 4.30 (1H, d, J=7.5 Hz), 4.29-4.20 (2H, m), 3.59 (1H, br. s, disappeared when D 2 O was added), 3.42 (1H, d, J=4.6 Hz), 3.13 (1H, d, J=4.6 Hz), 2.98 (1H, br. d, J=11.1 Hz), 2.35-2.20 (2H, m), 1.96 (1H, d, J=15.3 Hz), 1.92 (2H, m), 1.76 (1H, m), 1.70 (1H, m), 1.48 (3H, s), 1.09 (3H, d, J=7.1 Hz) and 1.03 (3H, s).
Compound 3
8.79 (1H, s), 8.12 (1H, m), 8.06 (1H, m), 7.80 (2H, m), 5.33 (1H, m), 4,46 (1H, m), 4.13 (1H, m), 4.08 (1H, d, J=11.0 Hz), 3.89 (1H, d, J=12.1 Hz), 3.36 (1H, d, J=4.8 Hz), 3.08 (1H, d, J=4.8 Hz), 2.88 (1H, br. s, disappeared when D 2 O was added), 2.35-2.20 (2H, m), 2.15 (1H, dd, J=9.1, 7.4 Hz), 1.85 (1H, m), 1.84 (2H, m), 1.77 (1H, dq, J=12.1, 7.3 Hz), 1.58 (1H, dd, J=15.0., 9.4 Hz), 1.17 (3H, s), 0.99 (3H, s) and 0.88 (3H, d, J=7.3 Hz).
REFERENCE EXAMPLE 2
Preparation of Acetylated o-phenylenediamine Adduct of UCT4-B
Compound 4
0.5 ml of pyridine and 0.5 ml of acetic anhydride were added to 2.4 mg of an equilibrium mixture (1:1) of the compounds 2 and 3 and stirred at room temperature for 15 hours. The reaction mixture was concentrated and the crude product thus obtained was purified by preparative thin layer chromatography [product of Merck Inc., Kieselguhr 60F 254 Art development solvent:hexane:ethyl acetate (1:1 by volume)]. Thus 1.9 mg of a single acetylated product (compound 4) was obtained.
Physicochemical Data of the Compound 4
Rf: 0.41 [product of Merck Inc., Kieselguhr 60F 254 Art 5719; development solvent: hexane:ethyl acetate (1:1 by volume)].
0.60 [product of Merck Inc., development solvent: chloroform:methanol (98:2 by volume)].
High resolution EI mass spectrum: m/z as C 32 H 38 O 8 N 2 : found: 578.2614 (M+). calculated: 578.2625.
EI mass spectrum: m/z 578 (M+), 536, 518, 494, 476, 460, 260, 235 and 207.
IR absorption spectrum: (KBr method) 2925, 1747, 1373, 1232, 1053, 1026 and 768 cm -1 .
1 H-NMR spectrum: (500 MHz, CDCl 3 solution) δppm. 8.76 (1H, m), 8.09 (1H, m), 8.02 (1H, m), 7.77 (2H, m), 5.88 (1H, d, J=10.2 Hz), 5.75 (1H, m), 5.51 (1H, m), 4.87 (1H, dd, J=12.7, 1.0 Hz), 4.66 (1H, dd, J=12.7, 0.7 Hz), 3.30 (1H, d, J=5.0 Hz), 3.10 (1H, d, J=5.0 Hz), 2.91 (1H, dd, J=10.5, 3.6 Hz), 2.58 (1H, d, J=15.1 Hz), 2.19 (2H, m), 2.15 (1H, dq, J=13.8, 6.9 Hz), 2.13 (3H, s), 2.12 (3H, s), 2.06 (3H, s), 1.79 (1H, dd, J=15.1, 10.2 Hz), 1.49 (3H, s), 1.16 (3H, s) and 1.01 (3), d, J=6.9 Hz).
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A clerodane-type diterpene derivative, which has antibacterial and antitumor activities, as well as chemically equivalent tautomers thereof and a process for producing said derivative using a microorganism belonging to the genus Streptomyces.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an electronic endoscope having a video-scope and a video-processor, especially, it relates to a signal process for displaying an observed image while recording a still image.
2. Description of the Related Art
In an electronic endoscope, an interline-transfer (IT) CCD is used to display a movie image on a monitor, wherein odd-field image-pixel signals and even-field image-pixel signals are alternately read from the CCD for one-field reading interval. When displaying or recording a still image generated by a one-time exposure, a shading or blind member is driven so as to block light that is emitted from a lamp and directed to an object, for a one-field reading interval. Thus, odd-line image-pixel signals and even-line image pixel signals are read from the CCD in order, for one-frame (two-field) reading interval, so that a high-quality still image is obtained without a blur.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an electronic endoscope system that is capable of smoothly and continuously displaying an observed image without an interruption of an image-display while recording a still image.
An electronic endoscope according to the present invention has a light source that radiates illuminating light, a movie-image processor, and a still-image processor. The movie-image processor alternately reads odd-field image-pixel signals corresponding to an odd-field and even-field image-pixel signals corresponding to an even-field to generate a movie-image. For example, one field worth of image-pixel signals is temporarily stored in a memory as image data and is updated in each filed interval. The still-image processor that alternately reads odd-line image-pixel signals and even-line image-pixel signals over two field interval to generate a still image on the basis of one frame worth of image-pixel signals generated by a one-time exposure (herein, designated as “still-image exposure”). The illuminating light being blocked for a latter filed interval in the two field interval. For example, blocking member such as a chopper is applied. As for an adjustment of an exposure-time, for example, a rotary shutter that has an aperture and a shading portion are provided. The aperture and the shading portion are formed so as to alternately pass and block the illuminating light, and that rotates so as to adjust an exposure-time.
The electronic endoscope has further has an image change processor and a provisional image displayer. The image change processor switches a performance of the movie-image processor for displaying the movie-image and a performance of the still-image processor for displaying the still-image. For example, a switch button for displaying and/or recording a still image is provided on the video-scope. While the still-image processor reads the odd-line and even-line image-pixel signals over the two field intervals, the provisional image displayer displays a provisional image on the basis of at least one of odd-field image-pixel signals and even-field image-pixel signals, which are obtained by an exposure before the still image exposure, namely, the one-time exposure for recording a still image.
While the odd-line and even-line image-pixel signals are read over the two field interval, the observed image is displayed regardless of the block of the illuminating light. Therefore, a blank interval wherein the observed image is not displayed and a screen becomes black does not occur, and the operator can properly continue a work such as an operation using an electronic endoscope when recording a still image.
To display the provisional image by adjusting an update-timing, for example, the provisional image displayer changes an update interval of the image data from one field interval to two field intervals when the performance of the still image processor is started. Optionally, the provisional image displayer stops an update of the image data while the one frame worth of pixel-image signals, generated by the still image exposure, is read over the two field interval.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be better understood from the description of the preferred embodiments of the invention set forth below together with the accompanying drawings, in which:
FIG. 1 is a block diagram of an electronic endoscope according to a first embodiment;
FIG. 2 is a plan view of a rotary shutter;
FIG. 3 is a plan view of a chopper;
FIG. 4 is a view showing a timing chart of a recording process; and
FIG. 5 is a view showing a timing chart of a recording process according to a second embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the preferred embodiments of the present invention are described with reference to the attached drawings.
FIG. 1 is a block diagram of an electronic endoscope according to the first embodiment.
The electronic endoscope has a video-scope 50 with a CCD 54 , and a video-processor 10 that has a lamp 12 and processes image-pixel signals read from the CCD 54 . The video-scope 50 is detachably connected to the video-processor 10 ; and a monitor 52 and a recorder 53 that records a still image are connected to the video-processor 10 .
When a lamp switch button (not shown) is turned ON, a lamp controller 11 supplies electric power to the lamp 12 so that the lamp 12 radiates illuminating light. Light emitted from the lamp 12 enters the incidence surface 51 A of a light-guide 51 via a rotary shutter 15 and a collecting lens 16 . The light-guide 51 is constructed of a fiber-optic bundle for directing the light to a tip end of the video-scope 10 . The light exits from the end portion 51 B of the light-guide 51 , and illuminates an observed object via a diffusion lens (not shown).
Light, reflected on the object, reaches the CCD 54 via an objective lens (not shown), so that an object image is formed on the photo-sensitive area of the CCD 54 . A color filter, checkered by four color elements of Yellow (Y), Magenta (M), Cyan (C), and Green (G), is arranged on the photo-receiving area such that the four color elements are opposite to pixels arranged in the photo-sensitive area. Based on the light passing through each color element, analog image-pixel signals are generated by the photoelectric transformation effect. The generated image-pixel signals are read from the CCD 54 at regular time intervals in accordance with clock pulse signals output from a CCD driver 54 . A timing control circuit 58 in the video-scope 50 adjusts an output-timing of the clock pulse signals.
The CCD 54 is an interline-transfer CCD, and as for the color imaging method using an on-chip color filter, the so called “color difference lines sequential system” is applied. Therefore, while displaying a movie image, the photo-generated charges in pixels neighboring each other are mixed, and odd-field image-pixel signals and even-field image-pixel signals are alternately read from the CCD 54 . The NTSC (or PAL) standard is herein applied as the TV standard, accordingly, the odd or even field image-pixel signals are read from the CCD 54 at a 1/60 (or 1/50) second time interval, and are then fed to an amplifier 55 . The image-pixel signals are amplified in the amplifier 55 and are subjected to given processes in a first signal processing circuit 57 . The processed image-pixel signals are fed to a second signal processing circuit 28 .
In the second signal processing circuit 28 , various processes, such a gamma correction process, a white balance process, and soon, are carried out on the image-pixel signals, so that digital image signals are generated and temporarily stored in an image memory 29 as digital image data. The digital image signals are read from the image memory and video signals such as NTSC signals are output to the monitor 52 at a given timing, thus an observed image is displayed on the monitor 52 as a movie image.
On the other hand, when displaying a still image on the monitor 52 and recording the still image in the recorder 53 by depressing a freeze button 53 A on the video-scope 50 , a one-time reading process, wherein one frame worth of image-pixel signals is generated by a one-time exposure, is performed. When electric charges are accumulated by a one-time exposure, image-pixel signals corresponding to an odd-line in the pixel-array are read from the CCD 54 over one-field reading interval, next, image-pixel signals corresponding to an even-line in the pixel array are read from the CCD 54 over one-field reading interval. One field worth of odd-line image-pixel signals and one field worth of even-line image-pixel signals are respectively fed to the amplifier 55 , the first signal processing circuit 57 , and the second signal processing circuit 28 . Then, odd-field image signals and even-field image signals are respectively output to the monitor 52 . Also, one field worth of odd-line image-pixel signals and one field worth of even-line image-pixel signals, which are processed in the second signal processing circuit 28 , are fed to the recorder 53 as still image data.
A system control circuit 22 including a CPU (not shown) controls each circuit in the video-processor 10 , and outputs control signals to the lamp controller 11 , the second signal processing circuit 28 , and so on. A timing control circuit, provided in the video-processor 10 (not shown), outputs clock pulse signals to each circuit in the video-processor 10 to adjust a process-timing, and outputs synchronous signals which are added to the video signals, to the second signal processing circuit 28 . The system control circuit 22 controls an output-timing of the clock pulse signals fed to each circuit. For example, the system control circuit 22 adjusts an output-timing of clock pulse signals, which are output to the image memory 28 in accordance with the operation of the freeze button 53 A to renew or rewrite image data, and adjusts an output-timing of clock pulse signals, which are output from the CCD driver 59 to drive the CCD 54 .
A scope controller 56 , provided in the video-scope 50 , controls the first signal processing circuit 55 and the timing control circuit 58 . The timing control circuit 58 outputs driving signals to the CCD driver 59 in accordance with the control signals output from the scope controller 56 . Thus, the reading process of the image-pixel signals is controlled. When the video-scope 50 is connected to the video-processor 10 , data are transmitted between the video-scope 50 and the video-processor 10 .
The rotary shutter 15 is attached to a motor (not shown), and rotates at a constant speed on the basis of driving signals fed from a motor driver 23 . A chopper 17 , which shades or blocks the light to be directed to the end portion of the video-scope 50 , is provided between the rotary shutter 15 and the collecting lens 16 , and has a DC solenoid (herein, not shown). The chopper 17 motions in accordance with a series of pulse signals fed from a PWM driving circuit 24 .
FIG. 2 is a plan view of the rotary shutter 15 . FIG. 3 is a plan view of the chopper 17 .
The rotary shutter 15 is constructed of an aperture 15 A that passes the light from the lamp 12 and a shading portion 15 B that shades or shields the light. The aperture 15 A is formed such that a pair of arc-shaped holes is opposite to each other. The rotary shutter 15 rotates by one-rotation in one-frame reading interval (= 1/30 or 1/25 second). Therefore, the half-circle 15 P of the rotary shutter 15 corresponds to one-field reading interval (= 1/60 or 1/50 second). While the rotary shutter 15 rotates by a half-rotation, the aperture 15 A and shading portion 15 B pass the light-path of the light emitted from the lamp 12 , in turn. Thus, an exposure interval and a shading interval alternately occur in one-field reading interval, which functions like an electronic shutter.
When displaying and recording the still image, one frame worth of image-pixel signals is obtained by light passing through one aperture 15 A, namely, by rotating the rotary shutter 15 by a half-rotation. Then, the obtained one frame worth of image-pixel signals is read from the CCD 54 over the one-frame reading interval (= 1/30 or 1/25 second). Since the other aperture 15 A passes the light-path for the remaining interval (= 1/60 or 1/50 second), the chopper 17 moves so as to block the illuminating light when the other aperture 15 A passes the light-path.
In FIG. 3 , the non-shading position of the chopper 17 , which enables light to pass through one arc-shaped hole of the aperture 15 A, is shown by a solid line, whereas the shading position of the chopper 17 , which blocks the light when the other arc-shaped hole of aperture 15 A passes the light-path, is shown by a broken line. The chopper 17 is a pivot-type solenoid, and has a DC solenoid 17 A and a plate member 17 B, which pivots around a center axis 17 C. When the chopper 17 motions so as to shade the illuminating light, an end portion 17 D of the plate member 17 B covers the light-path or the aperture 15 A of the rotary shutter 15 . The PWM driving circuit 24 is a PWM controller, which outputs a sequence of pulse signals to the solenoid 17 A.
FIG. 4 is a view showing a timing chart of the recording process.
In a state where the freeze button 53 A is not pressed, namely, a movie image is displayed, odd-field image-pixel signals and even-field image-pixel signals are alternately read from the CCD 54 at a 1/60 (or 1/50) of a second interval while mixing adjacent pixel signals, as described above. Since the CCD 54 is an interline type CCD, the photo-generated charges, which are accumulated by a given exposure-timing, are read in the next exposure-timing. For example, image-pixel signals, which are accumulated at “n−1” of the exposure-timing and correspond to the even-field, are read from the CCD 54 at “n” of the exposure-timing, as shown in FIG. 4 . Clock pulse signals, which update the image data in the image memory 29 , are output to the image memory 29 at 1/60 (or 1/50) time interval.
When the freeze button 53 A is pressed to start recording a still image, all pixel signals, which are obtained during a one-time exposure time (in FIG. 4 , the signals in the order of “n”), are read from the CCD 54 over a one-frame reading interval. Concretely, odd-line image-pixel signals and even-line image-pixel signals are read from the CCD 54 , in turn, over two field intervals. During the reading of all image-pixel signals, the chopper 17 motions to block the illuminating light.
Further, when the recording process is performed, the output-interval of the clock pulse signals for update is changed from one-field interval to two-field (one-frame) intervals. The two-field intervals are based on pulse signals “SP”, which are output at an exposure-time just before an exposure-time for recording the still image. Consequently, the odd-field image-pixel signals and the even-field image-pixel signals are respectively used to display the observed image over two field intervals. An observed image, formed by the odd-field image-pixel signals, is displayed for 1/30 (or 1/25) of a second, and an observed image, formed by the even-field image-pixel signals, is also displayed for 1/30 ( 1/25) of a second. After the one frame worth of image-pixel signals (odd-line image-pixel signals and even-line image-pixel signals) are read from the CCD 54 , the interval of the update returns to one field interval.
With reference to FIG. 5 , the second embodiment is explained. The second embodiment is different from the first embodiment in that image data is not renewed while recording the still image.
FIG. 5 is a view showing a timing chart of a recording process according to the second embodiment.
When the recording process is started by depressing the freeze button 53 A, as shown in FIG. 5 , clock pulse signals for update are not output to the image memory 29 over two-field intervals. Then, odd-field image-pixel signals, obtained by an exposure just before the exposure for recording the still image, are used to display the observed image until the one frame worth of image-pixel signals for the still image is read from the CCD 54 .
Finally, it will be understood by those skilled in the arts that the foregoing description is of preferred embodiments of the device, and that various changes and modifications may be made to the present invention without departing from the spirit and scope thereof.
The present disclosure relates to subject matter contained in Japanese Patent Application No. 2005-056979 (filed on Mar. 2, 2005), which is expressly incorporated herein, by reference, in its entirety.
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An electronic endoscope has a light source that radiates illuminating light, a movie-image processor, a still-image processor, an image-change processor, and provisional image displayer. The still-image processor that alternately reads odd-line image-pixel signals and even-line image-pixel signals over two field interval to generate a still image on the basis of one frame worth of image-pixel signals generated by a one-time still image exposure. The illuminating light being blocked for a latter filed interval in the two field interval. The image change processor switches between a performance of the movie-image processor for displaying the movie-image and a performance of the still-image processor for displaying the still-image. While the still-image processor reads the odd-line and even-line image-pixel signals over the two field intervals, the provisional image displayer displays a provisional image on the basis of at least one of odd-field image-pixel signals and even-field image-pixel signals, which are obtained by an exposure before the still image exposure.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to a safety device for the building field, for individually protecting against falls workers assigned to walking at high elevations in buildings under construction.
[0002] Safety devices for buildings are known for providing individual protection against falls of workers assigned to walking at high elevations in buildings under construction.
[0003] These devices generally comprise a plurality of metal poles, which are mutually spaced and are connected, at their base, to a horizontal surface of the building, constituted for example by a beam, and have, at their top end or in an intermediate region of their vertical extension, a passage for a cable, which is fixed to the building at its ends and is tensioned by means of suitable cable tensioning elements so as to form a safety parapet.
[0004] In these devices, the poles are merely meant to keep the cable at a preset height, so that it is easily engaged by the spring-clips of the safety belts or harnesses worn by workers.
[0005] U.S. Ser. No. 09/645,560 by the same Applicants, which is herein included by reference, illustrates a safety device significantly reducing the stresses transmitted from the cable to the pole transversely to the axis of the pole and allows to distribute over multiple poles the stresses transmitted along the cable, thus reducing the stresses discharged onto each pole.
[0006] Although this device ensures a better performance than conventional safety devices, it has limitations of application when the spacing between the poles becomes considerable. This device in fact offers adequate assurances of safety, with acceptable dimensions of the pole and of the system for connection to the surface of the building, for pole spacings up to approximately 10 m. When greater spacings are required, in order to work safely it would be necessary to oversize considerably the pole and the insert embedded in the concrete component to which the pole is rigidly coupled. This would inevitably entail an increase in the weight of the device and in its cost. Furthermore, with this device it is technically inadvisable to have pole spacings of more than 10 m, since beyond this limit in operating conditions the forces that become involved are different not only in terms of load but also in terms of multiple traction components: the pole might tip not only in the direction of the cable but also at right angles, since the cable would oscillate laterally. So-called “whiplash”, i.e., dynamic stresses that are highly amplified and are composed of forces that are parallel and perpendicular to the line of the cable, causing tipping or oscillations of the poles, might also occur.
[0007] Another limit that can be observed in known types of device is the fact that these devices have been conceived mainly to be installed on prefabricated beams, i.e., on components that have a reduced transverse dimension. Because of this, the accidental fall of the worker is very close to the ideal tension line of the cable and therefore produces on the cable a force that has a modest lateral component, which can be withstood easily both by means of the cable and by means of the base for interlocking and resting the pole in and on the beam.
[0008] If these safety devices were installed on wider structural elements, such as for example prefabricated concrete floor or covering slabs, the traction components directed laterally to the cable would increase considerably, since any fall of the worker would be laterally quite distant from the ideal tension line of the cable. The cable, by touching the lateral edge of the concrete component, would in fact generate an additional significant lever arm and would introduce a torque and/or flexural moment that are difficult to recenter on the pole.
[0009] Moreover, it should be noted that prefabricated slabs (which are usually 10-20 meters long but are sometimes as long as 30 m) are often transported when they are already pre-impermeabilized with bitumen coats, except for the ends where the inserts for facilitating their lifting are inserted.
[0010] In such cases it is unfeasible to maintain a limited spacing between the poles, since it would be necessary to pierce the coat at the insert in order to connect the base of the poles.
[0011] Particularly for these kinds of components, there is a need to have a safety device for individually protecting against falls workers assigned to walking at high elevations in buildings under construction, which offers adequate assurances of safety even with considerable pole spacings.
SUMMARY OF THE INVENTION
[0012] The aim of the present invention is indeed to provide a safety device for the building field, for individually protecting against falls workers assigned to walking at high elevations in buildings under construction which is capable of withstanding forces, even considerable ones, orientated transversely to the line of the cable in the presence of large pole spacings.
[0013] Within this aim, an object of the invention is to provide a device that can adapt itself without problems to different operating conditions and to different types of prefabricated component.
[0014] Another object of the invention is to provide a device that is simple to use and offers the greatest assurances of safety.
[0015] This aim and these and other objects that will become better apparent hereinafter are achieved by a safety device for the building field, for individually protecting against falls workers assigned to walking at high elevations in buildings under construction, which comprises at least one pole and means for detachably connecting the base of said pole to the surface of a building; said pole having, proximate to its top end, engagement means for a cable element that is suitable to form a safety parapet, characterized in that it comprises at least one leg which is connected laterally to said pole and can rest, with its lower end, on said surface of the building, laterally to the region engaged by the base of said pole, in order to form, for said pole, an auxiliary resting element for pushing against said surface of the building.
BIEF DESCRIPTION OF THE DRAWINGS
[0016] Further characteristics and advantages of the invention will become better apparent from the description of a preferred but not exclusive embodiment of the device according to the invention, illustrated only by way of non-limitative example in the accompanying drawings, wherein:
[0017] [0017]FIG. 1 is a perspective view of the device according to the invention;
[0018] [0018]FIG. 2 is a partially sectional side elevation view of the device, applied to a concrete component;
[0019] [0019]FIG. 3 is a partially sectional front elevation view of the device, applied to a concrete component;
[0020] [0020]FIG. 4 is a top plan view of the device;
[0021] [0021]FIG. 5 is an exploded perspective view of a leg of the device according to the invention;
[0022] [0022]FIG. 6 is an axial sectional view of the top end of the pole of the device according to the invention;
[0023] [0023]FIGS. 7 and 8 are schematic views of the use of the device with two types of prefabricated concrete component;
[0024] [0024]FIG. 9 is a schematic perspective view of the use of the device with another type of prefabricated concrete component.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] With reference to the figures, the device according to the invention, generally designated by the reference numeral 1 , comprises at least one pole 2 and connection means 3 for detachably associating the base of the pole 2 with the surface 4 of a building, particularly for associating the base of the pole 2 with a prefabricated concrete component which is part of the building. The pole 2 has, proximate to its top end, engagement means 5 for a cable element 6 that is suitable to form a safety parapet.
[0026] According to the invention, the device comprises at least one leg 7 , which is connected laterally to the pole 2 and can rest, with its lower end, on the surface 4 of the building on which the pole 2 is arranged, laterally to the region of said surface that is engaged by the base of the pole 2 , so as to form, for the pole 2 , an auxiliary resting element for pushing against the surface 4 of the building.
[0027] Instead of a single leg 7 , it is also possible to provide two legs 7 , connected laterally to the pole 2 and arranged angularly spaced from each other, around the axis 2 a of the pole 2 ; each one of these legs 7 can rest, with its lower end, on the surface 4 of the building laterally to the region engaged by the base of the pole 2 so as to form, for the pole 2 , two auxiliary resting elements for pushing against the surface 4 of the building.
[0028] Preferably, the device comprises three legs 7 , which are connected laterally to the pole 2 and are arranged angularly spaced from each other about the axis 2 a of the pole, so as to form three auxiliary resting elements for the pole 2 on the surface 4 , laterally to the region engaged by the pole 2 . In this case, one leg 7 is arranged on a first vertical plane that passes through the cable element 6 and the other two legs are arranged on a vertical plane that is substantially perpendicular to said first plane. In particular, the leg 7 , which lies on the first plane, is preferably arranged on the side of the pole 2 that is directed in the direction in which the cable element 6 runs, from the pole 2 being considered, toward a similar opposite pole 2 , to which the other end of the cable element 6 is fixed.
[0029] Each one of the legs 7 is pivoted, proximate to its upper end, to the pole 2 , about an axis 7 a , which is substantially perpendicular to the axis 2 a of the pole 2 and can open in a compass-like fashion laterally to the pole 2 . The pivoting axis 7 a is preferably arranged proximate to the top end of the pole 2 .
[0030] Conveniently, each leg 7 has a variable useful length, which is preferably obtained by providing each leg 7 with a telescopic structure.
[0031] More particularly, as shown, each leg 7 comprises two elements which are telescopically mutually coupled; respectively, a first element 8 , which is shaped like a hollow cylinder and partially coaxially accommodates a second element 9 , which is substantially cylindrical. The second element 9 has, on its axial end that is accommodated inside the first element 8 , a threaded shaft 10 , which couples to a through female thread 11 formed inside the first element 8 . The second element 9 can rotate about its own axis with respect to the first element 8 so as to achieve, as a consequence of the threaded coupling between the shaft 9 and the female thread 11 , an axial movement of the first element 8 with respect to the second element 9 , thus achieving a variation of the overall length of the leg 7 .
[0032] In order to facilitate the rotation of the second element 9 with respect to the first element 8 , on the portion of the cylindrical side wall of the second element 9 that is external with respect to the first element 8 there are holes 12 , which are arranged angularly spaced from each other around the axis of the leg 7 and in which it is possible to insert a lever or pin in order to turn the second element 9 . For the same reason, a portion 13 of the cylindrical side wall of the second element 9 , which is external with respect to the first element 8 , can be conveniently shaped like a hexagonal prism in order to allow to turn it by means of a wrench.
[0033] The upper end of the second element 9 , which protrudes upward from the first element 8 , has a pivot 14 whose axis coincides with the common axis of the first element 8 and of the second element 9 . Said pivot 14 couples, so that it can rotate about its own axis, inside a seat 15 formed in a block 16 . The pivot 14 is locked axially inside the seat 15 , for example by means of an elastic ring, and the block 16 is pivoted to the pole 2 about the pivoting axis 7 a.
[0034] A frame 17 is connected to the top end of the pole 2 , and the upper ends of the legs 7 are pivoted thereto about the corresponding pivoting axes 7 a.
[0035] Advantageously, each leg 7 has, at its lower end, a resting foot 18 , which is articulated to the remaining part of the leg 7 so as to allow to orientate the resting foot 18 in order to adapt its resting surface to the inclination of the surface 4 of the building. In particular, the resting foot 18 is pivoted to the remaining part of the leg 7 about a pivoting axis 18 a, which is substantially parallel to the pivoting axis 7 a.
[0036] It should be noted that the engagement of the foot or feet 18 on the surface 4 is a simple resting contact and therefore no prior installation of anchoring elements for the feet 18 in the surface 4 is required; moreover, one is provided with the greatest freedom in positioning the feet 18 .
[0037] Conveniently, means are provided for delimiting the compass-like opening angle of each leg 7 with respect to the pole 2 . Said delimiting means, in the illustrated embodiment, are constituted by chains 19 , which are connected, with one of their ends, to the corresponding leg 7 and can be coupled to suitable hooks 20 fixed to the pole 2 proximate to its base.
[0038] The pole 2 can be constituted by a pole of a known type used to anchor a safety cable element to the surface of a building.
[0039] Preferably, the pole 2 is constituted by the pole disclosed in the previously cited U.S. Ser. No. 09/645,560.
[0040] As disclosed in said patent application, the pole 2 is provided with engagement means 5 for the cable element 6 , and said engagement means comprise guiding means for the cable element 6 , which are suitable to divert, along a direction that is substantially parallel to the axis 2 a of the pole 2 , at least part of the stresses transmitted by the element 6 to the pole 2 . The pole 2 is furthermore provided with means for damping the stresses transmitted by the cable element 6 to the pole 2 along a direction that is substantially parallel to the axis 2 a of the pole 2 .
[0041] The pole 2 comprises a main structure, which can be fixed detachably, by way of the above cited connection means 3 , to the surface 4 of the building.
[0042] More particularly, the main structure of the pole 2 is constituted by a lattice-like box structure 39 , which tapers from the bottom upward.
[0043] The connection means 3 comprise an anchoring element 21 , which can be fixed to the surface 4 of the building or better still can be embedded in the prefabricated concrete component that forms said surface 4 , and in which there is a female seat 22 , which lies along an axis that is substantially perpendicular to the surface 4 with an access opening formed in said surface 4 of the building.
[0044] On the base of the pole 2 there is a male element 23 , which is provided in the same manner described in the above cited patent application and can be inserted and locked axially inside the female seat 22 formed by the anchoring element 21 .
[0045] The guiding means for the cable element 6 comprise elements for guiding the cable element 6 , which form, for said cable element 6 , proximate to the top end of the pole 2 , a portion of a path whose component is parallel to the axis 2 a of the pole 2 .
[0046] At least one of said guiding elements is mounted on a supporting element 24 , which can move with respect to the pole 2 along a direction that is substantially parallel to the axis 2 a . The above cited damping means are interposed between the main structure of the pole 2 and the supporting element 24 .
[0047] Conveniently, said guiding elements comprise two lateral pulleys 25 a and 25 b, which are associated with the frame 17 connected to the main surface of the pole 2 and are arranged so that their axes 26 a and 26 b are mutually parallel and substantially at right angles to the axis 2 a . The axes 26 a and 26 b are spaced laterally in mutually opposite directions with respect to the axis 2 a.
[0048] Preferably, the pulleys 25 a and 25 b are supported, so that they can rotate about their respective axes 26 a and 26 b, by two pairs of wings 27 a and 27 b of the frame 17 . More particularly, there are two wings 27 a , which are arranged side by side and support the pulley 25 a, and two wings 27 b, which are also arranged side by side and support the pulley 25 b.
[0049] Said guiding elements comprise, in addition to the pulleys 25 a and 25 b, an intermediate pulley 28 , which is arranged so that its axis 28 a is parallel to the axes 26 a and 26 b of the pair of pulleys 25 a and 25 b and is arranged between the pulleys 25 a and 25 b . The intermediate pulley 28 is further spaced from the pair of pulleys 25 a and 25 b along a direction that is substantially parallel to the axis 2 a in order to guide the cable element 6 from the pair of pulleys 25 a and 25 b to the intermediate pulley 28 along two path portions, designated by the arrows 30 and 31 , which have a component that is parallel to the axis 2 a of the pole.
[0050] The supporting element 24 , on which the intermediate pulley 28 is mounted, is supported by the main structure of the pole 2 so as to allow movement along the axis 2 a of the pole 2 .
[0051] The damping means can be constituted, as shown, by a spring 32 , for example a helical spring that is orientated so that its axis lies parallel to the axis 2 a , or can be constituted by a hydraulic or pneumatic damper interposed between the main structure of the pole 2 and the supporting element 24 .
[0052] The supporting element 24 is provided with a sleeve 33 , whose axis preferably coincides with the axis 2 a of the pole and is coupled, so that it can slide along its axis, to a coaxial sliding seat 34 formed in the top end of the pole 2 .
[0053] The spring 32 is mounted around the sleeve 33 and engages, with one of its ends, against a shoulder 35 a formed by the supporting element 24 and, with its other end, against a shoulder 35 b formed in the main structure of the pole 2 around the inlet of the sliding seat 34 .
[0054] It should be noted that in the end of the sleeve 33 that passes through the sliding seat 34 there is female thread 36 , with which a screw 37 engages; said screw protrudes upward from a through hole provided for this purpose in the frame 17 coaxially to the sliding seat 34 . By virtue of the rotation of the screw 37 , it is possible to vary the distance at rest between the shoulders 35 a and 35 b and therefore vary the preloading of the spring 32 .
[0055] The operation of the device according to the invention is as follows.
[0056] At least two poles 2 of the device according to the invention are fixed, in two mutually spaced regions, along the surface 4 of the building, using the connection means 3 and the female seats 22 of the anchoring elements 21 provided for this purpose inside the prefabricated component that forms the surface 4 of the building. After fixing the pole 2 to the prefabricated component that forms the surface 4 , the leg or legs 7 are rested on the surface 4 , in regions that are spaced laterally from the region where the base of the pole 2 rests, using the possibility to vary the length of the legs 7 and the orientation of the supporting foot 18 . In this manner it is possible to achieve correct resting of the feet 18 of the legs 7 on horizontal or variously inclined flat surfaces, as shown in FIGS. 7 to 9 , which illustrate the application of the device according to the invention to various kinds of prefabricated slab or covering. In practice, it is possible to achieve correct resting of the legs 7 for any type of prefabricated component currently in use.
[0057] A cable element 3 is then stretched between the two poles 2 , fixing it to said poles 2 , for example by means of a clamp with bolts 40 , and passing it through the pulleys 25 a , 25 b , 28 , so as to form a safety parapet to which the spring-clips of the safety belts or harnesses of workers can be anchored. If workers accidentally fall, the forces that are discharged onto the cable element 6 and by said element onto the poles 2 , thanks to the presence of the leg or legs 7 , are re-centered along the axis 2 a of the pole 2 and are discharged onto the component to which the poles 2 are anchored, without the danger of tearing out or tipping the poles even in the presence of intense forces orientated transversely to the cable element 6 .
[0058] Accordingly, the spacing between the poles 2 can be considerably longer than the spacing allowed by conventional safety devices.
[0059] Furthermore, it should be noted that the forces transmitted by the cable element 6 to the pole 2 are re-centered along the axis 2 a of the pole also due to the particular path of the cable element 6 imposed by the pulleys 25 a , 25 b , 28 and are also damped by the action of the spring 32 .
[0060] In practice, it has been found that the device according to the invention fully achieves the intended aim, since thanks to the additional resting provided by the leg or legs to the pole, it is capable of withstanding intense forces, generated by the accidental fall of workers connected to the cable element, even if said forces are applied in regions that are considerably spaced laterally from the ideal tension line of the cable element and even if the distance between the poles that support the cable element is, due to contingent requirements, considerably greater than the distance compatible with the use of safety devices of the conventional type. Accordingly, the device according to the invention can use just two poles connected proximate to the longitudinal ends of prefabricated components of considerable length, which do not allow to install a larger number of poles and are also quite wide, such as for example most of the prefabricated slabs currently in use.
[0061] The device thus conceived is susceptible of numerous modifications and variations, all of which are within the scope of the appended claims; all the details may further be replaced with other technically equivalent elements. In practice, the materials used, as well as the dimensions, may be any according to requirements.
[0062] The disclosures in Italian Patent Application No. M12001A000803 from which this application claims priority are incorporated herein by reference.
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A safety device for the building field, for individually protecting against falls workers assigned to walking at high elevations in buildings under construction. The device comprises at least one pole, a detachable connection for the pole base with the surface of a building, the pole having at its top end, an engagement for a cable element forming a safety parapet, at least one leg connected laterally to rest, with its lower end, on the surface of the building, laterally to the region engaged by the base of the pole, to form, for the pole, an auxiliary resting element for pushing against the surface of the building.
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BACKGROUND OF THE INVENTION
In the construction of window and door assemblies, it is common to use insulated glass panel units of the general type disclosed in U.S. Pat. Nos. 5,003,747 and 6,675,537 which issued to or are owned by the assignee of the present invention. Usually, the insulated glass units include two parallel spaced rectangular glass panels having peripheral edge portions which receive a rectangular spacer frame. The edge portions and spacer frame are bonded and sealed together by a bonding compound such as a butyl rubber compound or a similar bonding material surrounding the spacer frame. The insulated glass panel unit is assembled into a surrounding rectangular sash frame and is retained by glazing members or beads. Preferably the sash frame and glazing beads are formed from extrusions of plastics material such as polyvinyl chloride (PVC). Such insulated glass panel units are commonly used in fixed window assemblies such as picture windows, single hung windows, sliding windows, bow and bay windows and sliding and swinging patio door assemblies such as disclosed, for example, in U.S. Pat. No. 6,318,036 which issued to the assignee of the present invention.
In insulated glass panel units as described above, it is common for the outer edges of the glass panels to be exposed and unprotected during handling and shipping or be covered by a thin layer of the bonding and sealing compound. When the outer edges of the glass panels are relatively unprotected, insulated glass panel units must be carefully handled and carefully protected during shipping. Also, when the edge surfaces of the glass panels are exposed, the personnel handling the insulated glass panel units need to wear gloves in order to avoid cutting their fingers or receiving glass splinters. It is also desirable for a fixed window assembly, such as a picture window assembly, to provide for conveniently removing the insulated glass panel unit in the event of glass breakage or damage or moisture seeps into the space between the glass panels and results in etching the inner surfaces of the glass panels.
SUMMARY OF THE INVENTION
The present invention is directed to an improved window assembly having insulated glass panels and which is ideally suited for use in a fixed glass window unit such as a picture window, a single hung window and sliding and swinging patio doors assemblies. The window assembly of the invention provides for conveniently handling and shipping an insulated glass panel unit while protecting the unit and also provides for conveniently removing the insulated glass panel unit from the surrounding sash frame and from the inside of the window assembly in the event the unit requires repair or replacement. In addition, when the insulated glass panel unit is inserted into the surrounding sash frame, the unit locks to the sash frame so that it is precisely located and is prevented from shifting laterally relative to the sash frame without the use of spacers.
In accordance with one embodiment of the invention, a window assembly constructed in accordance with the invention includes a rectangular outer sash frame formed of sash frame members of extruded rigid plastics material and rigidly connected at the corners of the frame, for example, by miter cuts and welding. The outer sash frame includes a laterally inwardly projecting flange which engages and seals with the outer glass panel of the insulated glass panel unit. A rectangular inner sub-sash frame is formed with sub-sash frame members of extruded rigid plastics material and are also rigidly connected at the corners of the frame such as by miter cuts and welding. The sub-sash frame also includes a laterally inwardly projecting flange which overlaps a peripheral edge portion of one of the glass panels, and the flange is bonded to the glass panel. The sub-sash frame interlocks with the outer sash frame when assembled for precisely locating the sub-sash frame within the surrounding outer sash frame and to limit relative lateral movement. Extruded plastic glazing members have laterally inwardly projecting flange portions which overlap and seal with a peripheral edge portion of the inner glass panel. The glazing members engage a shoulder on an inner wall of the outer sash frame and have spring flange portions which project outwardly between the inner wall and the sub-sash frame and press against the sub-sash frame.
Other features and advantages of the invention will be apparent from the following description, the accompanying drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of a fixed window assembly constructed in accordance with the invention;
FIG. 2 is an enlarged vertical section taken generally on the line 2 - 2 of FIG. 1 and with a center portion broken away;
FIG. 3 is an enlarge horizontal section taken generally on the line 3 - 3 of FIG. 1 and with a center portion broken away; and
FIG. 4 is a fragmentary section similar to FIG. 3 and showing a modification of a window assembly constructed in accordance with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates a window assembly 10 which includes a rectangular outer sash frame 12 formed by elongated sash frame sections or members 14 and 16 which are extruded of a rigid plastics material such as rigid polyvinyl chloride (PVC). The sash frame members 14 and 16 are rigidly connected at the corners of the frame 12 by mitered cuts and welded corner joints 18 . As used herein, the term rectangular with respect to the shape of the frame 12 also includes a square frame. Also, instead of the mitered cuts and welded corner joints 18 , the frame sections or members 14 and 16 may be rigidly connected by mechanical fasteners such as screws.
Referring to FIGS. 2 and 3 , each of the frame sections or members 14 and 16 are shown with the same cross-sectional configuration, and the outer tubular portion of each sash frame member is shown as substantially rectangular in cross-section. However, it is to be understood that the outer portion of each sash frame section or member may have any desired cross-sectional configuration. As also shown in FIGS. 2 and 3 , each of the sash frame members 14 and 16 includes a laterally inwardly projecting flange portion 22 having an inwardly projecting longitudinally extending rib 24 and an inwardly projecting flexible lip seal 26 . As generally known in the industry, the flexible lip seals 26 are co-extruded of a PVC material having a lower durometer so that the lip seals are somewhat flexible when compared with the substantially rigid PVC material forming the sash members 14 and 16 . Each of the sash frame members 14 and 16 also has an inner wall 28 with an offset or step portion 29 forming a longitudinally extending shoulder 31 .
An insulated glass panel unit 35 includes a rectangular inner glass panel 36 and a parallel spaced rectangular outer glass panel 38 . In a conventional manner, the glass panels 36 and 38 are spaced parallel by an internal rectangular spacer frame 42 which is commonly formed from a roll formed aluminum sheet metal strip, but may also be formed from another form of spacer material. A bonding compound or material 44 , such as a compound of butyl rubber, surrounds the spacerframe 42 and bonds to the peripheral inner surfaces of the glass panels 36 and 38 to form a sealed air-tight space 46 between the glass panels. The space 46 may be filled with a suitable gas such as argon, and the spacer frame 42 may be used to enclose a desiccant material to absorb any moisture within the space 46 .
In accordance with the present invention, a rectangular inner sub-sash frame 50 is enclosed within the outer sash frame 12 and is formed by elongated sub-sash frame members 52 ( FIG. 2) and 54 ( FIG. 3 ) which are rigidly connected at the corners of the sub-sash frame, for example, by mitered cuts and welding or by mechanical fasteners such as screws. Each of the sub-sash frame members 52 and 54 are also extruded of a substantially rigid plastics material, such as rigid PVC, and have an outer base portion 56 with inwardly and outwardly facing slots 58 forming generally an H-shaped cross-sectional configuration. Each of the sub-sash frame members 52 and 54 also includes an integrally extruded flange portion 62 which projects laterally inwardly into overlapping relation with a peripheral edge portion of the outer glass panel 38 .
The flange portion 62 has an inwardly projecting inner lip 64 which contacts the outer surface of the outer glass panel 38 , and a bonding compound or material 66 , such as a butyl rubber compound, positively bonds the flange portion 62 to the outer peripheral portion of the glass panel 38 . As shown in FIGS. 2 and 3 , the base portion 56 of the sub-sash frame members 52 and 54 closely surround the glass panel unit 35 and has substantially the same width in order to cover and protect the outer edges of the glass panels 36 and 38 .
In the assembly of the window, the sub-sash frame 50 is placed on a table, and the bonding material 66 is placed on the flange portion 62 . The glass panel unit 35 is then lowered into the sub-sash frame 50 until the frame 50 is bonded and sealed to the outer glass panel 38 of the insulated glass panel unit 35 . The sub-sash frame 50 and attached glass panel unit 35 are then assembled into the outer sash frame 12 by laying the outer sash frame 12 on the table and then lowering the sub-sash frame 50 and glass panel unit 35 downwardly until the peripherally extending ribs 24 of the outer sash frame flanges 22 are received within the mating grooves 58 of the sub-sash frame members 52 and 54 , as shown in FIG. 3 . During this assembly, the flexible lip seals 26 engage the outer surface of the outer glass panel 38 and form a fluid-tight seal between the outer sash frame 12 and the glass panel unit 35 .
The sub-sash frame 50 and the attached insulated glass unit 35 are retained and secured within the outer sash frame 12 by a set of glazing sections or members 72 and 74 which are formed from an extrusion of rigid plastics material such as PVC . The glazing members 72 and 74 are not connected but have mitered or abutting corner joints on the inside of the window assembly 10 . Each of the glazing members 72 and 74 includes a flange portion 76 which projects laterally inwardly in overlapping relation with a peripheral edge portion of the inner glass panel 36 and has an integrally extruded flexible sealing lip 77 which is formed like the sealing lip 26 and engages the inner surface of the inner glass panel 36 to form a fluid-tight seal. Each of the glazing members 72 and 74 also includes an outer slightly curved flange portion 81 which is integrally extruded with the inner flange portion 76 and projects outwardly to engage the outer surface of the corresponding sub-sash frame member 52 or 54 . The flange portion 81 is slightly flexible and spring-like so that a corner portion of the glazing member is forced laterally outwardly into engagement with the shoulder 31 on the inner wall 28 of the corresponding outer sash frame member 14 or 16 . The glazing members 72 and 74 thereby lock the sub-assembly of the sub-sash frame 50 and glass panel unit 35 onto the outer sash frame, as shown in FIGS. 2 and 3 .
Referring to FIG. 4 which shows another embodiment of the invention, a window assembly 10 ′ includes and outer sash frame 12 and glazing member 72 and 74 as described above in connection with FIGS. 1-3 . In this embodiment, however, a sub-sash frame 50 ′ includes sub-sash frame members 54 ′ and 52 ′ (not shown) which are formed from an extrusion of rigid plastics or PVC material and have base portion 56 ′ with slots 58 ′. Each of the sub-sash frame members also includes integrally extruded and parallel spaced flanges or wall portions 78 which project laterally inwardly between the glass panels 36 and 38 and are bonded to peripheral edge portions of the glass panels by a suitable bonding material 80 such as a butyl rubber compound. With respect to the construction and attachment of the flanges or wall portions 78 to the inner surfaces of the glass panels 36 and 38 , The disclosures of U.S. Pat. Nos. 6,286,288 and 6,536,182, which are owned by SashLite, LLC, are herein incorporated by reference.
From the drawings and the above description, it is apparent that a window assembly constructed in accordance with the present invention, provides desirable features and advantages. For example, after the sash frame 12 , sub-sash frame 50 and glass panel unit 35 are assembled, as shown in FIGS. 2 and 3 , moisture from the outside is prevented from seeping into the space 46 between the glass panels 36 and 38 by not only the lip seal 26 and bonding compound 66 , but also the bonding compound 44 surrounding the spacer frame 42 . It is also apparent that when the sub-sash frame 50 is attached to the glass panel unit 35 , the frame 50 provides for not only protecting the outer edge portions of the glass panels 36 and 38 , but also for conveniently handling and transporting the glass panel unit 35 after it is assembled and until it is lowered into the outer sash frame 12 .
The assembly of the sub-sash frame 50 and attached glass panel unit 35 may also be conveniently removed from inside the building after the outer sash frame 12 has been installed simply by using a sharp blade and prying laterally inwardly on the glazing members 72 and 74 against the bias of the spring flanges 81 until the glazing members are released from the shoulders 31 on the outer sash frame 12 . Such convenient removal of the glass panel unit 35 with the sub-sash frame 50 is occasionally desirable from inside the building, for example, when a glass panel 36 or 38 has been damaged or broken. It is also apparent from FIGS. 2 and 3 that the interfitting connection of the outer sash frame 12 and the sub-sash frame 50 , by means of the peripherally extending rib 24 within one of the peripherally extending grooves 58 , effectively eliminates or limits any lateral movement of the sub-sash frame 50 and glass panel unit 35 relative to the outer sash frame 12 . The modification shown in FIG. 4 also provides all of the above advantages in addition to eliminating the spacer frame 42 and surrounding bonding material 44 .
While the forms of window assembly and the methods of assembly herein described constitute preferred embodiments of the invention, it is to be understood that the invention is not limited to the precise methods and forms of assembly described, and that changes may be made therein without departing from the scope and spirit of the invention as defined in the appended claims.
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A rectangular outer sash frame has extruded plastic frame members with inwardly projecting flange portions overlapping a peripheral edge portion of an outer glass panel of an insulated glass unit. A removable inner sub-sash frame interconnects with the outer sash frame and has extruded plastic frame members with inwardly projecting flange portions overlapping and bonded to a peripheral edge portion of at least one of the glass panels. Extruded plastic glazing members have flange portions overlapping a peripheral edge portion of the inner glass panel and include retaining flange portions projecting between the outer sash frame and the inner sub-sash frame. In another embodiment, the sub-sash frame has integrally extruded parallel spaced walls projecting inwardly between and bonded to the peripheral edge portions of both the inner and outer glass panels.
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TECHNICAL FIELD OF THE INVENTION
[0001] The present invention generally relates to semiconductor devices and more particularly to a method for removing a resist mask with high selectivity to a carbon hard mask used for semiconductor structuring.
BACKGROUND OF THE INVENTION
[0002] As is known in the art, mask layers, preferably hard mask layers, are deposited on semiconductor devices in order to structure the semiconductor devices in a predetermined manner. For photolithographically structuring the semiconductor device and/or the mask layer, a photo resist is commonly used. Such a photo resist is generally patterned by exposing the resist to electromagnetic waves of a predetermined wave-length range and patterned with a pattern device.
[0003] A cross-sectional view of a portion of a semiconductor device is shown in FIG. 2 which illustrates a semiconductor device 10 , constituted preferably of Si, wherein as an example, a recess 11 has basically a rectangular shape in the cross-section of FIG. 2 . A mask 12 , preferably a carbon hard mask with a thickness of 170 nm as an example, is deposited on the semiconductor substrate 10 . On top, a liner 13 , preferably SiON with a thickness of 60 nm as an example is deposited according to FIG. 2 .
[0004] For the structure shown in FIG. 2 , a known stripping process for removing a photo resist (not shown in FIG. 2 ) mask was utilized. The resist was a carbon-type film which was removed by an oxygen-based etchant. The etchant plasma comprised for example 2000 sccm O 2 as well as 100 sccm N 2 at a pressure of e.g. 150 Pa and a temperature of 250° C. While stripping the photo resist on top of the liner layer 13 , e.g. SiON, cavities 14 were formed in the carbon hard mask 12 as a parasitic side effect. Such erosion cavities 14 in the carbon hard mask 12 are highly undesirable since it leads to the etching of undesired features during subsequent processing. The formation of the cavities 14 is based on the attack of the carbon hard mask 12 by the oxygen rich plasma process used during the resist rework step at areas of weakness, especially at edges, corners and strongly bent portions of liner layer 13
[0005] FIG. 3 shows a structure basically similar to the structure according to FIG. 2 except that the cavities 14 and therefore the erosion of the carbon hard mask 12 on the semiconductor substrate 10 is substantially more pronounced. Leading to the structure of FIG. 3 , a wet etch process was carried out three times to remove a photo resist (not shown in FIG. 3 ) from the surface of liner 13 . Here, the vast cavities 14 formed in the carbon hard mask 12 on top of the semiconductor substrate 10 also result from the attack of the carbon hard mask by the wet etchant used during the resist stripping process at areas of weakness in the SiON liner layer 13 .
SUMMARY OF THE INVENTION
[0006] In an effort to reduce erosion of a mask layer during a resist strip process, it is desirable to develop a resist strip method with a high selectivity to the underlying mask, preferably a carbon hard mask.
[0007] A preferred embodiment of the present invention provides a method for removing a resist mask from a liner on a mask. The method includes, for example, providing a plasma comprising of hydrogen at a predetermined temperature level and a predetermined pressure level in a reaction chamber, and etching the resist selectively to the mask with the plasma for a predetermined period of time.
[0008] In accordance with a further preferred embodiment, the hydrogen plasma could be diluted with Nitrogen so as to obtain a cost-effective and safe Forming gas chemistry for the resist strip application. A 96:4 Nitrogen to Hydrogen gas mixture is a standard Forming gas chemistry used in the semiconductor industry as an example.
[0009] In accordance with a further preferred embodiment of the present invention, the plasma comprising of a predetermined amount of CF 4 , wherein the predetermined amount is for e.g. less than 5 per cent, preferably about 1 per cent. By the use of a small amount of CF 4 , the selectivity from the resist to the Carbon hard mask can be further enhanced.
[0010] In accordance with a further embodiment, the resist etching plasma is free from oxygen. This bears the advantage of a solely reductive etchant for the resist strip.
[0011] In accordance with a further preferred embodiment, the predetermined pressure level of the etching plasma is in the range of 50 to 300 Pa, preferably about 150 Pa.
[0012] In accordance with a further preferred embodiment, the predetermined temperature level is in the range of 150° C. to 350° C., preferably about 250° C. With these process parameters a high removal rate of the resist still supplying a desired selectivity from the mask to the resist is advantageously provided.
[0013] In accordance with a further preferred embodiment, the carbon hard mask deposited for example using a chemical vapor deposition technique is used as an etch mask for semiconductor structuring.
[0014] In accordance with a further preferred embodiment, the resist mask is a carbon-based photo resist material.
[0015] In accordance with a further preferred embodiment, the liner preferably SiON is deposited on the carbon hardmask prior to depositing and stripping the resist.
[0016] In accordance with a further preferred embodiment, the semiconductor substrate is a Si-substrate. Best results of the resist stripping process were identified with aforesaid advantageous materials.
[0017] In accordance with a further preferred embodiment, the selectivity of the mask to the resist is equal or higher than 10.
[0018] In accordance with a further preferred embodiment, the resist is stripped with an across wafer uniformity of <3% one-sigma. Thereby, a highly selective removal of resist on a liner on top of a mask can be achieved with a high level of across wafer resist strip uniformity.
[0019] The foregoing section outlines rather broadly the features and technical advantages of embodiments of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the present invention will be henceforth described. It should be appreciated that the concepts and specific embodiments disclosed may be readily utilized by those skilled in the art for carrying out the same purposes outlined in the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] For a more complete understanding of the present invention and the advantages thereof, reference is now made to the following description taken in conjunction with the accompanying drawings, in which:
[0021] FIG. 1 illustrates a schematic cross-sectional view of a semiconductor substrate explaining a preferred embodiment method of the present invention.
[0022] FIG. 2 illustrates a schematic cross-sectional view of a semiconductor substrate explaining a prior art formation process.
[0023] FIG. 3 illustrates a schematic cross-sectional view of a semiconductor substrate explaining a further prior art formation process.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The making and using of the presently preferred embodiments are discussed in detail below. It should be appreciated, however, that the present invention provides a widely applicable inventive concept that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative of specific ways to make and use the invention, and do not limit the scope of the invention.
[0025] The present invention will be described with respect to preferred embodiments in a specific context, namely carbon photo resist removal on a carbon hard mask deposited on a semiconductor substrate. The invention may also be applied, however, to other stripping processes, such as removal of a sacrificial layer on a semiconductor substrate. The concepts of the present invention can be used with a variety of semiconductor devices including memories, CPUs, digital signal processors and amplifying devices.
[0026] A first embodiment will now be described with respect to FIG. 1 . In FIG. 1 , an exemplified recess 11 is provided in a semiconductor substrate 10 . The semiconductor substrate 10 e.g. a semiconductor wafer is preferably a Si-semiconductor substrate. On the surface of the semiconductor substrate 10 , a mask 12 is deposited. The mask 12 is preferably a hard mask, such as a carbon hard mask preferably deposited by CVD (chemical vapor deposition) and extends for example about 200 nm above the surface of said semiconductor substrate 10 . The recess 11 in the semiconductor substrate as shown has a rectangular cross-section on which hard mask 12 is deposited. The convex shape of the hard mask 12 in the recess 11 is an unintentional result of the deposition of the hard mask 12 in the recess 11 .
[0027] The carbon hard mask 12 outside the recess 11 protrudes the vertical etch line of the semiconductor substrate 10 also unintentionally as a result of the formation process of the carbon hard mask 12 . An overlying liner 13 , preferably consisting of SiON, is deposited basically evenly on the surface of the carbon hard mask The liner 13 acts as a barrier liner separating the mask 12 from a overlying resist. A resist, preferably a carbon photo resist (not shown in FIG. 1 ), which has been deposited on the shown structure is completely removed from the structure in accordance with FIG. 1 .
[0028] For stripping the resist from the liner 13 overlying the carbon hard mask 12 , a reductive etchant comprising hydrogen is/was used. Preferably an etching plasma with a flow of 1000 sccm of forming gas, comprising 96 per cent nitrogen N 2 and 4 per cent hydrogen H 2 , was used for a predetermined time, for example 270 seconds, at a predetermined temperature level, for example 250° C., and a predetermined pressure level, for example 150 Pa. Using such an oxygen-free etching plasma, the selectivity between the liner 13 and the stripped resist of more than 10, can be reached.
[0029] As is apparent from FIG. 1 , the carbon hard mask 12 shows no erosion symptoms, especially not in the areas of weakness existing in the liner layer 13 where said liner 13 is strongly bent around feature corners. Therefore, the stripping process to remove photo resist from a semiconductor wafer selectively to a mask 12 in accordance with the present invention using a reductive etchant comprising hydrogen is superior to the known stripping processes as described with reference to FIG. 2 and FIG. 3 .
[0030] In a further preferred embodiment, the etching plasma with 1000 SCCM of said nitrogen and hydrogen ratio, a predetermined amount of preferably below 4 per cent, especially 1 per cent of CF 4 equivalent to 10 sccm, is used to remove the photo resist from said liner 13 . With the etchant comprising about 1 per cent CF 4 , a selectivity from liner 12 to the resist of more than 16 is possible. While using said plasmas in accordance with the preferred embodiments of the present invention, an across wafer non-uniformity of less than 8 per cent, especially less than 4 per cent, could be obtained.
[0031] While not shown, it is understood that other elements could be included in the semiconductor substrate 10 . Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, manufacture, materials, methods or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, manufacture, materials, means, methods or steps.
[0000] Reference Signs
[0032] 10 semiconductor substrate/device, preferably Si-wafer
[0033] 11 recess, preferably rectangular
[0034] 12 mask, preferably carbon hard mask
[0035] 13 liner, preferably SiON
[0036] 14 cavity, especially mask erosion area
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The present invention relates to a method for removing a resist selective to a carbon hard mask including providing an etching plasma comprising of at least hydrogen at a predetermined temperature level and a predetermined pressure level in a reaction chamber, and etching the resist selectively to the mask with said plasma for a predetermined period of time.
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FIELD OF THE INVENTION
[0001] This invention relates to a fluoropolymer, the manufacture thereof, and the use thereof for imparting oil and water repellency to leather substrates. In particular, the fluoropolymer of this invention is made from monomers having very few or no hydrophilic groups.
BACKGROUND OF THE INVENTION
[0002] Various fluoropolymers have been proposed for imparting oil and water repellency to leather. Commonly, these fluoropolymers are amphiphilic; i.e., they are made from at least one monomer which is hydrophobic and at least one monomer which is hydrophilic. The present invention identifies and remedies disadvantages associated with the ability of amphiphilic fluoropolymers to impart oil and water repellency to leather.
[0003] Proposals of amphiphilic fluoropolymers for imparting oil and water repellency are summarized herein and include U.S. Pat. No. 5,316,860 which discloses amphiphilic copolymers for improving the strength, temper, and water resistance of the leather. The amphiphilic copolymers are formed from a predominant amount of at least one hydrophobic monomer and a minor amount of at least one copolymerizable hydrophilic monomer. U.S. Pat. No. 5,534,604 discloses copolymers comprising ethylenically unsaturated dicarboxylic acid anhydrides, long chain olefins and fluoroolefin. U.S. Pat. No. 5,124,181 discloses copolymers polymerized from (a) alkyl methacrylates, vinyl esters of carboxylic acids or mixtures thereof and (b) monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated dicarboxylic anhydrides, monoesters or monoamides of monoethylenically unsaturated dicarboxylic acids, amides of monocarboxylic acids. U.S. Pat. No. 5,741,434 discloses water-dispersible and/or water-emulsifiable co-oligomers containing (a) fatty crotonates; (b) radically copolymerizable, hydrophilic, ethylenically unsaturated acids and/or their anhydrides; and possibly (c) minor amounts of other copolymerizable comonomers.
[0004] Use of the aforementioned amphiphilic copolymers appears to be predicated on the belief that the hydrophilic portion (typically a carboxylic acid group) of these copolymers is necessary for imparting water resistance to leather. An expression of this conventional thinking may be found in U.S. Pat. No. 6,294,103 which advises: “if the carboxylic acid content is low the copolymer may not adequately penetrate the leather structure and/or may not bind sufficiently into the leather.”
BRIEF SUMMARY OF THE INVENTION
[0005] Contrary to conventional thinking, it has now been discovered that the incorporation of hydrophilic groups in a fluoropolymer undesirably reduces its ability to impart water resistance to leather. Correspondingly, it has also been discovered that a fluoropolymer incorporating fewer or no hydrophilic groups imparts superior oil and water repellency to leather when compared to fluoropolymers incorporating more hydrophilic groups.
[0006] Therefore, this invention provides fluoropolymers which incorporate reduced levels of hydrophilic groups. Preferably, the fluoropolymers of the invention are produced from monomers comprising hydrophobic monomers and no more than 5 weight percent of any hydrophilic monomer, preferably no more than 3.5 weight percent, and more preferably no more than 1 weight percent. Most preferably, the fluoropolymers of the invention are produced from monomers comprising only hydrophobic monomers and absent of any hydrophilic monomers.
[0007] The fluoropolymers of the invention are produced from monomers comprising at least one hydrophobic fluorinated acrylate and at least one hydrophobic vinyl compound such an alkyl acrylate, acrylamide, or styrene. When used herein, the term “acrylate” may include acrylate or methacrylate. When used herein, the term “acrylamide” may include acrylamide or methacrylamide. Preferably, the fluoropolymer is produced from a monomer mixture predominately comprising a fluorinated acrylate and a vinyl compound wherein the amount of any other hydrophobic monomer present is less than 20 weight percent, more preferably less than 10 weight percent, even more preferably less than 5 weight percent, and still even more preferably less that 1 weight percent. Most preferably, the fluoropolymer is produced from a monomer mixture comprising a fluorinated acrylate monomer, a vinyl compound monomer, and is absent of any other hydrophobic monomer. The amount of fluorinated acrylate monomer in the monomer mixture is preferably at least 20 weight percent, more preferably at least 30 weight percent, and most preferably at least 40 weight percent. The preferable amount of vinyl compound in the monomer mixture is at least 20 weight percent, more preferably at least 30 weight percent, and most preferably at least 35 weight percent.
[0008] The acrylate monomer used to make the fluoropolymer in the invention is represented by the following:
[0000]
[0000] wherein R f represents a perfluorinated alkyl group, optionally interrupted by oxygen, having at least 2 carbon atoms and preferably having 6 or fewer carbon atoms; each R 1 is independently chosen from a C 1 -C 20 hydrocarbylene, preferably C 1 -C 5 , more preferably linear, and even more preferably ethyl; R 8 is chosen from a C 1 -C 20 hydrocarbyl or hydrogen, preferably C 1 -C 5 , preferably linear, and more preferably hydrogen or methyl; R 2 is chosen from hydrogen, fluorine, or a C 1 -C 4 alkyl and is preferably hydrogen or methyl; m is 0 or 1, preferably 1.
[0009] The vinyl compound monomer used to make the fluoropolymer in the invention is represented by the following:
[0000]
[0000] wherein R h represents a linear or branched hydrocarbon group having at least 4 carbon atoms; each Z is divalent and independently selected from the group consisting of —OC(O)—, —HNC(O)—, and —C 6 H 4 —, preferably —OC(O)—; and R 3 is chosen from hydrogen or a C 1 -C 4 alkyl group and is preferably hydrogen or methyl.
[0010] Addition polymerization (e.g., free radical polymerization) using a monomer mixture comprising the aforementioned fluorinated acrylate (I) and vinyl compound (II) is conducted under conditions to produce the fluoropolymers of the invention. The polymerization process of the invention can be enabled with a free radical initiator and an optional chain transfer agent both of which are preferably absent of any fluorine atoms. The polymerization may be conducted in a homogeneous or heterogeneous medium resulting in fluoropolymers of the invention comprising hydrophobic fluorinated acrylic units, hydrophobic vinylic units, and optionally other monomeric units said fluoropolymer represented by the following:
[0000]
[0000] wherein x is a non-zero positive integer denoting the number of hydrophobic fluorinated acrylic units; y is a non-zero positive integer denoting the number of hydrophobic vinylic units; the ratio of x:y is preferably from 2:8 to 8:2, more preferably from 3:7 to 7:3, and most preferably from 4:6 to 6:4; the sum of x and y is at least 21; each R f independently represents a perfluorinated alkyl group, optionally interrupted by oxygen, having at least 2 carbon atoms and preferably having 6 or fewer carbon atoms; each R 1 is independently chosen from a C 1 -C 20 hydrocarbylene, preferably C 1 -C 5 , more preferably linear, and even more preferably ethyl; each R 8 is independently chosen from a C 1 -C 20 hydrocarbyl or hydrogen, preferably C 1 -C 5 , preferably linear, and more preferably hydrogen or methyl; each R 2 is independently chosen from hydrogen, fluorine, or a C 1 -C 4 alkyl and is preferably hydrogen or methyl; each m is independently 0 or 1, preferably 1; each R h independently represents a linear or branched hydrocarbon group having at least 4 carbon atoms; each Z is divalent and independently selected from the group consisting of —OC(O)—, —HNC(O)—, and —C 6 H 4 —, preferably —OC(O)—; and each R 3 is independently chosen from hydrogen or a C 1 -C 4 alkyl group and is preferably hydrogen or methyl.
[0011] Referring to Formula III, the fluoropolymer of the invention comprises no more than 5 weight percent of any monomeric units which are hydrophilic, preferably no more than 3.5 weight percent, and more preferably no more than 1 weight percent. Most preferably, the fluorocopolymer of the invention comprises no monomeric units which are hydrophilic. Other than fluorinated acrylic units and vinylic units, the fluoropolymers of the invention preferably comprise no more than 10 weight percent of any monomeric units which are hydrophobic, more preferably no more than 5 weight percent, and still more preferably no more than 1 weight percent. Preferably, at least 20 weight percent of the fluoropolymer of the invention is composed of fluorinated acrylic units, more preferably at least 30 weight percent, and most preferably at least 40 weight percent. Preferably, at least 20 weight percent of the fluoropolymer of the invention is composed of vinylic units, more preferably at least 30 weight percent, and most preferably at least 35.
[0012] When applied to leather, the fluoropolymers of the invention provide superior oil and water repellency compared to fluoropolymers incorporating higher amounts of hydrophilic groups. Application to leather can be performed by core (drum application) or surface (spray application) treatments.
[0013] Another advantage of the invention relates to fluoropolymers which incorporate perfluoroalkyl chains (R f ) having no more than six carbon atoms. Higher levels of fluorine incorporation in a fluoropolymer are thought to impart higher water repellency which may explain why conventional fluoropolymers typically have eight or more carbon atoms in their perfluoroalkyl chains. The reduction of the length of the R f chain in the invention represents economic savings attributable to the lowered expense of fluorine incorporation. Although the fluoropolymers of the invention have lower levels of incorporated fluorine, they are still able to impart adequate or superior water repellency thereby delivering the same or better performance at lower cost; i.e., better “fluorine efficiency.”
DETAILED DESCRIPTION OF THE INVENTION
[0014] The fluoropolymer of the invention is made by conducting free radical polymerization using hydrophobic monomers comprising a fluorinated acrylate monomer of Formula (I) and a vinyl compound of Formula (II) as follows:
[0000]
[0000] wherein R f represents a perfluorinated alkyl group, optionally interrupted by oxygen, having at least 2 carbon atoms and preferably having 6 or fewer carbon atoms; each R 1 is independently chosen from a C 1 -C 20 hydrocarbylene, preferably C 1 -C 5 , more preferably linear, and even more preferably ethyl; R 8 is chosen from a C 1 -C 20 hydrocarbyl or hydrogen, preferably C 1 -C 5 , preferably linear, and more preferably hydrogen or methyl; R 2 is chosen from hydrogen, fluorine, or a C 1 -C 4 alkyl and is preferably hydrogen or methyl; m is 0 or 1, preferably 1; R h represents a linear or branched hydrocarbon group having at least 4 carbon atoms; each Z is divalent and independently selected from the group consisting of —OC(O)—, —HNC(O)—, and —C 6 H 4 —, preferably —OC(O)—; and R 3 is chosen from hydrogen or a C 1 -C 4 alkyl group and is preferably hydrogen or methyl.
[0015] Examples of suitable fluorinated acrylate monomers of Formula (I) wherein s=0 are disclosed in U.S. Pat. Nos. 4,174,851, 2,642,416, 3,384,627, 3,392,046, 3,282,905, 3,532,659, 3,102,103, all of which are hereby incorporated by reference to the extent permitted by applicable law. Specific examples of suitable fluorinated acrylate monomers of Formula (1) wherein s=0 include perfluorobutylethyl acrylate, perfluorohexylethyl acrylate, perfluorobutylethyl methacrylate, and perfluorohexylethyl methacrylate. Examples of suitable fluorinated acrylate monomers of Formula (1) wherein s=1 are disclosed in U.S. Pat. No. 5,439,998 which is hereby incorporated by reference to the extent permitted by applicable law. Specific examples of suitable fluorinated acrylate monomers of Formula (1) wherein s=1 include 2-[methyl[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonyl]amino]ethyl acrylate; 2-[methyl[(3,3,4,4,5,5,6,6,6-nonafluorohexyl)sulfonyl]amino]ethyl acrylate; 2-[methyl[(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)sulfonyl]amino]ethyl acrylate; 2-[methyl[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)sulfonyl]amino]ethyl methacrylate; [methyl[(3,3,4,4,5,5,6,6,6-nonafluorohexyl)sulfonyl]amino]ethyl methacrylate; and 2-[methyl[(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)sulfonyl]amino]ethyl methacrylate.
[0016] Examples of suitable vinyl compounds of Formula (II) useful in the invention wherein Z is —OC(O)— are acrylates including long chain C 8 to C 40 alkyl acrylates, C 8 to C 40 alkyl methacrylates, and mixtures thereof. Examples of suitable compounds of this type are 2-ethylhexyl acrylate, n-decyl acrylate, dodecyl acrylate, isotridecyl acrylate, tetradecyl acrylate, C 16 to C 18 tallow fatty alcohol acrylate, octadecyl acrylate, palrityl acrylate, n-eicosyl acrylate, and mixtures thereof. Also suitable are mixtures of long chain alkyl acrylates. Preferable acrylates are acrylic and methacrylic esters derived from alcohols of 4 to 28 carbon atoms. Examples of suitable vinyl compounds of Formula (II) useful in the invention wherein Z is —HNC(O)— are acrylamides including n-decyl-2-propenamide, n-octadecyl-2-propenamide, n-dodecyl-2-propenamide, n-hexadecylmethacrylamide, n-decylmethacrylamide, n-stearylmethacrylamide, and n-dodecylmethacrylamide, and mixtures thereof. Examples of suitable vinyl compounds of Formula (II) useful in the invention wherein Z is —C 6 H 4 — are syrenic compounds including p-dodecylstyrene, 4-octylstyrene, p-pentylstyrene, and p-dexylstyrene, and mixtures thereof.
[0017] Preferably, the fluoropolymer is produced from monomers predominately comprising the aforementioned fluorinated acrylate and vinyl compound wherein the amount of any other hydrophobic monomer present is less than 20 weight percent, more preferably less than 10 weight percent, even more preferably less than 5 weight percent, and still even more preferably less that 1 weight percent.
[0018] While not wishing to be bound by any particular theory, it is thought that the ability of fluoropolymers of this invention to impart improved oil and water repellency is attributable, at least in part, from being made with monomers having the terminal perfluorinated R f chain possessed by incorporated fluorinated acrylate monomers of Formula (I). Accordingly, a sufficient amount of fluorinated acrylate monomer should be present such that fluoropolymers made therefrom impart acceptable water and oil resistance to leather. The amount of fluorinated acrylate monomer in the monomers used to make the fluoropolymer is preferably at least 20 weight percent, preferably at least 30 weight percent, and most preferably at least 40 weight percent.
[0019] The use of vinyl compound monomers is necessary to endow fluoropolymers made therefrom with the ability to lubricate and thereby impart acceptable suppleness to leather. While not wishing to be bound by any particular theory, it is thought the ability of fluoropolymers of this invention to impart lubricity and suppleness is attributable, at least in part, to incorporation of monomers having terminal R h chains possessed by vinyl compounds of Formula (II) wherein the R h chains undergo London dispersion force interactions with the leather substrate including chemicals therein which were applied during tanning. Accordingly, a sufficient amount of vinyl compound should be present such that fluoropolymers made therefrom impart acceptable lubricity and suppleness to leather. The preferable amount of vinyl compound in the monomer mixture used to make the fluoropolymer is at least 20 weight percent, preferably at least 30 weight percent, and most preferably at least 35 weight percent.
[0020] Because it has now been discovered that the incorporation of too many hydrophilic groups in a fluoropolymer undesirably reduces its ability to impart water and oil resistance to leather, the monomers used to make the fluoropolymers of the invention should comprise no more than 2.5 weight percent of any hydrophilic monomer, preferably no more than 1 weight percent, more preferably no more than 0.5 weight percent. Most preferably, the fluoropolymer of the invention is produced from monomers comprising only hydrophobic monomers absent any hydrophilic monomers. Hydrophobic monomers are generally defined as compounds which do not have the ability to form hydrogen bonds with water and do not readily dissolve in or absorb water. Hydrophilic monomers which should be minimized or absent from monomers used to make the fluoropolymers of the invention are exemplified in U.S. Pat. Nos. 5,316,860; 5,534,604; 5,124,181; 5,741,434; and U.S. Pat. No. 6,294,103. Specific examples of hydrophilic monomers include anhydrides, carboxylic acids, alcohols, and salts thereof.
[0021] It should be noted that residues from free radical initiators and optional chain transfer agents can be incorporated in the fluoropolymers of the invention. It should be understood that the term “monomer” or “monomeric unit” used herein does not include free radical initiators, optional chain transfer agents or the residues therefrom.
[0022] The fluoropolymers of the invention comprise hydrophobic fluorinated acrylic units, hydrophobic vinylic units, and optionally other monomeric units said fluoropolymer represented by the following:
[0000]
[0000] wherein x is a non-zero positive integer denoting the number of hydrophobic fluorinated acrylic units; y is a non-zero positive integer denoting the number of hydrophobic vinylic units; the sum of x and y is at least 21; each R f independently represents a perfluorinated alkyl group, optionally interrupted by oxygen, having at least 2 carbon atoms and preferably having 6 or fewer carbon atoms; each R 1 is independently chosen from a C 1 -C 20 hydrocarbylene, preferably C 1 -C 5 , more preferably linear, and even more preferably ethyl; each R 8 is independently chosen from a C 1 -C 20 hydrocarbyl or hydrogen, preferably C 1 -C 5 , preferably linear, and more preferably hydrogen or methyl; each R 2 is independently chosen from hydrogen, fluorine, or a C 1 -C 4 alkyl and is preferably hydrogen or methyl; each m is independently 0 or 1, preferably 1; each R h independently represents a linear or branched hydrocarbon group having at least 4 carbon atoms; each Z is divalent and independently selected from the group consisting of —OC(O)—, —HNC(O)—, and —C 6 H 4 —, preferably —OC(O)—; and each R 3 is independently chosen from hydrogen or a C 1 -C 4 alkyl group and is preferably hydrogen or methyl.
[0023] The ratio of x:y may be determined by balancing the water and oil resistance thought to be provided by terminal R f groups with the lubricity and suppleness thought to be provided by terminal R h groups. Accordingly, and the ratio of x:y is preferably from 2:8 to 8:2, more preferably from 3:7 to 7:3, and most preferably from 4:6 to 6:4.
[0024] Referring to Formula III, the fluoropolymer of the invention comprises no more than 5 weight percent of any monomeric units which are hydrophilic, preferably no more than 3.5 weight percent, and more preferably no more than 1 weight percent. Incorporation of high amounts of hydrophilic monomeric units have been discovered to detrimentally affect the resulting fluoropolymer's ability to impart oil and water repellency.
[0025] Accordingly, the fluorocopolymer of the invention most preferably comprises no monomeric units which are hydrophilic. Examples of monomeric units which are hydrophilic include those that have the following groups: anhydrides, carboxylic acids, alcohols, and salts thereof. Other than fluorinated acrylic units and vinylic units, the fluoropolymers of the invention preferably comprise no more than 10 weight percent of any monomeric units which are hydrophobic, more preferably no more than 5 weight percent, and still more preferably no more than 1 weight percent.
[0026] As discussed earlier, it is believed that the terminal R f chain in the fluorinated acrylic units improves the ability of the fluoropolymer to impart oil and water repellency. Accordingly, at least 20 weight percent of the fluoropolymer of the invention is preferably composed of fluorinated acrylic units, more preferably at least 30 weight percent, and most preferably at least 40 weight percent. As discussed earlier, it is believed that the terminal R h chain in the vinylic units improves the ability of the fluoropolymer to impart lubricity and suppleness to leather. Accordingly, at least 20 weight percent of the fluoropolymer of the invention is preferably composed of vinylic units, more preferably at least 30 weight percent, and most preferably at least 35.
[0027] As described herein, the molecular weight of the fluoropolymers of the invention can be controlled by use of a chain transfer agent and is preferably at least 10,000 grams/mole. The molecular weight can be chosen depending upon the final use of the fluoropolymer. If the fluoropolymer is delivered in an organic solvent intended for use in a spray application, a high molecular weight is chosen; e.g., greater than about 50,000 grams/mole. If the fluoropolymer is delivered in an aqueous dispersion or emulsion intended for use in a spray or drum application, a medium molecular weight is chosen; e.g., from about 10,000 to about 50,000 grams/mole.
[0028] One advantage of using the fluoropolymers of the invention for treatment of leather is their increased fluorine efficiency; i.e., the fluoropolymers of the invention are able to impart water and oil repellency while incorporating less fluorine. Conventional fluoropolymers typically require perfluoroalkyl chains having eight or more carbon atoms to achieve an adequate ability to impart water and oil repellency to leather. In advantageous contrast, the fluoropolymers of the invention only require perfluoroalkyl chains (denoted as R f in Formulae I and III) having six or fewer carbon atoms to achieve an adequate ability to impart water and oil repellency to leather. A short R f perfluorinated alkyl chain results in lower incorporated levels of costly fluorine. Despite the short R f chain, the fluoropolymers of the invention effectively impart water and oil repellency to leather.
[0029] In a preferred embodiment of the invention, a mixture of monomers comprising a fluorinated acrylate monomer of Formula (I) and a vinyl compound of Formula (II) is dissolved in an organic solvent thereby producing an monomer mixture which be used in a solution polymerization (optionally followed by dispersion in water) or emulsion polymerization.
[0030] During solution polymerization, free radical polymerization of monomers comprising a fluorinated acrylate of Formula (I) and a vinyl compound of Formula (II) is conducted by dissolving the monomers, free radical initiator, and chain transfer agent in an organic solvent. The solution is then heated and maintained at about 40 to 100° C., more preferably about 55 to 90° C., and allowed to react under inert conditions for a period of time to obtain at least 95 percent yield of polymer. Polymer yield may be determined by measuring the amount of residual monomer by gas chromatography. The concentration of monomers in the organic solvent is preferably from 30 to 70 weight percent. Initiator is preferably added in an amount of 0.01 to 2 molar percentage of total monomers. Chain transfer agent(s) can be added in an amount to yield a polymer with a desirable targeted molecular weight which can be determined by summing the weight of monomers in grams, dividing this sum by the total moles of chain transfer agent(s) used, and then adding to this quotient the weighted average of the molecular weight of the chain transfer agent(s) used.
[0031] Examples of free radical initiators useful during solution polymerization include: azo compounds, such as azobisisobutyronitrile and azo-2-cyanovaleric acid; hydroperoxides, such as cumene, t-butyl and t-amyl hydroperoxide; dialkyl peroxides, such as di-t-butyl and dicumylperoxide; peroxyesters, such as t-butylperbenzoate and di-t-butylperoxy phthalate; and diacylperoxides, such as benzoyl peroxide and lauryl peroxide.
[0032] Examples of chain transfer agents useful during solution polymerization include n-dodecyl mercaptan, mercaptoethanol, mercaptoacetic acid, stearylmercaptane, tert-dodecylmercaptane, trichloromethane, diethyl phosphate, methanol, and mixtures thereof. Examples of suitable organic solvents include: acetates, such as ethyl acetate, butyl acetate, and isopropyl acetate; alcohols, such as 2-methylpropan-2-ol, isopropanol, 2-methoxypropan-2-ol; and ketones, such as acetone, methylisobutyl ketone, and methylethyl ketone, such as n-methyl-2-pyrrolidone, and mixtures thereof.
[0033] By using the solution polymerization process described in the invention, an organic solution of fluoropolymers is obtained which is useful for treating leather substrates by spray application. The fluoropolymers of the present invention can also take the form of an aqueous fluoropolymer dispersion which can be made by mechanically mixing (e.g., with a homogenizer) water, at least one surfactant, and an organic solution of fluoropolymers made by the aforementioned solution polymerization process. Aqueous fluoropolymer dispersions of the invention are useful for treating leather substrates by spray and drum application.
[0034] An alternative method for making the aqueous fluoropolymer dispersions of the invention involves emulsion polymerization wherein free radical polymerization of monomers comprising a fluorinated acrylate monomer of Formula (I) and a vinyl compound of Formula (II) is conducted by reacting a mixture comprising the monomers, free radical initiator(s), chain transfer agent(s), organic solvents, and water. In a preferred embodiment of the invention, emulsion polymerization is conducted using three vessels: a monomer staging vessel, an initiator staging vessel, and a reaction vessel. In the monomer staging vessel, a monomer mixture is prepared by mixing ingredients comprising water, a water soluble organic solvent, a pH buffer, a surfactant (preferably non-fluorinated), a fluorinated acrylate monomer of Formula (I), chain transfer agent and a vinyl compound of Formula (II). When delivered, the fluorinated acrylate monomer is typically dissolved in an organic solvent such as acetone and/or alcohol. In the initiator staging vessel, an initiator mixture is prepared by mixing water with a water soluble free radical initiator. The monomer mixture is introduced to the reactor vessel and heated to the reaction temperature (typically from 40-90° C.); after which, the initiator mixture is introduced and the polymerization is conducted. Although the emulsion polymerization process of the invention can involve a single addition of monomer mixture and a single addition of initiator mixture as described above, serial or continuous additions of monomer mixture and initiator mixture are preferred.
[0035] Suitable water soluble initiators for use in the emulsion polymerization process of this invention include: inorganic salts of persulfuric acid, such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox initiators, such as persulfate-bisulfite couple, persulfate-hydrosulfite couple; peroxides such as hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide; and azoic compounds, such as 4,4′-azobis(cyano-4-pentanoic acid). Suitable chain transfer agents for use in the emulsion polymerization process of this invention include: mercaptoethanol, mercaptoacetic acid, stearylmercaptane, tert-dodecylmercaptane, trichloromethane, and the like, and mixtures thereof. Examples of suitable organic co-solvents include: acetates, such as ethyl acetate, butyl acetate, and isopropyl acetate; alcohols, such as 2-methylpropan-2-ol, isopropanol, 2-methoxypropan-2-ol; and ketones, such as acetone, methylisobutyl ketone, and methylethyl ketone; and, such as n-methyl-2-pyrrolidone and the like, and mixtures thereof.
[0036] As an alternative to the chain transfer agents mentioned above, fluoropolymers of the invention can be prepared by any known process of controlled polymerization including: Atom Transfer Radical Polymerization (ATRP), Reversible Addition Fragmentation chain Transfer polymerization (RAFT), Iodine Transfer Polymerization (ITP), Reversible Iodine Transfer Polymerization (RITP), Macromolecular Design via the Interchange of Xanthates (MADIX), and Nitroxide Mediated Polymerization (NMP). Of these mechanisms, RAFT and ITP are preferred for use in the invention. Specifically, the RAFT mechanism employs a dithioester group containing compounds, such as 1-(ethoxycarbonyl)eth-1-yl dithiobenzoate), as free radical initiators and is described in U.S. Pat. No. 6,642,318; hereby incorporated by reference to the extent permitted by applicable law. The ITP mechanism employs an iodo containing chain transfer agent, such as perfluorohexyliodine, and is described in U.S. Pat. Nos. 4,158,678; 5,231,154; both of which are hereby incorporated by reference to the extent permitted by applicable law
[0037] The fluoropolymers of the invention can be applied to leather by well known techniques. Preferred methods of application include core (drum application) or surface (spray application) treatments.
[0038] In drum application, leather is placed in a “drum” which typically comprises a cylindrical structure mounted on axles with a sealable door. The axles can be hollow thereby allowing the introduction and removal of a liquid for treatment of the leather. In accordance with the invention, leather is placed in a drum and contacted with a chosen liquid treatment. The drum is sealed then agitated back and forth and/or rotated like a washing machine for a length of time suitable to complete the chosen treatment. The drum may be equipped with internal shelves, pegs, and/or paddle to help improve penetrability.
EXAMPLES
[0039] In all the examples, the fluorinated acrylate monomer used was 2-[methyl[(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl sulfonyl]amino]ethyl ester of 2-propenoic acid, used as a 80.4 wt. % solution in acetone). In all of the examples, the vinyl compound monomer used was lauryl acrylate. When referring to certain ingredients below the term “CASRN” is used as an acronym for Chemical Abstract Service Registry Number which are assigned in sequential order to unique, new substances identified by Chemical Abstracts Service for inclusion in their database named, the CAS Registry. Application procedures and repellency tests are described below.
Drum Application Procedure #1
[0040] The substrate used in this procedure was bovine nubuck with a thickness of 1.8-2.0 mm. The substrate was placed in a drum and subjected to a treatment procedure according to the Table 1 below after which: 1) the resulting treated substrate is dried at room temperature for 7 days at room temperature; 2) then the treated substrate is dried at 60° C. for 4 hours; and 3) then the treated substrate is cooled to room temperature.
[0000]
TABLE 1
Treatment
Step
solution (1)
Temperature
Time
Wetting back
600% water
40° C.
30 min
Neutralization
600% water
40° C.
1% sodium
30 min
formate
0.5% sodium
30 min
bicarbonate
Wash
600% water
40° C.
10 min
Fatliquoring/dyeing
400% water
50° C.
60 min
10% Fatliquor
3% Dyestuff
Fluoropolymer
200% water
50° C.
60 min
introduction
fluoropolymer (2)
Fixation
2.2% formic acid (3)
50° C.
20 min
Rinse
600% water
40° C.
10 min
(1) Amounts added are weight percent based on the weight of the substrate.
(2) The amount of fluoropolymer added varies and is specified below.
(3) Delivered as 25 wt. % formic acid in water.
Drum Application Procedure #2
[0041] The substrate used in this procedure was bovine full grain from wet blue with a thickness of 1.8-2.0 mm. The substrate was placed in a drum and subjected to a treatment procedure according to the Table 2 below after which: 1) the resulting treated substrate is dried at room temperature for 7 days at room temperature; 2) then the treated substrate is dried at 60° C. for 4 hours; and 3) then the treated substrate is cooled to room temperature.
[0000]
TABLE 2
Treatment
Step
solution (1)
Temperature
Time
Wetting back
400% water
40° C.
30 min
Neutralization
400% water
40° C.
2% sodium
15 min
formate
0.5% sodium
30 min
bicarbonate
Wash
400% water
40° C.
5 min
Retanning/
200% water
50° C.
Fatliquoring/dyeing
5% Polymer
45 min
Tanning agent
10% Fatliquor
45 min
3% Dyestuff
Fluoropolymer
200% water
50° C.
45 min
introduction
fluoropolymer (2)
Fixation
4% formic acid (3)
50° C.
20 min
Rinse
400% water
40° C.
10 min
(1) Amounts added are weight percent based on the weight of the substrate.
(2) The amount of fluoropolymer added varies and is specified below.
(3) Delivered as 25 wt. % formic acid in water.
Drum Application Procedure #3
[0042] The substrate used in this procedure was lamb from stain with a thickness of 1.8-2.0 mm. The substrate was placed in a drum and subjected to a treatment procedure according to the Table 3 below after which: 1) the resulting treated substrate is dried at room temperature for 7 days at room temperature; 2) then the treated substrate is dried at 60° C. for 4 hours; and 3) then the treated substrate is cooled to room temperature.
[0000]
TABLE 3
Treatment
Step
solution (1)
Temperature
Time
Wetting back
1000% water
60° C.
15 min
Neutralization
1000% water
35° C.
5
0.5% ammonia (3)
60 min
1.5% ammonia (3)
15 min
Wash
1000% water
35° C.
10 min
Fatliquoring/dyeing
400% water
50° C.
4% fatliquor
3% dyestuff
60 min
Fluoropolymer
400% water
50° C.
60 min
introduction
fluoropolymer (2)
Fixation
2.5% formic acid (4)
50° C.
20 min
Rinse
1000% water
40° C.
10 min
(1) Amounts added are weight percent based on the weight of the substrate.
(2) The amount of fluoropolymer added varies and is specified below.
(3) Delivered as 28 wt. % ammonia in water.
(4) Delivered as 25 wt. % formic acid in water.
Drum Application Procedure #4
[0043] The substrate used in this procedure was lamb skin from wet blue with a thickness of 1.8-2.0 mm. The substrate was placed in a drum and subjected to a treatment procedure according to the Table 4 below after which: 1) the resulting treated substrate is dried at room temperature for 7 days at room temperature; 2) then the treated substrate is dried at 60° C. for 4 hours; and 3) then the treated substrate is cooled to room temperature.
[0000]
TABLE 4
Treatment
Step
solution (1)
Temperature
Time
Wetting back
300% water
40° C.
60 min
1% oxalic acid
Wash
1000% water
35° C.
5 min
Neutralization/
100% water
40° C.
Retanning
5% Polymer
60 min
Tanning agent
2% sodium acetate
30 min
0.5% sodium
60 min
bicarbonate
Wash
1000% water
35° C.
5 min
Fatliquoring/dyeing
150% water
40° C.
10% Fatliquor
2% dyestuff
60 min
2% formic acid (3)
45 min
Wash
1000% water
35° C.
5 min
Fluoropolymer
150% water
40° C.
40 min
introduction
fluoropolymer (2)
Fixation
1% formic acid (3)
40° C.
20 min
Rinse
1000% water
40° C.
10 min
(1) Amounts added are weight percent based on the weight of the substrate.
(2) The amount of fluoropolymer added varies and is specified below.
(3) Delivered as 25 wt. % formic acid in water.
Drum Application Procedure #5
[0044] The substrate used in this procedure was pig suede from wet blue with a thickness of 0.6-0.8 mm. The substrate was placed in a drum and subjected to a treatment procedure according to the Table 4 below after which: 1) the resulting treated substrate is dried at room temperature for 7 days at room temperature; 2) then the treated substrate is dried at 60° C. for 4 hours; and 3) then the treated substrate is cooled to room temperature.
[0000]
TABLE 5
Treatment
Tem-
Step
solution (1)
perature
Time
Wetting back
300% water
50° C.
30 min
Wash
300% water
30° C.
10 min
Neutralization
200% water
30° C.
2% sodium formate
3% sodium
90 min
bicarbonate
Wash
300% water
30° C.
10 min
Dyeing/
50% water
Fatliquoring
1% ammonia (4)
3% dyestuff
30° C.
30 min
200% water
60° C.
10 min
15% Fatliquors
90 min
2% formic acid (3)
15 min
1.5% formic acid (3)
15 min
Wash
300% water
60° C.
10 min
Fluoropolymer
200% water
50° C.
10 min
introduction
fluoropolymer (2)
20 min
Fixation
1% formic acid (3)
50° C.
20 min
3% chromitan B
60 min
Rinse
300% water
40° C.
10 min
(1) Amounts added are weight percent based on the weight of the substrate.
(2) The amount of fluoropolymer added varies and is specified below.
(3) Delivered as 25 wt. % formic acid in water.
(4) Delivered as 28 wt. % ammonia in water.
[0045] Spray Application Procedure #1
[0046] The substrate used in this procedure was lamb from stain with a thickness of 1.8-2.0 mm. A treatment solution comprising a fluoropolymer diluted in water (as specified in the examples below) was sprayed onto the substrate. The deposit applied on substrate was 150 g/m 2 (with an error of about 20 g/m 2 ). The treated substrate was then dried at room temperature for 24 hours and then was dried at 60° C. for 2 hours.
Spray Application Procedure #2
[0047] The substrate used in this procedure was lamb from stain with a thickness of 1.8-2.0 mm. A treatment solution comprising a fluoropolymer diluted in isopropyl alcohol or ethyl acetate water (as specified in the examples below) was sprayed onto the substrate. The deposit applied on substrate was 100 g/m 2 (with an error of about 10 g/m 2 ). The treated substrate was then dried at room temperature for 24 hours.
Water Repellency Test
[0048] Water repellency was measured according to AATCC Test Method 193-2005, except that test solutions 9-12, measuring higher water repellency, were added as shown in Table 1, below. Higher test liquid numbers indicate increased water repellency.
[0000]
TABLE 6
Compositions of Water Repellency Test Liquids
Water Repellency
De-ionized
Isopropanol
Surface Tension
Test Liquid Number
Water (Vol. %)
(Vol. %)
(mN · m −1 )
0
None (fails 98% water/2% isopropanol)
1
98
2
59.00
2
95
5
49.75
3
90
10
41.60
4
80
20
32.50
5
70
30
27.40
6
60
40
25.40
7
50
50
24.50
8
40
60
24.00
9*
30
70
23.40
10*
20
80
22.70
11*
10
90
21.90
12*
0
100
21.80
*Test liquids added to AATCC Test Method 193-2005.
Oil Repellency Test
[0049] Oil repellency was measured according to AATCC Test Method 118-2002. Oil Repellency Grades are 0-8. Higher values indicate increased oil repellency.
Example 1
[0050] To a double-jacketed 1 liter reactor was added vinyl compound monomer (32.5 g, 0.136 mol), fluorinated acrylate monomer (40.1 g, 0.059 mol), t-butanol (130.0 g, 1.76 mol), and n-dodecyl mercaptan (0.63 g, 3.1 mmol) with stirring. The temperature was raised to 75° C. Oxygen was removed from the reactor by 30 minutes of a nitrogen flow. Azobisisobutyronitrile (0.52 g, 3.16 mmol) was added to the solution. The temperature was maintained for 20 h under nitrogen. The solids content of the final solution was 36.0 wt. % (theoretical value: 35.9 wt. %). This solution was dried by distillation to remove t-butanol at 70° C. and 350 to 20 mbar vacuum (35 to 2 kPa). Ethyl acetate was added in order to obtain an organic solution with a solids content of 45.05 wt. %.
[0051] To a 100-mL flask was added water (28.2 g), propylene glycol (3.18 g), SULFRAMIN acid B (Alkylbenzene sulfonic acid, mixture of C10-C13 isomers, CASRN 85536-14-7, Akzo Nobel, 0.38 g), and NOURACID CZ80 (castor oil fatty acid, CASRN 61789-44-4, Akzo Nobel, 0.13 g) at room temperature with stirring. The solution of polymer in ethyl acetate was added drop-by-drop to this aqueous solution under high shear (ULTRATURAX T2, IKA, 8000 rpm) and maintained under shear for 3 min. The dispersion obtained was left under ultrasound (Vibracell, Sonics&Material) for 3 min. Ethyl acetate was removed by distillation at 70° C. under 350 to 180 mbar vacuum (35 to 18 kPa). The solids content of the dispersion was 45.4 wt. % and the fluorine content of the fluoropolymer therein was 22.8 wt. %.
Example 2
[0052] Example 1 was repeated except that perfluorohexyliodine (CASRN 355-43-1, PFHI, DuPont, 1.47 g, 3.1 mmol) was used instead of n-dodecyl mercaptan. The product made by Example 2 had a solids content of 31.3 wt. % and the fluorine content of the fluoropolymer therein was 21.8 wt. %.
Example 3
[0053] Example 1 was repeated except that 1-(ethoxycarbonyl)eth-1-yl dithiobenzoate (0.79 g instead of n-dodecyl mercaptan. Synthesis of 1-(ethoxycarbonyl)eth-1-yl dithiobenzoate is described in the following reference: Severac R., Lacroix-Desmazes P., Boutevin B., Polymer International, 2005 (51) 1117-1122, hereby incorporated by reference to the extent permitted by applicable law. The product made by Example 3 had a solids content of 37.6 wt. % and the fluorine content of the fluoropolymer therein was 23.0 wt. %.
Repellency Evaluation #1: Examples 1-3
[0054] Three pieces were cut from the same sample of bovine nubuck and identified as Bovine Nubuck #1, Bovine Nubuck #2, and Bovine Nubuck #3.
[0055] The product made by Example 1 was applied to Bovine Nubuck #1 in accordance with Drum Application Procedure #1 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.33 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 7.
[0056] The product made by Example 2 was applied to Bovine Nubuck #2 in accordance with Drum Application Procedure #1 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 2 in water, thereby yielding a treatment solution with a fluorine content of 0.33 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 7.
[0057] The product made by Example 3 was applied to a Bovine Nubuck #3 in accordance with Drum Application Procedure #1 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 3 in water, thereby yielding a treatment solution with a fluorine content of 0.33 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 7.
[0000]
TABLE 7
Wt. % Fluorine
Oil Re-
Water Re-
Example
Chain Transfer Agent
Incorporated in
pellency
pellency
#
Used
Fluoropolymer
Rating
Rating
1
n-dodecyl mercaptan
22.8
6
12
2
perfluorohexyliodine
21.8
6
11/12*
3
1-(ethoxycarbonyl)eth-
23.0
5
10/11*
1-yl dithiobenzoate
*indicates a rating in-between these two numbers
[0058] Table 7 shows that various chain transfer agents can be employed to make the fluoropolymers of the invention having approximately the same fluorine incorporation and the same ability to impart repellency.
Comparative Example A
[0059] To a double-jacketed 1 liter reactor was added vinyl compound monomer (22.6 g, 0.0923 mol), fluorinated acrylate monomer (28.2 g, 0.042 mol), acrylic acid (19.41 g, 0.269 mol), t-butanol (120.0 g, 1.62 mol), and n-dodecyl mercaptan (0.63 g, 3.1 mmol) with stirring. The temperature was raised to 75° C. Oxygen was removed from the reactor by 30 minutes of a nitrogen flow. Azobisisobutyronitrile (0.52 g, 3.11 mmol) was added to the solution. The temperature was maintained for 20 h under nitrogen. The solids content of the final solution was 35.6 wt. % (theoretical value: 35.9 wt %). This solution was dried by distillation to remove t-butanol at 70° C. and 350 to 20 mbar vacuum (35 to 2 kPa). Ethyl acetate was added in order to obtain an organic solution with a solids content of 44.9 wt. %.
[0060] To a 100-mL flask was added water (28.2 g), propylene glycol (3.18 g), SULFRAMIN acid B (Alkylbenzene sulfonic acid, mixture of C10-C13 isomers, CASRN 85536-14-7, Akzo Nobel, 0.38 g), and NOURACID CZ80 (castor oil fatty acid, CASRN 61789-44-4, Akzo Nobel, 0.13 g) at room temperature with stirring. The solution of polymer in ethyl acetate was added drop-by-drop to this aqueous solution under high shear (ULTRATURAX T2, IKA, 8000 rpm) and maintained under shear for 3 min. The dispersion obtained was left under ultrasound (Vibracell, Sonics&Material) for 3 min. Ethyl acetate was removed by distillation at 70° C. under 350 to 180 mbar vacuum (35 to 18 kPa). The solids content of the dispersion was 45.2 wt. % and the fluorine content of the fluoropolymer therein was 16.0 wt. %.
[0000] Repellency Evaluation #2: Example 1 versus Comparative Example A
[0061] Two pieces were cut from the same sample of bovine nubuck and identified as Bovine Nubuck #4 and Bovine Nubuck #5. It should be noted that the sample of bovine nubuck used in Repellency Evaluation #2 was different from the sample of bovine nubuck used in Repellency Evaluation #1.
[0062] The product made by Example 1 was applied to Bovine Nubuck #4 in accordance with Drum Application Procedure #1 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.33 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0063] The product made by Comparative Example A was applied to Bovine Nubuck #5 in accordance with Drum Application Procedure #1 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Comparative Example A in water, thereby yielding a treatment solution with a fluorine content of 0.33 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0064] Two pieces were cut from the same sample of bovine full grain from wet blue and identified as Bovine Full Grain #1 and Bovine Full Grain #2.
[0065] The product made by Example 1 was applied to Bovine Full Grain #1 in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0066] The product made by Comparative Example A was applied to Bovine Full Grain #2 in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Comparative Example A in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0067] Two pieces were cut from the same sample of lamb skin from wet blue and identified as Lamb Blue #1 and Lamb Blue #2.
[0068] The product made by Example 1 was applied to Lamb Blue #1 in accordance with Drum Application Procedure #4 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.22 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0069] The product made by Comparative Example A was applied to Lamb Blue #2 in accordance with Drum Application Procedure #4 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Comparative Example A in water, thereby yielding a treatment solution with a fluorine content of 0.22 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0070] Two pieces were cut from the same sample of pig suede from wet blue and identified as Pig Suede #1 and Pig Suede #2.
[0071] The product made by Example 1 was applied to Pig Suede #1 in accordance with Drum Application Procedure #5 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0072] The product made by Comparative Example A was applied to Pig Suede #2 in accordance with Drum Application Procedure #5 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Comparative Example A in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 8.
[0000]
TABLE 8
Water
Oil Repellency
Repellency
Substrate
Example #
Rating
Rating
bovine nubuck
1
6
12
A
0
4
bovine full grain from wet
1
4
8
blue
A
0
4
lamb skin from wet blue
1
5
10
A
0
5
pig suede from wet blue
1
6
11
A
0
4
[0073] Table 8 demonstrates that the incorporation of a hydrophilic monomer (acrylic acid) detrimentally affects the ability of a fluoropolymer to impart repellency. A comparison is made of: 1) substrates treated with Example 1, a fluoropolymer without incorporation of acrylic acid; versus 2) substrates treated with Comparative Example A, a fluoropolymer incorporating acrylic acid. This comparison shows that substrates treated by the same process had significantly better repellency to oil and water when treated with a fluoropolymer without incorporation of a hydrophilic monomer (acrylic acid).
Example 4
[0074] To a double-jacketed 1 liter reactor was added vinyl compound monomer (18.8 g, 78.1 mmol), fluorinated acrylate monomer (35.1 g, 52.4 mmol), t-butanol (110.2 g, 1.49 mol), and n-dodecyl mercaptan (0.47 g, 2.32 mmol) with stirring. The temperature was raised to 75° C. Oxygen was removed from the reactor by 30 minutes of a nitrogen flow. Azobisisobutyronitrile (0.35 g, 2.15 mmol) was added to the solution. The temperature was maintained for 20 h under nitrogen. The solids content of the final solution was 29.2 wt. % (theoretical value: 28.7 wt. %). This solution was dried by distillation to remove t-butanol at 70° C. and 350 to 20 mbar vacuum (35 to 2 kPa). Ethyl acetate was added in order to obtain an organic solution with a solids content of 45.05 wt. %.
[0075] To a 100-mL flask was added water (20.4 g), propylene glycol (2.30 g), SULFRAMIN acid B (Alkylbenzene sulfonic acid, mixture of C10-C13 isomers, CASRN 85536-14-7, Akzo Nobel, 0.27 g), and NOURACID CZ80 (castor oil fatty acid, CASRN 61789-44-4, Akzo Nobel, 0.09 g) at room temperature with stirring. The solution of polymer in ethyl acetate was added drop-by-drop to this aqueous solution under high shear (ULTRATURAX T2, IKA, 8000 rpm) and maintained under shear for 3 min. The dispersion obtained was left under ultrasound (Vibracell, Sonics&Material) for 3 min. Ethyl acetate was removed by distillation at 70° C. under 350 to 180 mbar vacuum (35 to 18 kPa). The solids content of the dispersion was 39.1 wt. % and the fluorine content of the fluoropolymer therein was 27.5 wt %.
Repellency Evaluation #3: Examples 1 and 4
[0076] Two pieces were cut from the same sample of bovine nubuck and identified as Bovine Nubuck #6 and Bovine Nubuck #7. It should be noted that the sample of bovine nubuck used in Repellency Evaluation #3 was different from both: the sample of bovine nubuck used in Repellency Evaluation #1; and the sample of bovine nubuck used in Repellency Evaluation #2.
[0077] The product made by Example 1 was applied to Bovine Nubuck #6 in accordance with Drum Application Procedure #1 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.33 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0078] The product made by Example 4 was applied to Bovine Nubuck #7 in accordance with Drum Application Procedure #1 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 8 in water, thereby yielding a treatment solution with a fluorine content of 0.33 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0079] Two pieces were cut from the same sample of bovine full grain from wet blue and identified as Bovine Full Grain #3 and Bovine Full Grain #4. It should be noted that the sample of bovine full grain from wet blue used in Repellency Evaluation #3 was different from the sample of bovine full grain from wet blue used in Repellency Evaluation #2.
[0080] The product made by Example 1 was applied to Bovine Full Grain #3 in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0081] The product made by Example 4 was applied to Bovine Full Grain #4 in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 8 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0082] Two pieces were cut from the same sample of lamb from stain and identified as Lamb Stain #1 and Lamb Stain #2.
[0083] The product made by Example 1 was applied to Lamb Stain #1 in accordance with Drum Application Procedure #3 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0084] The product made by Example 4 was applied to Lamb Stain #2 in accordance with Drum Application Procedure #3 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 8 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0085] Two pieces were cut from the same sample of lamb skin from wet blue and identified as Lamb Blue #3 and Lamb Blue #4. It should be noted that the sample of lamb skin from wet blue used in Repellency Evaluation #3 was different from the sample of lamb skin from wet blue used in Repellency Evaluation #2.
[0086] The product made by Example 1 was applied to Lamb Blue #3 in accordance with Drum Application Procedure #4 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.22 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0087] The product made by Example 4 was applied to Lamb Blue #4 in accordance with Drum Application Procedure #4 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 8 in water, thereby yielding a treatment solution with a fluorine content of 0.22 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0088] Two pieces were cut from the same sample of pig suede from wet blue and identified as Pig Suede #3 and Pig Suede #4.
[0089] The product made by Example 1 was applied to Pig Suede #3 in accordance with Drum Application Procedure #5 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0090] The product made by Example 4 was applied to Pig Suede #4 in accordance with Drum Application Procedure #5 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 8 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 9.
[0000]
TABLE 9
Oil Repellency
Water Repellency
Substrate
Example #
Rating
Rating
bovine nubuck
1
5
9
4
5
10
bovine full grain from
1
3
5
wet blue
4
4
8
lamb from stain
1
3
8/9
4
5
10
lamb skin from wet
1
3
5
blue
4
4
8
pig suede from wet
1
4
8
blue
4
5
10
[0091] This Table shows that fluoropolymers of the invention made from different weight ratios of monomers yield roughly the same repellency performance. The weight ratio of fluorinated acrylate monomer to vinyl compound monomer of Example 1 is 50:50 compared to 60:40 in Example 4. As seen in Table 9, higher proportions of fluorinated acrylate monomer yield higher water repellency ratings.
Example 5
[0092] To a double-jacketed 1 liter reactor (reactor vessel) was added water (96.4 g), 1-methoxypropan-2-ol (5.76 g, 6.17×10 −2 mol), and n-dodecyl mercaptan (0.78 g, 3.85×10 −3 mol) with stirring. To a second double jacketed 1 liter reactor (monomer staging vessel) was added vinyl compound monomer (56.5 g, 2.35×10 −1 mol), fluorinated acrylate monomer (99.5 g, 1.48×10 −1 mol), water (165.4 g), propan-2-ol (37.8 g, 6.29×10 −1 mol), disodium tetraborate (0.51 g, 2.53×10 −3 mol), sodium 1,2-bis(tridecyloxycarbonyl)ethanesulphonate (4.07 g, 6.96×10 −3 mol), 1-methoxypropan-2-ol (37.58, 4.17×10 −1 mol) with stirring. Then 25 wt. % of the contents of the monomer staging vessel was loaded into the reactor vessel. After the temperature was stabilized at 85° C., 0.78 g of n-dodecyl mercaptan (3.85×10 −3 mol) was added to the reactor vessel. A solution of potassium persulfate (0.28 g, 1.04×10 −3 mol) in water (17.9 g) was loaded to a 25 mL syringe (initiator vessel). Oxygen was removed from the initiator vessel by 30 minutes of a nitrogen flow. To start the polymerization, a solution of potassium persulfate (0.07 g, 2.59×10 −4 mol) in water (4.48 g) was added into the reactor vessel from the initiator vessel. After minutes, the remaining contents of the monomer staging vessel and the initiator staging vessel were fed over the course of 120 minutes, and then, the temperature was maintained at 85° C. for over 150 minutes. Solvents were removed by a vacuum distillation (reactor vessel pressure: 0.5 bar [50 kPa], reactor vessel temperature from 65° C. to 80° C.). The reactor vessel was cooled down to 30° C. 14.53 g of water was added to the reactor vessel in order to obtain 450.4 g of a product with a solids content of 30.0 wt. % and the fluorine content of the fluoropolymer therein was 27.1 wt. %. The targeted molecular weight of the polymer made in this example was 17,800 grams/mole.
Repellency Evaluation #4: Examples 4 and 5
[0093] Seven pieces were cut from the same sample of bovine full grain from wet blue and identified as Bovine Full Grain #5, Bovine Full Grain #6, Bovine Full Grain #7, Bovine Full Grain #8, Bovine Full Grain #9, Bovine Full Grain #10, and Bovine Full Grain #11. It should be noted that the sample of bovine full grain from wet blue used in Repellency Evaluation #4 was different from both: the sample of bovine full grain from wet blue used in Repellency Evaluation #2; and the sample of bovine full grain from wet blue used in Repellency Evaluation #3.
[0094] The product made by Example 4 was applied to Bovine Full Grain #5 in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 4 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 10.
[0095] The product made by Example 5 was applied to Bovine Full Grain #6 in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 5 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 10 and Table 11.
[0000]
TABLE 10
Wt. % Fluorine
Oil
Water
Incorporated in
Repellency
Repellency
Example #
Fluoropolymer
Rating
Rating
4
27.5
4/5*
10
5
27.1
5
10
*indicates a rating in-between these two numbers
[0096] Table 10 compares fluoropolymer compositions of the invention made by two different processes: Example 4, solution polymerization in organic solvent followed by dispersion in water; and Example 5, emulsion polymerization. Table 10 shows that fluoropolymers compositions of the invention can be made by different processes while still achieving substantially the same properties including incorporation of fluorine, oil repellency, and water repellency.
Example 6
[0097] Example 5 was repeated except that: 1) the amount of dodecyl mercaptan added toe the reactor vessel was lowered to 0.65 g (3.21×10 −3 mol), and 2) the amount of dodecyl mercaptan added to the monomer staging vessel was lowered to 0.65 g (3.21×10 −3 mol). The product made by Example 6 had a solids content of 30.0 wt. % and the fluorine content of the fluoropolymer therein was 27.3 wt. %. The targeted molecular weight of the polymer made in this example was 21,400 grams/mole.
Example 7
[0098] Example 5 was repeated except that: 1) the amount of dodecyl mercaptan added toe the reactor vessel was raised to 0.91 g (4.50×10 −3 mol), and 2) the amount of dodecyl mercaptan added to the monomer staging vessel was raised to 0.91 g (4.50×10 −3 mol). The product made by Example 7 had a solids content of 30.0 wt. % and the fluorine content of the fluoropolymer therein was 27.3 wt. %. The targeted molecular weight of the polymer made in this example was 15,300 grams/mole.
Example 8
[0099] Example 5 was repeated except that: 1) the amount of dodecyl mercaptan added toe the reactor vessel was lowered to 0.06 g (3.21×10 −4 mol), and 2) the amount of dodecyl mercaptan added to the monomer staging vessel was lowered to 0.06 g (3.21×10 −4 mol). The product made by Example 8 had a solids content of 30.0 wt. % and the fluorine content of the fluoropolymer therein was 27.5 wt. %. The targeted molecular weight of the polymer made in this example was 106,500 grams/mole.
Repellency Evaluation #5: Examples 5-8
[0100] The repellency evaluation of Example 5 was conducted in Repellency Evaluation #4.
[0101] The product made by Example 6 was applied to Bovine Full Grain #7 (see Repellency Evaluation #4) in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 6 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 11 and Table 12.
[0102] The product made by Example 7 was applied to Bovine Full Grain #8 (see Repellency Evaluation #4) in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 7 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 11.
[0103] The product made by Example 8 was applied to Bovine Full Grain #9 (see Repellency Evaluation #4) in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Example 8 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 11 and Table 12.
[0000]
TABLE 11
Wt. % Fluorine
Oil
Water
Targeted MW
Incorporated in
Repellency
Repellency
Example #
grams/mole
nDDM (1)
Fluoropolymer
Rating
Rating
5
17,800
8.47 × 10 −3
27.1
5
10
6
21,400
6.42 × 10 −3
27.3
5
10
7
15,300
9.00 × 10 −3
27.3
5
9/10 (2)
8
106,500
6.42 × 10 −4
27.5
4
8
(1) Total moles of n-dodecyl mercaptan added during polymerization
(2) indicates a rating in-between these two numbers
[0104] Table 11 shows that the fluoropolymers of the invention can vary by molecular weight and still yield similar repellency ratings. Table 11 also shows that, for drum application, lower molecular weight polymers (such as Examples 10-13) yield improved repellency ratings over higher molecular weight polymers (such as Example 14).
Comparative Example B
[0105] Example 6 was repeated except that 5.08 g (2.41×10 −2 mol) of N-hydroxymethyl acrylamide (CASRN 924-42-5) was also added to the monomer staging vessel. The targeted molecular weight of the polymer made in this example was 22,200 grams/mole. The product of this example had a solids content of 30.0 wt. % and the fluorocopolymer therein had a fluorine content of 27.3 wt. %.
Comparative Example C
[0106] Comparative Example B repeated except that: 1) the amount of dodecyl mercaptan added toe the reactor vessel was lowered to 0.06 g (2.96×10 −4 mol), and 2) the amount of dodecyl mercaptan added to the monomer staging vessel was lowered to 0.06 g (2.96×10 −4 mol). The targeted molecular weight of the polymer made in this example was 239,300 grams/mole. The product of this example had a solids content of 30.0 wt. % and the fluorocopolymer therein had a fluorine content of 27.0 wt. %.
Repellency Evaluation #6: Examples 6 and 8; Comparative Examples B and C
[0107] The repellency evaluation of Examples 6 and 8 was conducted in Repellency Evaluation #5.
[0108] The product made by Comparative Example B was applied to Bovine Full Grain #10 (see Repellency Evaluation #4) in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Comparative Example B in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 12.
[0109] The product made by Comparative Example C was applied to Bovine Full Grain #11 (see Repellency Evaluation #4) in accordance with Drum Application Procedure #2 wherein the treatment solution for the fluoropolymer introduction step was made by diluting an aliquot from the product of Comparative Example C in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 12.
[0000]
TABLE 12
Wt. %
Fluorine
Incorporated
Oil
Water
Targeted MW
in
Repellency
Repellency
Example #
grams/mole
nDDM*
Fluoropolymer
Rating
Rating
6
21,400
3.21 × 10 −3
27.3
5
10
B
22,200
3.21 × 10 −3
27.3
4
6
8
106,500
6.42 × 10 −4
27.5
4
8
C
239,300
2.96 × 10 −4
27.0
3
6
*Total moles of n-dodecyl mercaptan added during polymerization
[0110] Table 12 demonstrates that the incorporation of a hydrophilic monomer (N-hydroxymethyl acrylamide) detrimentally affects the ability of a fluoropolymer to impart repellency. A first comparison is made of lower molecular weight fluorocopolymers: 1) substrates treated with Example 6, a fluoropolymer without incorporation of N-hydroxymethyl acrylamide; versus 2) substrates treated with Comparative Example B, a fluoropolymer incorporating N-hydroxymethyl acrylamide. A second comparison is made of higher molecular weight fluorocopolymers: 1) substrates treated with Example 8, a fluoropolymer without incorporation of N-hydroxymethyl acrylamide; versus 2) substrates treated with Comparative Example C, a fluoropolymer incorporating N-hydroxymethyl acrylamide. Both first and second comparisons show that, irrespective of molecular weight, substrates treated by the same process had significantly better repellency to oil and water when treated with a fluoropolymer without incorporation of hydrophilic monomer (N-hydroxymethyl acrylamide).
Example 9
[0111] To a double-jacketed 1 liter reactor was added vinyl compound monomer (82.5 g, 0.337 mol), fluorinated acrylate monomer (101.1 g, 0.150 mol), t-butanol (271.0 g, 3.66 mol) with stirring. The temperature was raised to 75° C. Oxygen was removed from the reactor by 30 minutes of a nitrogen flow. Azobisisobutyronitrile (1.34 g, 8.03 mmol) was added to the solution. The temperature was maintained for 20 h under nitrogen. The solids content of the final solution was 39.2 wt. % (theoretical value: 38.6 wt. %). This solution was dried by distillation to remove t-butanol at 70° C. and 350 to 20 mbar vacuum (35 to 2 kPa). Ethyl acetate was added in order to obtain an organic solution with a solids content of 45.1 wt. %.
[0112] To a 100-mL flask was added water (71.6 g), propylene glycol (8.07 g), SULFRAMIN acid B (Alkylbenzene sulfonic acid, mixture of C10-C13 isomers, CASRN 85536-14-7, Akzo Nobel, 0.96 g), and NOURACID CZ80 (castor oil fatty acid, CASRN 61789-44-4, Akzo Nobel, 0.33 g) at room temperature with stirring. The solution of polymer in ethyl acetate was added drop-by-drop to this aqueous solution under high shear (ULTRATURAX T2, IKA, 8000 rpm) and maintained under shear for 3 min. The dispersion obtained was left under ultrasound (Vibracell, Sonics&Material) for 3 min. Ethyl acetate was removed by distillation at 70° C. under 350 to 180 mbar vacuum (35 to 18 kPa). The solids content of the dispersion was 45.0 wt. % and the fluorine content of the fluoropolymer therein was 22.8 wt. %.
Repellency Evaluation #7: Examples 1, 6, and 9; Comparative Example A
[0113] Four pieces were cut from the same sample of lamb skin from wet blue and identified as Lamb Blue #5, Lamb Blue #6, Lamb Blue #7, and Lamb Blue #8.
[0114] The product made by Example 1 was applied to Lamb Blue #5 in accordance with Spray Application Procedure #1 wherein the treatment solution was made by diluting an aliquot from the product of Example 1 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 13.
[0115] The product made by Example 6 was applied to Lamb Blue #6 in accordance with Spray Application Procedure #1 wherein the treatment solution was made by diluting an aliquot from the product of Example 6 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 13.
[0116] The product made by Example 9 was applied to Lamb Blue #7 in accordance with Spray Application Procedure #1 wherein the treatment was made by diluting an aliquot from the product of Example 9 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 13.
[0117] The product made by Comparative Example A was applied to Lamb Blue #8 in accordance with Spray Application Procedure #1 wherein the treatment was made by diluting an aliquot from the product of Example 9 in water, thereby yielding a treatment solution with a fluorine content of 0.17 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 13.
[0000]
TABLE 13
Wt. % Fluorine
Oil
Water
Incorporated in
Repellency
Repellency
Example #
Fluoropolymer
Rating
Rating
1
22.8
4
9
6
27.3
5
9
9
22.8
5
9
A
16.0
0
4
[0118] Table 13 demonstrates that the incorporation of a hydrophilic monomer (acrylic acid) detrimentally affects the ability of a fluoropolymer to impart repellency. Significantly higher oil and water repellency is seen for substrates treated with fluoropolymers that do not incorporate a hydrophilic monomer (Examples 1, 6, and 9) when compared to substrates treated with a fluorocopolymer incorporating a hydrophilic monomer (acrylic acid).
Example 10
[0119] To a double-jacketed 2 liter reactor was added vinyl compound monomer (298.5 g, 1.24 mol), fluorinated acrylate monomer (411.9 g, 0.6 mol), t-butanol (1081.0 g, 12.3 mol) with stirring. The temperature was raised to 75° C. Oxygen was removed from the reactor by 30 minutes of a nitrogen flow. Azobisisobutyronitrile (4.96 g, 29.7 mmol) was added to the solution. The temperature was maintained for 20 h under nitrogen. The solids content of the final solution was 35.7 wt. % (theoretical value: 34.9 wt. %). This solution was dried by distillation to remove t-butanol at 70° C. and 350 to 20 mbar vacuum (35 to 2 kPa). Ethyl acetate was added in order to obtain an organic solution with a solids content of 45.10 wt. %. The fluoropolymer in this example had a fluorine content of 22.8 wt. %.
Example 11
[0120] To a double-jacketed 1 liter reactor was added vinyl compound monomer (32.5 g, 0.136 mol), fluorinated acrylate monomer (40.1 g, 0.059 mol), t-butanol (130.0 g, 1.76 mol), and n-dodecyl mercaptan (0.63 g, 3.1 mmol) with stirring. The temperature was raised to 75° C. Oxygen was removed from the reactor by 30 minutes of a nitrogen flow. Azobisisobutyronitrile (0.52 g, 3.16 mmol) was added to the solution. The temperature was maintained for 20 h under nitrogen. The solids content of the final solution was 36.0 wt. % (theoretical value: 35.9 wt. %). This solution was dried by distillation to remove t-butanol at 70° C. and 350 to 20 mbar vacuum (35 to 2 kPa). Ethyl acetate was added in order to obtain an organic solution with a solids content of 45.05 wt. %. The targeted molecular weight of this example was 21,100 grams/mole The fluoropolymer in this example had a fluorine content of 22.8 wt. %.
Comparative Example D
[0121] To a double-jacketed 1 liter reactor was added vinyl compound monomer (22.6 g, 0.0923 mol), fluorinated acrylate monomer (28.2 g, 0.419 mol), acrylic acid (19.41 g, 0.269 mol), t-butanol (120.0 g, 1.62 mol), and n-dodecyl mercaptan (0.63 g, 3.1 mmol) with stirring. The temperature was raised to 75° C. Oxygen was removed from the reactor by 30 minutes of a nitrogen flow. Azobisisobutyronitrile (0.52 g, 3.11 mmol) was added to the solution. The temperature was maintained for 20 h under nitrogen. The solids content of the final solution was 35.6% (theoretical value: 35.9%). This solution was dried by distillation to remove t-butanol at 70° C. and 350 to 20 mbar vacuum (35 to 2 kPa). Ethyl acetate was added in order to obtain an organic solution with a solids content of 44.9%. The targeted molecular weight of this example was 14,800 grams/mole. The fluoropolymer in this example had a fluorine content of 16.0 wt. %.
Repellency Evaluation #8: Examples 10 and 11; Comparative Example D
[0122] Three pieces were cut from the same sample of lamb skin from wet blue and identified as Lamb Blue #9, Lamb Blue #10, and Lamb Blue #11.
[0123] The product made by Example 10 was applied to Lamb Blue #9 in accordance with Spray Application Procedure #2 wherein the treatment solution was made by diluting an aliquot from the product of Example 10 in isopropyl alcohol thereby yielding a treatment solution with a fluorine content of 0.09 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 14.
[0124] The product made by Example 11 was applied to Lamb Blue #10 in accordance with Spray Application Procedure #2 wherein the treatment solution was made by diluting an aliquot from the product of Example 11 in isopropyl alcohol thereby yielding a treatment solution with a fluorine content of 0.09 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 14.
[0125] The product made by Comparative Example D was applied to Lamb Blue #11 in accordance with Spray Application Procedure #2 wherein the treatment solution was made by diluting an aliquot from the product of Comparative Example D in isopropyl alcohol thereby yielding a treatment solution with a fluorine content of 0.09 wt. %. The resulting treated leather substrate was subjected to water and oil repellency tests, the results of which are shown in Table 14.
[0000]
TABLE 14
Targeted
Wt. % Fluorine
Oil
Water
MW
Incorporated in
Repellency
Repellency
Example #
grams/mole
Fluoropolymer
Rating
Rating
10
*
22.8
7
12
11
21,100
22.8
4
10
D
14,800
16.0
5
5
* No chain transfer agent was used therefore there is no targeted molecular weight but it is assumed to be higher than Example 11 and Comparative Example D.
[0126] Table 14 demonstrates that the incorporation of a hydrophilic monomer (acrylic acid) detrimentally affects the ability of a fluoropolymer to impart repellency. Significantly higher oil and water repellency is seen for substrates treated with fluoropolymers that do not incorporate a hydrophilic monomer (Examples 10 and 11) when compared to substrates treated with a fluorocopolymer incorporating a hydrophilic monomer (acrylic acid). Comparing Example 10 to Example 11 shows that a fluorocopolymer made without a chain transfer agent imparts higher oil and water repellency when sprayed in a homogenous organic medium.
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Various fluoropolymers have been proposed for imparting oil and water repellency to leather. Commonly, these fluoropolymers are amphiphilic; i.e., they are made from at least one monomer which is hydrophobic and at least one monomer which is hydrophilic. The present invention identifies and remedies disadvantages associated with the ability of amphiphilic fluoropolymers to impart oil and water repellency to leather. Contrary to conventional thinking, it has now been discovered that the incorporation of hydrophilic groups in a fluoropolymer undesirably reduces its ability to impart water resistance to leather. Correspondingly, it has also been discovered that a fluoropolymer incorporating fewer or no hydrophilic groups imparts superior oil and water repellency to leather when compared to fluoropolymers incorporating more hydrophilic groups. Therefore, this invention provides fluoropolymers which incorporate reduced levels of hydrophilic groups.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No. 09/356,640,entitled PLUMBING SLIDER BRACKET AND DOUBLE RATCHET ARM PIPE CLAMP ASSEMBLY, which was filed on Jul. 19, 1999 and application Ser. No. 08/965,302, entitled. PLUMBING SLIDER BRACKET AND DOUBLE RATCHET ARM PIPE CLAMP ASSEMBLY, which was filed on Nov. 6, 1997 now U.S. Pat. No. 6,126,122.
FIELD OF THE INVENTION
The present invention relates to a slider bracket and clamp system for plumbing support, and, more particularly, to such a slider bracket in which a first and a second U-shaped bracket section are shaped to allow the first bracket section to be telescopically received in the second bracket section such that it can slide back and forth within the second bracket section to collectively make a single, length adjustable, slider bracket. One or more flexible tabs are provided on the exposed end of each of the first and second bracket sections. A special ratchet operated pipe clamp assembly has a base which is shaped to be received and retained in either the first or the second bracket section and the clamp assembly is designed such that, when a pipe is secured in place within the clamp assembly, a resilient insert within the clamp base is forced into contact with a bottom wall of the slider bracket to anchor the clamp, and the secured pipe, stationary with respect to the slider bracket.
BACKGROUND OF THE INVENTION
Manufacturers of plumbing supplies are constantly seeking to improve the convenience and efficiency of their products for the tradesman. Brackets and plumbing supports are increasingly designed for ease of installation and for universal application. An early example of an adjustable bracket is illustrated and described in U.S. Pat. No. 3,163,386, entitled Adjustable Duct Hanger. In this patent, an “outer” and an “inner rectilinear member” are engaged with each other such that they can be telescopically extended and retracted relative to each other. A prong is attached to the terminal end of each of the telescoping members such that the bracket can be telescopically extended to the full width of an adjacent pair of joists where a duct is to be supported and the prongs driven into the sides of the joists to hold the bracket, and the duct, in place. While the ′386 patent discusses duct support, it can also be used for plumbing support as well.
An example of a plumbing bracket which is designed for easy installation in a variety of different environments is found in U.S. Pat. No. 5,060,892 to Glen Dougherty, entitled Plumbing Hanger Bracket Assembly. The Dougherty bracket is a slider bracket in which a first bracket section is received within a second, slightly larger bracket section such that the first bracket section can be telescopically extended and retracted relative to the second section to adjust the overall length of the bracket. The bracket has a plurality of spaced openings in the rear of the bracket and a plastic pipe support sleeve is received within the combined bracket sections such that, when the sleeve is aligned with one of the openings in the bracket a plumbing pipe can extend straight through the sleeve and bracket to be supported thereby. The Dougherty bracket is designed primarily for installation of hot and cold water supply pipes behind plumbing installations such as tub and shower or lavatory supplies. However, brackets such as Dougherty's are very limited in their application. They are capable only of supporting pipes extending from front to back through the bracket, and the support sleeves do not lock into place, but are slidable within the bracket, i.e. they are held in position only by the pipes themselves. Placement of supported pipes is also limited by the placement of the bracket openings.
It is clear that a need exists for a slider bracket which is length adjustable to allow installation in a variety of plumbing support applications between wall studs, floor and ceiling joists, and other building members and to allow for installation either inside or outside of the building component pairs. Such a slider bracket should allow pipes to be supported in any orientation relative to the opening in which it is positioned and should accommodate specialized pipe clamp assemblies which can be secured into a stable position along the length of the bracket.
SUMMARY OF THE INVENTION
The present invention is directed to a plumbing slider bracket and clamp assembly for securing plumbing pipes or other conduit in fixed positions within spaces defined by adjacent wall studs, joists and other building or bracketing members. The slider bracket includes inner and outer bracket sections which are U-shaped in cross section, each of which has opposing depending extensions extending into the U shaped channel. The inner bracket section is slightly smaller in dimension that the outer bracket section which allows the inner bracket section to be telescopically received within the outer bracket section such that it is slidable back and forth within the outer bracket section to collectively make a single, length adjustable slider bracket. At least one respective flexible tab is provided on the distal ends of each of the inner and outer bracket sections with the tabs extending in opposing directions and being foldable between an extended position which allows the bracket to be installed on the outside of a pair of stud or joists, i.e. the tabs can be attached to the outer stud surface, or bent inward at a 90 degree angle relative to the bracket which allows the bracket to be installed within the stud spacing in any desired orientation, i.e. the tabs are attached to the inward facing stud or joist surface.
Specialized double ratchet arm pipe clamp assemblies for use in the slider bracket are of a three part construction with a base member, a resilient insert and a keeper block engageable with the resilient insert within the base member to clamp a pipe therebetween. Each base member has a rectangular base frame with two pair of opposing gripping steps formed in it at different levels such that it can be received and retained in either the first or the second, or both slider bracket sections. Each base member has a pair of elongate ratchet arms extending outward or upward from the base frame. Each ratchet arm has a plurality of ratchet teeth formed along an outside surface. Each keeper block has a pair of ratchet arm receiving apertures extending through opposite ends thereof, with each arm receiving aperture having an anvil surface. A respective pawl member is positioned within each aperture with each pawl member being resiliently urged toward the anvil surface of the respective aperture. The keeper block is received on the clamp base member with each ratchet arm extending through a respective arm receiving aperture. The ratchet teeth on each ratchet arm engage the respective pawl member in the aperture through which the arm extends. Each pawl member includes an extension which protrudes outward from the keeper block which, if pushed outward, disengages the pawl member from the ratchet teeth to thereby release the ratchet arm.
The resilient insert is designed to accomplish two functions, i.e. it forms a resilient upper surface which combines with the keeper block to clamp a pipe in place and, as the keeper block is cinched down against the pipe, the clamped pipe exerts a force against the resilient upper surface, which forces it downward to engage the bottom wall of the slider bracket, thus firmly anchoring the clamp assembly in place within the slider bracket.
An alternative embodiment of the pipe clamp assembly is similar to the double ratchet arm pipe clamp assembly except that it includes only a single ratchet arm which is longer and more flexible than those of the double ratchet arm assembly. The flexible ratchet arm is adapted to be looped over a pipe cradled against the upper surface of the resilient insert and pulled downwardly into a ratchet arm receiving aperture connected to the clamp base frame. The flexible ratchet arm is cinched down against the pipe, simultaneously anchoring the pipe in place relative to the clamp assembly and forcing the resilient insert downward to anchor the clamp assembly in place within the slider bracket.
OBJECTS AND ADVANTAGES OF THE INVENTION
The principal objects of the present invention include: providing a plumbing slider bracket and double ratchet arm pipe clamp assembly; providing such a plumbing slider bracket and double ratchet arm pipe clamp assembly which can be telescopically extended to fit between studs, joists, or other building members spaced at varying widths; providing such a plumbing slider bracket and double ratchet arm pipe clamp assembly in which the slider includes a first bracket section telescopically received within a second bracket section; providing such a plumbing slider bracket and double ratchet arm pipe clamp assembly in which a number of the double ratchet arm clamp assemblies can be securely fitted into a single slider bracket, either in a portion of the slider bracket where the first and second bracket sections overlap, or in a portion where they do not overlap; providing such a plumbing slider bracket and double ratchet arm pipe clamp assembly including an insert extending through a base member of the pipe clamp assembly, an upper surface of which engages a pipe secured therein and a lower surface which is driven into a bottom wall of the slider bracket to prevent sliding of the base member relative to the slider bracket; providing such a plumbing slider bracket and double ratchet arm pipe clamp assembly in which each double ratchet arm pipe clamp assembly includes a resilient insert which provides a cushioned clamping surface for securing a pipe in position within the clamp assembly and which also pushes downward against the bottom wall of the slider bracket in response to clamping forces applied to the pipe which causes the pipe clamp assembly to be anchored in position within the slider bracket; providing such a plumbing slider bracket and double ratchet arm pipe clamp assembly which is universally useful to hold plumbing pipes in place within a structure regardless of their configuration, spacing and routing; and providing such a plumbing slider bracket and double ratchet arm pipe clamp assembly which is effective yet economical and which is particularly well adapted for its intended purpose.
Other objects and advantages of this invention will become apparent from the following description taken in conjunction with the accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of this invention.
The drawings constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a first embodiment of a plumbing slider bracket secured in position between a pair of wall studs with three double ratchet arm pipe clamp assemblies respectively securing three pipes in position, as for a tub and shower stub out.
FIG. 2 is a greatly enlarged, fragmentary, cross sectional view of the plumbing slider bracket and double ratchet arm pipe clamp assembly of FIG. 1, taken along line 3 — 3 of FIG. 1, but with no pipe clamped in position within a clamp assembly, and thus with the resilient insert undistorted.
FIG. 3 is an enlarged, cross sectional view of the plumbing slider bracket and double ratchet arm pipe clamp assembly of FIG. 1, taken along line 3 — 3 of FIG. 1, but with a pipe secured in a pipe clamp assembly and the resilient insert distorted thereby into contact with the bottom wall of the slider bracket.
FIG. 4 is a greatly enlarged, fragmentary, cross sectional view of the plumbing slider bracket and double ratchet arm pipe clamp assembly of FIG. 1, taken along line 4 — 4 of FIG. 1, showing a pipe clamp assembly being retained by just the outer slider section.
FIG. 5 is a greatly enlarged, fragmentary, cross sectional view of the plumbing slider bracket and double ratchet arm pipe clamp assembly of FIG. 1, taken along line 5 — 5 of FIG. 1, showing a pipe clamp assembly being retained by just the inner slider section.
FIG. 6 is an exploded view of one of the inventive double ratchet arm pipe clamp assemblies designed for use with either the slider bracket of FIGS. 7 and 8 or the slider bracket of FIG. 9 .
FIG. 7 is an exploded view of the first embodiment of the inventive slider bracket.
FIG. 8 an assembled view of the slider bracket of FIG. 7 .
FIG. 9 is an exploded view of a second embodiment of the inventive slider bracket.
FIG. 10 is a greatly enlarged, fragmentary end view of the second embodiment of the inventive slider bracket and a double ratchet arm pipe clamp assembly.
FIG. 11 is a greatly enlarged, fragmentary end view of the second embodiment of the inventive slider bracket and a double ratchet arm pipe clamp assembly which shows the pipe clamp assembly being retained by just the outer slider section.
FIG. 12 is a greatly enlarged, fragmentary end view of the second embodiment of the inventive slider bracket and a double ratchet arm pipe clamp assembly which shows the pipe clamp assembly being retained by just the inner slider section.
FIG. 13 is a partial, exploded, perspective view of a flexible ratchet arm pipe clamp assembly designed for use with either the slider bracket of FIGS. 7 and 8 or the slider bracket of FIG. 9 .
FIG. 14 is a side view of the flexible ratchet arm pipe clamp assembly of FIG. 13 .
FIG. 15 is an end view of the flexible ratchet arm pipe clamp assembly of FIG. 13 installed in the slider bracket of FIG. 12 .
DETAILED DESCRIPTION OF THE INVENTION
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure.
First Embodiment of the Slider Bracket
Referring to FIG. 1, an inventive plumbing slider bracket and pipe clamp assembly including a plumbing slider bracket 1 and three double ratchet arm pipe clamp assemblies 2 is illustrated as being installed between two wall studs 3 . The slider bracket 1 (FIGS. 7 and 8) includes an inner bracket section 4 and an outer bracket section 5 which are each substantially U-shaped in cross section with the inner bracket section 4 being slightly smaller in dimension that the outer bracket section 5 , which allows the inner bracket section 4 to be telescopically received within the outer bracket section 5 .
Referring to FIGS. 1 and 3, the inner bracket section 4 has a proximate end 4 a, a distal end 4 b, and a bottom wall 6 connecting a front wall 7 to a rear wall 8 . The front and rear walls 7 and 8 each have a respective wall extension or flange 9 which extends inwardly from the respective front wall 7 or rear wall 8 and downwardly toward the bottom wall 6 . The wall extensions 9 are bent back on the respective front wall 7 or rear wall 8 at approximately 180 degrees as shown in FIG. 5, and include a depending ridge 10 which extends along the length of the inner bracket section 4 and extends inward from the wall extensions 9 into the channel formed by the front and rear walls 7 and 8 and the bottom wall 6 . The ridges 10 thus present opposing gripping surfaces within the inner bracket section 4 for retention of the pipe clamp assemblies 2 or 202 , as will be fully explained below.
Similarly, the outer bracket section 5 also has a proximate end 5 a, a distal end 5 b, and a bottom wall 11 connecting a front wall 12 to a rear wall 13 . Each of the front and rear walls 12 and 13 has a respective wall extension or flange 14 . The wall extensions 14 are bent back from the respective front or rear wall 12 or 13 at approximately 180 degrees as shown in FIG. 4, and include a depending ridge 15 which extends along the length of the outer bracket section 5 and extends inward from the wall extensions 14 into the channel formed by the front and rear walls 12 and 13 and the bottom wall 11 . The ridges 15 thus also present opposing gripping surfaces within the outer bracket section 5 for retention of the pipe clamp assemblies 2 , as explained below. A preferred angle for both the ridges 10 and 15 is approximately 20 degrees from vertical.
The slider bracket 1 also includes at least one, and preferably two flexible tab 16 which are attached to and extend outward from the distal end 4 b of the inner bracket section 4 and at least one and preferably two matching, flexible tabs 17 , attached to and extending outward from the distal end 5 b of the outer bracket section 5 . The tabs 16 and 17 may, respectively, extend outward from the rear walls 8 and 13 , the bottom walls 6 and 11 , the front walls 7 and 12 , or any combination of the above. The tabs 16 and 17 preferably include a number of pre-drilled holes 18 which accommodate fasteners, such as screws 21 (FIGS. 7 and 8 ). The screws 21 can be factory “pre-loaded” into the holes 18 in the tabs 16 and 17 for ease of use by plumbers in the field. The tabs 16 and 17 are flexible enough that they can be easily bent to an angle of at least 90 degrees to allow the slider bracket 1 to be attached to the inward facing surface of two adjacent building members, such as within a wall between the studs 3 , as shown in FIG. 1 . Alternatively, the tabs 16 and 17 can be left in the extended position of FIGS. 7 and 8 to allow the slider bracket 1 to be installed on the outside surface of a single or an adjacent pair of studs, joists, etc.
Double Ratchet Arm Pipe Clamp Assembly
The first embodiment of the pipe clamp assembly for use with the slider bracket 1 is a double ratchet arm pipe clamp assembly 2 of a three part construction, as shown in FIG. 6 . Each clamp assembly 2 includes a base member 22 , a resilient insert 23 , and a keeper block or clamping member 24 engageable with the resilient insert 23 and with the clamp base member 22 to clamp a pipe 25 therebetween. Each base member 22 has a substantially rectangular base frame 26 with two pairs of depending legs 31 , each with a lower gripping step 32 and an upper gripping step 33 formed therein.
Each clamp assembly 2 can be snapped into position within the slider bracket 1 or, alternatively, slid into the bracket from the open ends of the channels formed in the inner bracket section 4 or the outer bracket section 5 . When the clamp assemblies 2 are placed into the slider bracket 1 (as shown in FIG. 2 ), the opposing lower gripping steps 32 engage the ridges 10 of the inner bracket section 4 while the opposing upper gripping steps 33 engage the ridges 15 of the outer bracket section 5 . This insures that the clamp assemblies 2 will be securely held in place within the slider bracket 1 at portions of the slider bracket 1 where the inner bracket section 4 overlaps the outer bracket section 5 . In addition, the clamp assemblies 2 will be securely held in place within the slider bracket 1 at portions where the inner bracket section 4 is telescoped away from the outer bracket section 5 or by the lower gripping steps 32 , as shown in FIGS. 5 and 12, and at portions where the outer bracket section 5 is telescoped away from the first bracket section 4 by the upper gripping steps 33 , as shown in FIG. 4 .
Each of the lower gripping steps 32 has a top surface 34 and each of the upper gripping steps 33 has a top surface 35 , with the surfaces 34 and 35 each preferably extending outward and downward slightly at an angle of approximately 5 degrees from horizontal. The upper gripping step 33 can extend lengthwise along the entire base frame 26 to provide a more effective gripping surface. Experimentation has shown that the approximate 5 degree angles of the gripping step top surfaces 34 and 35 and the approximate 20 degree angle of the ridges 10 and 15 allow the base frame 26 to be easily snapped into position within the slider bracket 1 while making it very difficult to remove the clamp assembly 2 by pulling outward on it or twisting it.
Each pipe clamp assembly base member 22 is preferably made of molded plastic and also includes a pair of elongated ratchet arms 41 and 42 extending outward from the base frame 26 . Each ratchet arm 41 and 42 has a plurality of ratchet teeth 43 formed along an outside surface thereof. The clamp base frame 26 includes a central aperture 44 and a pair of upstanding walls 45 positioned on respective sides of an upper portion 46 of the central aperture 44 which walls 45 each include a notch 51 for cradling a pipe, such as the pipes 25 of FIGS. 1 and 3. The notch 51 may be substantially V-shaped, U-shaped, or semicircular in configuration. The central aperture 44 also includes a lower portion 47 which may be smaller or larger in cross sectional area than the upper portion 46 .
Each clamp keeper block 24 includes a keeper block plate 53 with a pair of arm receiving apertures 54 formed therethrough near respective opposite ends and sized to receive respective ones of the ratchet arms 41 and 42 , as shown in FIGS. 1, 3 and 6 . Each of the arm receiving apertures 54 has an inner anvil surface 55 and a respective pawl member 61 is positioned within and hingedly attached to an outside wall of the keeper block defining each aperture 54 with each pawl member 61 including a series of teeth 62 spaced to engage the corresponding ratchet teeth 43 on the respective ratchet arm 41 or 42 extending through the aperture 54 . Each pawl member 61 is molded in a manner such that it is resiliently urged toward the anvil surface 55 of the respective aperture 54 so that the ratchet arm teeth 43 are captured by the teeth 62 on the pawl member 61 . Each pawl member 61 includes an extension 64 which protrudes outward from the keeper block plate 53 . The extensions 64 , when pushed outward, disengage the pawl member teeth 62 from the ratchet teeth 43 to thereby release the ratchet arms 41 and 42 .
The keeper block 24 also includes a pair of keeper block walls 65 positioned along respective sides of the keeper block plate 53 with each keeper block wall 65 also including a notch 66 . As with the notches 51 of the base member 22 , the notches 66 may be substantially V-shaped, U-shaped, or semicircular in configuration. When the keeper block 24 is ratcheted downward along the ratchet arms 41 and 42 , the notches 66 on the keeper block 24 are positioned in opposition to the notches 51 on the base member 22 to cradle the pipe 25 therebetween.
The resilient insert 23 is preferably made of a flexible material which is compatible with all types of plastic used in plumbing applications, including CPVC (chlorinated polyvinyl chloride). Dow Affinity (TM) has proven to be a particularly acceptable material. The resilient insert 23 includes a base portion 71 with a first footprint which allows it to be received within the lower portion 47 of the base member central aperture 44 , and an elongate upper portion 72 extending upward from the base portion 71 which has a second footprint which allows it to be received within the upper portion 46 of the base member central aperture 44 .
The upper portion 72 of the resilient insert 23 is also shaped as a notch 73 with a shape that matches, but extends slightly above the notches 51 of the base member 22 . The notch 73 of the resilient insert 23 forms a resilient receiving surface which receives a pipe 25 , and is forced downward within the base member central aperture 44 as the keeper block 24 is ratcheted downward on the base member ratchet arms 41 and 42 . This downward movement of the resilient insert 23 forces a bottom surface 74 of the base portion 72 to come into contact with the bottom wall 6 of the inner bracket section 4 and to spread outward along that bottom wall 6 . Also, as shown in FIG. 4, in portions of the slider bracket 1 where the outer bracket section 5 is telescoped beyond that of the first bracket section 4 , the bottom surface 74 will be forced downward into contact with the bottom wall 11 of the outer bracket section 5 . This causes the clamp assemblies 2 to be anchored in a set position along the slider bracket 1 since the distorted base portion 71 forces the clamp upward so that the gripping steps 32 and 33 into contact with the respective ridges 10 and 15 , thus forming a spring action which wedges the base frames 26 into place.
Second Embodiment of the Slider Bracket
An alternative version of the slider bracket 101 , adapted for use with clamp assemblies 2 , is shown in FIGS. 9-12. The slider bracket 101 includes an inner bracket section 104 and an outer bracket section 105 which are each substantially U-shaped in cross section with the inner bracket section 104 being slightly smaller in dimension that the outer bracket section 105 , which allows the inner bracket section 104 to be telescopically received within the outer bracket section 105 .
Referring to FIGS. 9 and 12, the inner bracket section 104 has a proximate end 104 a, a distal end 104 b, and a bottom wall 106 connecting a front wall 107 to a rear wall 108 . The front and rear walls 107 and 108 each have a respective wall extension or flange 109 which extend inwardly from the respective front wall 107 or rear wall 108 and downwardly toward the bottom wall 106 . The wall extensions 109 of the inner bracket section 104 are angled inwardly from the respective front wall 107 or rear wall 108 and downwardly toward the bottom wall 106 at an angle of approximately 15 degrees. The slider bracket 101 generally functions in the same manner as slider bracket 1 , with the lower edges of the wall extensions 109 forming the gripping surfaces for retaining the pipe clamp assemblies 2 . No ridges, such as the ridges 10 of the slider bracket 1 , are required to perform this function in slider bracket 101 .
The outer bracket section 105 , as best seen in FIGS. 9 and 11, has a proximate end 105 a, a distal end 105 b, and a bottom wall 111 connecting a front wall 112 to a rear wall 113 . Each of the front and rear walls 112 and 113 has a respective wall extension or flange 114 . The wall extensions 114 of the outer bracket section 105 are angled inwardly from the respective front wall 112 or rear wall 113 and downwardly toward the bottom wall 111 at an angle of approximately 30 degrees with the lower edge of the wall extension 114 performing the gripping function of the ridges 15 of the slider bracket 1 .
As with the slider bracket 1 , the slider bracket 101 includes at least one, and preferably two, flexible tabs 116 which are attached to and extend outward from the distal end 104 b of the inner bracket section 104 and at least one, and preferably two, matching, flexible tabs 117 , attached to and extending outward from the distal end 105 b of the outer bracket section 105 . The flexible tabs 116 and 117 are structurally and functionally identical to the flexible tabs 16 and 17 of the slider bracket 1 described above.
When the clamp assemblies 2 are placed into the slider bracket 101 (as shown in FIG. 10 ), the opposing lower gripping steps 32 engage the lower edges of the wall extensions 109 of the inner bracket section 104 while the opposing upper gripping steps 33 engage the lower edges of the wall extensions 114 of the outer bracket section 105 . This insures that the clamp assemblies 2 will be securely held in place within the slider bracket 101 at portions of the slider bracket 101 where the inner bracket section 104 overlaps the outer bracket section 105 . In addition, the clamp assemblies 2 will be securely held in place within the slider bracket 101 at portions where the inner bracket section 104 is telescoped away from the outer bracket section 105 by the lower gripping steps 32 , as shown in FIG. 12, and at portions where the outer bracket section 105 is telescoped away from the first bracket section 104 by the upper gripping steps 33 , as shown in FIG. 11 .
Similar to the slider bracket 1 , the 30 degree angle of the wall extensions 114 and the 15 degree angle of the extensions 109 combine with the approximate 5 degree angle of the gripping step top surfaces 34 and 35 to allow the base frame 26 to be easily snapped into position within the slider bracket 101 while making it very difficult to remove the clamp assembly 2 .
Flexible Ratchet Arm Pipe Clamp Assembly
An alternative embodiment of the pipe clamp assembly is a flexible ratchet arm pipe clamp 202 as shown in FIGS. 13-15. Each clamp assembly 202 includes a base member or clamp base 222 with a base frame 226 which is similar in construction to the base frame 26 of the double ratchet arm pipe clamp assembly 2 described above. The base frame 226 accepts a resilient insert 223 which is generally identical to the insert 23 of the double ratchet arm clamp assembly 2 . Unlike the double ratchet arm pipe clamp assembly 2 , however, the flexible ratchet arm pipe clamp assembly 202 has only a single elongate flexible ratchet arm or ratchet strap 241 extending outwardly from the base frame 226 of the respective base member 222 . The flexible ratchet arm 241 includes a plurality of ratchet teeth or ratchet members 243 formed along an outside surface thereof.
On the side of the base frame 226 opposite the flexible ratchet arm 241 , the clamp assembly 202 includes an extension arm 275 having a head or ratchet arm receiving block or member 277 with a ratchet arm receiving aperture 279 formed therethrough and sized to receive the flexible ratchet arm 241 . The arm receiving aperture 279 is angled downwardly and away from the flexible ratchet arm 241 . The flexible ratchet arm 241 is longer and more pliable than the ratchet arms 41 and 42 of the clamp assembly 2 so as to be capable of being looped over a pipe 25 cradled in the notch 273 of the resilient insert 223 and pulled downwardly to be received by the ratchet arm receiving aperture 279 .
An inner anvil surface 281 is formed within the ratchet arm receiving block 277 along the ratchet arm receiving aperture 279 . A pawl member 283 is hingedly attached to an outside wall of the ratchet arm receiving block 277 and extends into the ratchet arm receiving aperture 279 . The pawl member 283 including a series of teeth 285 spaced to engage the corresponding ratchet teeth 243 on the flexible ratchet arm 241 extending through the aperture 279 . The pawl member 283 is molded in a manner such that it is resiliently urged toward the anvil surface 281 of the aperture 279 so that the ratchet arm teeth 243 are captured by the teeth 285 on the pawl member 283 . The pawl member 283 includes an extension 287 which protrudes outward from the head 277 of the extension arm 275 . The extension 287 , when pushed outward, disengages the pawl member teeth 285 from the ratchet teeth 243 to thereby release the flexible ratchet arm 241 .
As the flexible ratchet arm 241 is pulled through the ratchet arm receiving aperture 279 around a pipe 25 cradled in the notch 273 of the resilient insert 223 , the pipe 25 is secured relative to the clamp assembly 202 and the resilient insert 223 is simultaneously forced downward within the base member central aperture 244 . This downward motion of the resilient insert 223 forces the bottom surface 274 of the base portion 271 to come into contact with the respective bottom wall 6 or 11 of the slider bracket 1 , or bottom wall 106 or 111 of the slider bracket 101 , causing the clamp assembly 202 to be anchored in a set position along the slider bracket 1 or 101 .
Conclusion
While the plumbing slider brackets 1 and 101 and ratchet arm pipe clamp assemblies 2 and 202 have been described and illustrated for use with plumbing pipes, they can be equally useful with other conduits including electrical or communications cables, fiber optic bundles, wire bundles, or any other elongate structure to be routed through a building structure, therefore, the terms “pipe” and “plumbing” are intended for illustrative purposes only and are not intended to be limiting. Particular details such as the generally rectangular cross sectional shape of the inner and outer bracket sections 4 and 5 , the number and placement of the gripping steps 32 and 33 , etc. are meant to be exemplary only, and can be varied considerably and still accomplish the intended results.
It is to be understood that slider brackets 1 and 101 are fully interchangeable, as are the pipe clamp assemblies 2 and 202 . Either of the clamp assemblies 2 or 202 may be used with either of the brackets 1 or 101 . It is also to be understood that other ratchet assemblies could be utilized for drawing down and holding a clamping member. For example, it is foreseen that the ratchet assembly could be constructed as a cable tie such as one comprising a strand of balls which can be threaded through a conical ratchet receiver with an inlet approximately the same size as the balls and an outlet formed from resilient quarter sections of the cone and being smaller in diameter than the balls. It is also to be understood that other mechanisms currently known in the art or later developed for drawing down the clamping member could be used, including but not limited to a hose clamp assembly and other threaded mechanisms or with straps drawn through clasps or the like. It is thus to be understood that while certain forms of the present invention have been illustrated and described herein, it is not to be limited to the specific forms or arrangement of parts described and shown.
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A plumbing slider bracket and ratchet arm conduit clamp includes a slider bracket with an inner bracket section which is telescopically received within an outer bracket section such that it is slidable back and forth within the outer bracket section to make an extendable slider bracket. Flexible tabs extending from either end of the slider bracket allow attachment of the bracket to an outer stud surface, or within the stud spacing in any desired orientation. Each ratchet arm conduit clamp is received by the slider bracket and is movable along the length of the slider bracket until a conduit is clamped therein. The clamping action both secures the conduit in place within the clamp, and also forces a resilient insert downward against the bottom wall of the slider bracket to anchor the clamp in position within the slider bracket.
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This application is a continuation-in-part of 09/186,989, filed Nov. 5, 1998, now U.S. Pat. No. 6,096,327.
FIELD OF THE INVENTION
The present invention relates to cosmetic compositions containing human serine protease inhibitors. More particularly, there is provided cosmetic compositions containing anti-chymase, anti-tryptase and/or anti-elastase protease inhibitors which improves or revitalizes atmosphere damaged skin including chapped lips, wind burn, sun burn and wrinkles resulting therefrom, as well as natural skin eruptions.
BACKGROUND OF THE INVENTION
Alpha 2-macroglobulin is a glycoprotein containing 8-11% carbohydrate which can be isolated from plasma by gel filtration chromatography.
Alpha 1-proteinase inhibitor (alpha 1-antitrypsin) is a glycoprotein having a molecular weight of 53,000 determined by sedimentation equilibrium centrifugation. The glycoprotein consists of a single polypeptide chain to which several oligosaccharide units are covalently bonded. Human alpha-1 proteinase inhibitor has a role in controlling tissue destruction by endogenous serine proteinases. A genetic deficiency of alpha-1 proteinase inhibitor, which accounts for 90% of the trypsin inhibitory capacity in blood plasma, has been shown to be associated with the premature development of pulmonary emphysema. The degradation of elastin associated with emphysema probably results from a local imbalance of elastolytic enzymes and the naturally occurring tissue and plasma proteinase inhibitors. Alpha-1 proteinase inhibitor inhibits human pancreatic and leukocyte elastases. See Pannell et al, Biochemistry. 13, 5339 (1974); Johnson et al, Biochem, Biophys. Res. Commun., 72 33 (1976); Del Mar et al, Biochem. Biophys. Res. Commun., and Heimburger et al, Proc. Int. Res. Conf. Proteinase Inhibitors. 1st, 1-21 (1970).
SUMMARY OF THE INVENTION
The present invention provides a topical cosmetic composition for improving or revitalizing the texture of skin or as a prophylactic against skin irritations or degradations resulting from exposure to the sun. The composition is especially useful for treating skin damaged by the atmosphere such as sun damaged or wrinkled skin, chapped lips or skin on face and hands, or to prevent skin eruptions.
The serine protease inhibitors which can be used in the present invention include natural or recombinant alpha 1-antitrypsin, secretory leucocyte protease inhibitor (SLPI), and alpha 2-macroglobulin. The most preferred is alpha 1-antitrypsin used alone or in combination.
The wound healing properties of alpha 1-antitrypsin are helpful in cosmetic preparations which are intended to cover blemishes or skin eruption.
The compositions of the invention contain at least about 0.5 percent of the protease inhibitors. The amount of protease inhibitor which generally can be used is about one percent by weight, preferably, about 1 to 10% by weight of composition. Greater amounts can be utilized but are not required to achieve the desired results.
The compositions of the invention can be used in the form of a lotion, creme, gel or solution, depending on the use or treatment contemplated. The extract can be formulated into cosmetic compositions such as lipsticks, hand cremes, after sun compositions, and the like.
The protease inhibitors can be used alone or with other skin treatment compounds such as aloe vera.
It is a general object of the invention to provide a cosmetic composition which contains an effective amount of the protease inhibitor to improve the quality of the skin.
It is another object to provide a cosmetic composition for treating sensitive skins.
It is yet another object to provide a topical composition which helps revitalize environmentally damaged skin.
It is a still further object of the invention to provide a method for improving damaged skin as a result of ultra-violet radiation.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides an improvement in cosmetic compositions by providing safe and natural chymase, tryptase and/or elastase inhibitors which are non-irritating to human skin. The anti-viral characteristic of alpha 1-antitrypsin and SLPI are useful in compositions which can transmit viral infections from one user to another exposed to viral infection.
The favorable cosmetic activity of the protease inhibitors is believed to be the results of the chymase, tryptase and elastase inhibition by the protease inhibitors before or during inflammation. Also, the control of the elastase permits the laying down of new tissue without degradation resulting from the presence of the combination of excess elastase and Cathepsin G. After a solar peel or removal of the upper dermal layer mechanically or naturally, the new tissue layer which is layed down is more resilient and thereby reduces the wrinkles unless scarring or degradation occurs due to excess elastase or cathepsin G. In aging skin, the protease inhibitor appears to revitalize as well as soften the existing skin. The compositions with the protease inhibitor have a prophylactic effect and reduce the incidence of skin eruptions or inflammations as a result of the action against serine proteases or mast cell involvement.
The compositions according to the invention may be presented in all forms normally used for topical application, in particular in the form of aqueous, aqueous-alcoholic or, oily solutions, or dispersions of the lotion or serum type, or anhydrous or lipophilic gels, or emulsions of liquid or semi-solid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase (O/VV) or vice versa (VV/O), or of suspensions or emulsions of soft, semi-solid consistency of the cream or gel type, or alternatively of microemulsions, of microcapsules, of microparticles or of vesicular dispersions to the ionic and/or nonionic type. These compositions are prepared according to standard methods.
The amounts of the different constituents of the compositions according to the invention are those traditionally used in the cosmetic field.
These compositions constitute, in particular, cleansing, protective, treatment or skin care creams for the face, hands, feet, major anatomical folds or the body (for example day creams, night creams, make-up removal creams, foundation creams, sun-protection creams), fluid foundations, make-up removal milks, protective or skin care body milks, after-sun milks, skin care lotions, gels or foams, such as cleansing or disinfecting lotions, bath compositions, deodorant compositions, aftershave gels or lotions, compositions for treating certain skin disorders such as those mentioned above.
The sun can produce a series of lesions on the skin which can be precancerous (e.g. seborrheic, keratoses or actinic keratoses).
The compositions according to the invention may also consist of solid preparations constituting cleansing bars or soaps.
The compositions may also be packaged in the form of an aerosol composition containing a propellent agent under pressure.
When the composition of the invention is an emulsion, the proportion of the fatty phase can range from 5% to 80% by weight, and preferably from 5% to 50% by weight, relative to the total weight of the composition. The oils, emulsifiers and coemulisifiers used in the composition in emulsion form are chosen from those traditionally used in the cosmetics. The emulsifier and the coemulsifier are present in the composition in a proportion ranging from 0.3% to 30% by weight, and preferably 0.5 to 30% or, better still, from 0.5 to 20%, by weight relative to the total weight of the composition. The emulsion can, in addition, contain lipid vesicles.
When the compositions of the invention is an oily gel or solution, the fatty phase can represent more than 90% of the total weight of the composition.
In a known manner, the composition of the invention may also contain adjuvants which are customary in the cosmetics, such as hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preservatives, antioxidants, solvents, perfumes, fillers, screening agents, bactericides, odor absorbers and coloring matter. The amounts of these different adjuvants are those traditionally used in the cosmetic, or dermatological field, and are, for example, from 0.01% to 10% of the total weight of the composition. Those adjuvants, depending on their nature, may be introduced into the fatty phase, into the aqueous phase and/or into lipid spherules.
As oils which can be used in the invention, mineral oils (liquid paraffin), vegetable oils (liquid fraction of shea butter, sunflower oil), animal oils (perhydrosquatene), synthetic oils (Purcellin oil), silicone oils (cyclomethicone) and fluorinated oils (perfluoro polyethers) may be mentioned.
Fatty alcohols, fatty acids (stearic acid) and waxes (paraffin, carnauba, beeswax) may also be used as fatty substances.
As emulsifiers which can be used in the invention, glycerol stearate, polysorbate 60 and the PEG-6/PEG-32/glycol stearate mixture sold under the name Tefose® 63 by the company Gattefosse may be mentioned as examples.
As hydrophilic gelling agents, carboxyvinyl polymers (carbomer), acryl copolymers such as acrylate/alkylacrylate copolymers, polyacrylamides, polysaccharides such as hydroxypropylcellulose, clays and natural gums may mentioned, and as lipophilic gelling agents, modified clays such as bentone metal salts of fatty acids such as aluminum stearates and hydrophobic silic or alternatively ethylcellulose and polyethylene may be mentioned.
As hydrophilic active agents, proteins or protein hydrolysates, amino acids, polyols, urea, allanloin, sugars and sugar derivatives, water-soluble vitamins, starch and plant extracts, in particular those of Aloe vera may be used.
As lipophilic active, agents, retinol (vitamin A) and its derivatives, tocopherol (vitamin E) and its derivatives, essential fatty acids, ceramides and essential oils may be used. These agents add extra moisturizing or skin softening features when utilized.
The compositions of the invention may include other plant or herbal extracts. For example, there may be utilized extracts of Paraguay tea, Kola and Guarana, which provide a source of methylxanthines, saponius, tannins and glycosides that have been shown to reduce swelling and redness. The extract of Paraguay tea is known as “Mate extract” and is described in the “International Cosmetic Ingredient Dictionary”, 5th Edition. Mate extract is commercially available in combination with extracts of Kola and Guarana which is sold by Cosmetic Ingredient Resources of Stamford, Conn. under the trademark “QUENCHT.”
Each of mate extract, serine protease inhibitor and aloe vera extract are known to provide anti-inflammatory activity. The anti-elastase and anti-tryptase activity of the protease inhibitor has been shown to provide a synergistic effect in treating skin inflammations including sun burn.
A surfactant can be included in the composition so as to provide deeper penetration of the ingredients. Although natural surfactants are preferred, others such as isopropyl myristate can be used.
U.S. Pat. Nos. 4,916,117; 5,215,965; 5,093,316; 5,217,951, which are herein incorporated by reference, disclose the anti-inflammatory characteristics of serine protease inhibitors.
Alpha 1-antitrypsin and alpha 2-macroglobulin have been demonstrated as having anti-viral activity against a wide variety of viruses including HIV and Herpes Simplex.
Since it is quite common that the same cosmetic compositions are often utilized by more than one person so that disease can be spread, it is advantageous to provide a cosmetic composition which possesses anti-viral characteristics. This need exists in both lipsticks and eyeliners or eye shadows.
The following examples illustrating the compositions of the invention are not intended to limit the scope of the invention. The amounts indicated are by weight percent unless otherwise noted.
EXAMPLE 1
A gel is prepared by admixing the following ingredients.
Ingredient
Wt %
Carbomer 940
4.10
Xantham gum
0.15
Propylene glycol
51.94
Dipropylene glycol
10.00
Ethoxydiglycol
15.00
Dimethylisosorbide
10.00
Aloe Vera gel
8.00
Surfactant
0.05
Alpha 1-antitrypsin
1.76
100%
This composition is useful to reduce wrinkles.
In lieu of alpha 1-antitrypsin, SLPI can be utilized alone or in combination with alpha 1-antitrypsin.
EXAMPLE 2
A gel is prepared by admixing the following ingredients:
Ingredient
Wt %
1. Propylene Glycol
51.94
2. Carbomer 940
2.10
3. Dipropylene glycol
10.00
4. Xanthan gum
0.15
5. Ethoxydiglycol
15.00
6. Dimethylisosorbide
10.00
7. Ascorbic Acid
2.00
8. Chloroxylenol
0.20
9. Linoleamidopropyl PG-diammonium chloride phosphate
1.50
10. Glycereth 4.5 Lactate
2.00
11. Aloe Vera Gel
2.00
12. Alpha 1-anitrypsin
2.00
13. Tetrasodium EDTA
0.10
14. Citric Acid
0.010
15. Cocamidopropyl PG-dimonium chloride phosphate
1.00
Ingredients 1 and 2 are mixed to disperse and form a gel. About 80% of ingredient 3 is mixed with ingredient 4, added to the gel and slightly heated with admixture. The balance of 3 is mixed with ingredients 5-10 and added to the gel. Ingredients 11-15 are then admixed and added to the gel at 38 degrees C. After mixing, the gel is brought to room temperature.
This gel composition can be used as an after-sun treatment.
EXAMPLE 3
A lotion is prepared by admixing the following ingredients:
Ingredient
Wt %
Propylene Glycol Stearate
9.50
Isocetyl alcohol
5.00
PEG-100 Stearate
1.20
Water
69.90
Methyl paraben
0.20
Propylene glycol
13.10
Sorbitan palmitate
0.60
Alpha 1-antitrypsin
6.00
Mate extract
0.50
100%
The lotion can be used to relieve inflammation after exposure to the sun.
EXAMPLE 4
A cream is prepared by mixing the following ingredients:
Ingredient
Wt %
Glycerol stearate
8.0
PEG-100 stearate
2.0
Cetostearyl alcohol
2.5
Disodium EDTA
0.1
Methyl Paraben
0.1
Propylene glycol
6.0
Sorbitan stearate
0.7
Alpha 1-antitrypsin
2.5
Aloe vera gel
5.0
Water
13.5
100%
EXAMPLE 5
An after-sun composition is prepared by admixing the following ingredients:
Ingredient
Wt %
Carbomer
2.80
Propylene Glycol
40.05
Disodium EDTA
1.10
Methyl Paraben
0.20
Alpha 1-antitrypsin
2.00
SLPI
2.00
Mate extract
0.35
Aloe Vera Gel
52.50
100%
EXAMPLE 6
A solution according to the invention is prepared by admixing the following ingredients:
Ingredient
Wt %
Ethoxyglycol
15.00
Propylene Glycol
35.00
Water
q.s.
Disodium EDTA
0.10
Alpha 1-antitrypsin
4.50
Aloe Vera Gel
36.75
100%
EXAMPLE 7
A shampoo is prepared by admixing the following ingredients:
Ingredient
Wt %
C12-15 Pareth-7 Carboxylic Acid
10.0
Isosteareth -6 Carboxylic Acid
5.0
Hexylene Glycol
8.0
Chloroxylenol
0.5
Alpha 1-antitrypsin
2.0
Mate Extract
0.5
Aloe Vera Gel
2.0
Na2 EDTA
0.1
Water
71.9
100%
The shampoo is useful in the treatment of scalp inflammation or itch after exposure to the sun.
The shampoo can be used for sensitive scalps which have sensations of purities, that is to say by itching or prickling to different factors such as inflammation triggered by local factors such as soaps, surfactants, erythema, and the like.
Experiment 1
5 adults over 50 years of age for one week were exposed to the summer sun, swam in a fresh water lake and did not utilize a sunscreen during the day. At the end of each day, each adult applied a commercial suntan lotion (Coppertone®) to one half of the face and to the other half applied the composition of Example 4.
At the end of one week, the faces were examined. On each adult the part of the face which was treated with suntan lotion had a noticeable increase in wrinkles around the eyes and some erythema. The side of the face on which the composition of Example 4 was applied had a reduction in the depth of the wrinkles, the skin was smoother and not erythemous. The greater and more numerous the wrinkles before hand, the greater the visible effect of the treatment.
After three weeks without the use of suntan lotion or the alpha 1-antitrypsin composition, skin peeling occurred over a greater part of the face wherein suntan lotion was applied.
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Cosmetic compositions and methods are provided for revitalizing the skin especially where it is placed in an environment that can cause injury to the skin. The compositions contain an effective amount of a serine protease inhibitor to reduce damage to the skin resulting from exposure to the sun.
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BACKGROUND OF THE INVENTION
CH-A5-688 568 discloses a crop treatment or conditioner implement for agricultural crops, both with and without a front-mounted mower. Downstream of the treatment device a hood is provided, which guides the mowed crop released from the treatment device downstream in order to discharge it appropriately onto the ground. On the bottom of the hood cover, several symmetrically arranged guide vanes are provided, which scatter the conditioned crop.
It is also known that a so-called swath plate can be mounted in the path of crop flow on the bottom of the hood cover at a site where the hood is wider than at its ordinary discharge end. In this manner a relatively wide swath can be formed.
The problem underlying the invention is seen in the fact that the guide vanes must be disassembled to use a swath plate and vice-versa.
SUMMARY OF THE INVENTION
According to the present invention, there is provided an improved crop guide arrangement for use with a crop mowing and/or conditioning implement.
An object of the invention is to provide a crop guide arrangement, for use with a crop mowing and/or conditioning implement, the guide arrangement including guide elements which may be easily selectively placed in the stream of crop created by the mowing and/or conditioning devices so as to alter the width or density of a swath of crop material deposited behind the implement.
A more specific object of the invention is to provide an implement, as set forth in the immediately preceding object, wherein the guide elements include a swath plate vertically pivotally mounted beneath the top of a hood of the implement, and a guide vane arrangement vertically pivotally mounted above the top of the hood, with the hood and guide vane including slits or slots vertically aligned with respective guide vanes so as to permit the vanes to be moved from a retracted position above the hood to a working position below the swath plate.
These and other objects will become apparent from a reading of the ensuing description together with the appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top, somewhat schematic view of a mower-conditioner including a crop guide arrangement constructed in accordance with the present invention.
FIG. 2 is a horizontal sectional view, of the crop guide arrangement shown in FIG. 1, with parts being omitted for simplicity.
FIG. 3 is a top plan view, of the crop guide arrangement shown in FIG. 1, but omitting the swath plate and adjustable side plates, with the housing top broken away, the plate carrying the guide vanes being shown in a lowered working position wherein the vanes extend through respective vertically aligned openings provided in the top of the hood.
FIG. 4 is an enlarged vertical sectional view taken through the crop guide arrangement of FIG. 1, at line 4—4, showing the swath plate and the plate carrying the guide vanes.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, there is shown a harvesting implement 10 depicted as a mower-conditioner including a frame 12 , a draft tongue 14 , a pair of ground support wheels 16 , a mower and conditioner housing 18 , a crop mowing device 20 , a crop conditioning device 22 and a crop guide arrangement including a guide surface or swath plate 24 and a guide vane device 26 .
Although the harvesting implement 10 is designed in this practical example in the fashion of a mower-conditioner, this is not essential to the invention, and a design as a pure mower or as a pure conditioning or treatment implement is also possible instead. The harvesting implement 10 has the task of mowing and conditioning or treating the mowed crop and depositing the crop on the ground behind in a swath. It is desirable to be able to vary the width or location and density of the swath so that the swath lies more or less wide or offset or tight so that a subsequent harvesting machine, for example, a field chopper or a baler can pick up the harvested crop without problem.
Frame 12 is essentially designed as a bridge having an inverted U-shape and extends crosswise to the direction of travel in order to accommodate on each end one of the wheels 16 in a known vertically pivotable fashion using a vertically pivotable wheel support arm.
The draft tongue 14 , in this practical example, extends forwardly from, and is connected to pivot horizontally on the left side of, the frame 12 . The tongue 14 performs the usual function of connecting the harvesting implement 10 to a towing vehicle (not shown). The tongue 14 can also be connected on the right side or in the center of the frame 12 .
The wheels 16 support the frame 12 on the ground through their respective support arms that are pivotally coupled to the corresponding vertical arms of the frame 12 . Thus an intermediate space is formed between the wheels 16 in which the harvested crop can be discharged in a more or less broad swath.
The housing 18 is formed essentially box-like from sheet metal and mounted in the forward part thereof is the crop mowing device 20 followed by the crop conditioning device 22 , the housing 18 forming a channel in whose interior the mowed crop is guided up to a discharge site behind and beneath the harvesting implement 10 . While the housing 18 reaches at least the outer edges of the wheels 16 in a front region positioned on the bottom in FIG. 1, it is designed narrow in its rear region so that sufficient room is present in the intermediate space of frame 12 . The housing 18 extends behind frame 12 and, depending on the version, also behind the wheels 16 . In the rear region of housing 18 , a cover 28 is provided, which grades into opposite side walls 30 . On the rear edges of the side walls 30 , side plates 34 are respectively connected by means of vertical pivot bearings 32 , the side plates 34 acting for funneling the mowed crop laterally toward the center of the machine.
The crop mowing device 20 in this practical example is designed as a rotary disk mower. As an alternative, a drum design, a sickle bar, or the like, could also be used. The mowing device 20 serves to separate standing crop from the ground and convey it rearward to be deposited on the ground. Instead of the mowing device 20 , a crop conditioning rotor could be used to pick up already mowed crop, condition the crop and then release it rearward to be deposited on the ground.
The crop conditioning device 22 is as wide as or narrower than the crop mowing device 20 and conditions the crop so that it dries more quickly and then conveys the conditioned crop to the guide surface 24 . The crop conditioning device 22 can be designed as a tined rotor, as a brush rotor, as a double roll or the like.
The guide surface 24 , in this case, is formed from a so-called swath plate, which is situated in the housing 18 beneath cover 28 and can be moved by means of a shaft 36 (see FIGS. 2 and 4) more or less directly or indirectly into the crop stream coming from the crop conditioning device 22 . Generally, any surface on which the harvested crop passes along after leaving the crop conditioning device 20 can be considered as forming the guide surface 24 .
The guide surface 24 is designed essentially rectangular and is rigidly connected to the shaft 36 . The shaft 36 is mounted in bearings (not further shown) to pivot in the side walls 30 and is connected to a long edge of the guide surface 24 . Openings 40 , in the form of slits, extend in the direction of shaft 36 from a rear end edge 38 located on the opposite side of the guide surface 24 from the shaft 36 .
The openings 40 are open in the region of end edge 38 and run sloping, here shown angled to the right from rear to front, relative to the longitudinal center axis of the harvesting implement 10 . The slope of openings 40 is chosen so that they diverge slightly from each other from the front to the rear. The openings 40 extend over a significant part of the guide surface 24 . As an alternative (not shown), the openings can also extend parallel to each other or diverge in the fashion of a “V”.
The openings 40 , in a version not shown, can also be closed on the end, which is conceivable in an arrangement designed such that the harvested crop does not become caught and held in the openings 40 .
The shaft 36 is provided on one end with a crank arm 42 , with which the position of the guide surface 24 can be changed manually. The position can also be secured by locking devices (not shown), like cranks, locks, brakes or the like. Depending on the position of guide surface 24 , the crop stream is more or less strongly deflected downward and forms a wide swath. Without using the guide surface 24 the crop stream would be forced together by the side sheets 34 across the direction of crop flow.
The guide device 26 includes a support plate 44 , a shaft 46 and guide elements 48 .
The support plate 44 is designed rectangular, roughly of the same size as the guide surface 24 , and has a long, front side fixed to the shaft so that the plate 44 rotates in unison with the shaft 46 . Alternatively, the support plate 44 can be mounted on the top of cover 28 . Instead of support plate 44 , another structure could also be used, for example, a frame, rail or the like, as long as the purpose, namely connecting the guide elements 48 to each other, is achieved.
The shaft 46 is longer than support plate 44 and has opposite end portions respectively mounted to rotate in brackets 50 fixed to the top of the cover 28 . On one end of the shaft 46 , there is provided an integral crank arm 52 with which shaft 46 can be pivoted. In the same manner as with crank arm 42 , the crank arm 52 can also be secured in any position with any well known device. As an alternative, the crank arm 52 , like crank arm 42 , can be adjusted by an operating device, for example, in the form of a motor, a linkage or cable pull.
The guide elements 48 correspond in number, position and alignment to those of openings 40 . When the guide elements 48 are narrower than the openings 40 , they can also assume a position deviating from alignment of the openings. Like the openings 40 , the guide elements 48 can also run parallel to each other or diverge relative to a center plane. Whereas in the first case only lateral offset of the crop stream occurs, a “V”-shaped arrangement leads to wide scattering of the crop stream. However, generally a lateral offset of the crop stream and broad scattering is preferred, which leads to a swath whose width maximally corresponds to the harvesting width. The guide elements 48 are designed according to FIG. 4, in the side view, essentially triangular, in which one side is attached to 35 the support plate 44 , one side runs perpendicular to the first side on the downstream end and a hypotenuse extends from the upstream end to the downstream end and thus has a slope toward the ground in the operating condition according to FIG. 4 . The guide elements 48 are formed from a plate and are suitable for taking up significant lateral forces.
FIG. 4 shows the assembly of the housing 18 , guide surface 24 and guide device 26 in a vertical section. According to FIG. 4, the support plate 44 is situated above the cover 28 so that openings 54 are present in the form of slits congruent with the openings 40 in the cover 28 , through which the guide elements 48 can extend. Alternatively, in a version (not shown), the support plate 44 could be accommodated in a cutout in the cover 28 . In the depicted version, the guide surface 24 is situated in an upper position in which it does not extend into the crop stream. As a result, the crop stream reaches the region between guide elements 48 and is then scattered or deflected broadly.
If broad scattering or lateral deflection is not desired, the guide device 26 is pivoted counterclockwise upward so as to be out from the inner region of housing 18 and thus becomes inactive. In this case, the crop stream slides on the bottom of cover 28 and along the bottom of guide surface 24 until it contacts side plates 34 , if they are present. After contact with side plates 34 , a narrow swath is produced.
If a wide swath is to be formed, the guide surface 24 is pivoted downward clockwise and the crop stream impinges on it in order to fall on the ground in a wide swath. It is not essential that the guide device 26 be brought into the position of FIG. 4 where it is depicted with the dashed line.
According to all this, the harvested product can be deposited according to the invention in several ways, for example, narrow swath, wide swath or broadly scattered on the ground, without having to refit the harvesting implement 10 . In addition, by the degree of penetration of the guide elements 48 into the internal space of the housing 18 , the intensity of the effect on the crop stream can be varied.
In the present practical example, the position of the guide elements 48 on support plate 44 is fixed. However, it is also possible to mount the guide elements 48 on one end or in the center to pivot around an axis perpendicular to the support plate 44 . In this case, the guide elements 48 must maintain a spacing with their upper edge relative to the support plate 44 which corresponds at least to the thickness of the cover 28 and the guide surface 24 . Moreover, it must be guaranteed that the guide elements 48 have the alignment of openings 40 and 54 , when the guide device 26 is pivoted vertically. By virtue of this pivoting capability of the guide elements 48 , both the discharge direction and the scattering width or swath width can be varied.
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A mower-conditioner includes a crop guide arrangement for intercepting a stream of crop impelled to the rear by the mower and conditioner devices, where guide elements, in the form of vertical, triangular plates, may be selectively rotated down through slots provided in a crop guide surface so as to change the density and width of a swath of crop material deposited onto the ground behind the mower-conditioner.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an information processing apparatus and to a method for appropriately terminating processing that is currently being performed.
2. Related Background Art
Conventionally, to terminate the use of a device, for example, a computer performs a predetermined end process in accordance with an end instruction. However, in an environment wherein multiple users can employ a device, problems may arise if they freely terminate the processing that is currently being performed or the operation of the device.
For a client/server system, for example, there is not merely one end process that is required in accordance with the situation, instead, there are multiple end processes, such as the termination of a client process or the shutting down of a system. The termination of a client process should be the responsibility of a client processing unit.
SUMMARY OF THE INVENTION
It is, therefore, one objective of the present invention to provide an information processing apparatus and method for preventing the execution of an end process that a user is not permitted to perform.
It is another objective of the present invention to provide an information processing apparatus and method for using a password to control an end process.
It is an additional objective of the present invention to provide an information processing apparatus and a method for appropriately terminating a client process in a client/server system.
It is a further objective of the present invention to provide an information processing apparatus and method for performing a specific process at a client processing unit in a client/server system.
According to one aspect, the present invention, which achieves these objectives, relates to an information processing apparatus comprising:
end instruction means for instructing termination of information processing;
end processing means for performing an end process when termination is instructed by the end instruction means;
input means for entering a password; and
control means for identifying the password and for controlling the end process performed by the end processing means based on the password that is identified.
According to another aspect, the present invention, which achieves these objectives, relates to an information processing apparatus comprising:
client means for, in accordance with an operation performed by a user, generating and transmitting a request for the performance of a process, and for receiving operating screen information and providing the operating screen information to the user;
server means for interpreting the request and adding object information to a database, and for generating and transmitting operating screen information to the client means; and
execution means for monitoring the database, and for detecting object information that is to be processed and for processing the object information,
wherein, in accordance with a specific operation selected by the user, the client means internally performs a process, instead of generating and transmitting a request for the performance of the process.
According to still another aspect, the present invention, which achieves these objectives, relates to an information processing method comprising:
an end instruction step of instructing termination of information processing;
an end processing step of performing an end process when termination is instructed at the end instruction step;
an input step of entering a password; and
a control step of identifying the password, and of controlling the end process at the end processing step based on the password that is identified.
According to yet another aspect, the present invention, which achieves these objectives, relates to an information processing method comprising:
a client process for generating and transmitting a request for performing a process in accordance with an operation performed by a user;
a server process for interpreting the request and adding object information to a database, and for generating and transmitting operating screen information to the client process; and
an execution process for monitoring the database and detecting object information that is to be processed, and for processing the object information,
wherein in the client process, the operating screen information is received and provided for the user, and wherein, in accordance with a specific operation selected by the user, a corresponding process is performed by the client process, instead of a request for the performance of the process being generated and transmitted.
According to a further aspect, the present invention, which achieves these objectives, relates to a computer-readable storage medium on which a program for controlling a computer is stored, the program comprising codes for causing the computer to operate;
an end instruction step for instructing termination of information processing;
an end processing step of performing an end process when termination is instructed at the end instruction step;
an input step of entering a password; and
a control step of identifying the password and of controlling the end process at the end processing step based on the password that is identified.
According to one further aspect, the present invention, which achieves these objectives, relates to a computer-readable storage medium on which a program for controlling a computer is stored, the program comprising:
a client process for, in accordance with an operation performed by a user, generating and transmitting a request for the performance of a process, and for receiving operating screen information and providing the operating screen information to the user;
a server process for interpreting the request and adding object information to a database, and for generating and transmitting operating screen information to the client process; and
an execution process for monitoring the database and for detecting object information that is to be processed, and for processing the object information,
wherein in accordance with a specific operation selected by the user, a corresponding process is performed by the client process, instead of a request for the performance of the process being generated and transmitted.
Other objectives and advantages, in addition to those discussed above, will become apparent to those skilled in the art during the course of the description of a preferred embodiment of the invention that follows. In the description, reference is made to accompanying drawings, which form a part of the description and which illustrate an example of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing the functional arrangement for one embodiment of the present invention;
FIG. 2 is a diagram illustrating the system configuration according to the embodiment of the present invention;
FIG. 3 is a functional block diagram illustrating a printer according to the embodiment of the present invention;
FIG. 4 is a diagram showing an example screen for an initial menu;
FIG. 5 is a flowchart showing the processing that begins with the initial menu screen;
FIG. 6 is a flowchart showing the login processing;
FIG. 7 is a diagram showing an example main menu;
FIG. 8 is a flowchart showing the processing that begins with the main menu;
FIG. 9 is a flowchart showing the end processing;
FIG. 10 is a flowchart showing the shutdown processing; and
FIG. 11 is a diagram showing an example end screen.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment of the present invention will now be described while referring to the accompanying drawings.
A detailed explanation will be given for one embodiment of the present invention while referring to the drawings.
In FIG. 1 is shown the functional arrangement of the embodiment. The relationship existing between a user 101 , a client 102 , a server 103 , a database 104 , and a daemon 105 is shown. The client 102 and the server 103 may be provided either on the same device, or on separate devices connected by a network.
When the user 101 performs a specific operation for the client 102 , the client 102 generates a request that corresponds to the operation, and transmits it to the server 103 . The server 103 interprets the received request, and communicates with the database 104 for the deletion or the addition of a job, or to obtain data. As a result, the server 103 prepares a corresponding HTML page as needed, and transmits it to the client 102 . The client 102 displays the received HTML page, and permits the user 101 to initiate a new operation.
Jobs stored in the database 104 are monitored by the daemon 105 . The daemon 105 performs the printing, the transmission, or the notification required for a job for which the performance condition has been satisfied.
FIG. 2 is a diagram showing the system configuration according to the embodiment.
In FIG. 2, various devices are connected to a network 201 , and data are exchanged across the network 201 . A printer 202 , which prints data received via the network 201 , includes an input/output operation unit 203 . The input/output operation unit 203 provides various displays for a user, and accepts instructions from the user. A scanner 204 and a multi-function device 205 also include the same input/output operation unit. The scanner 204 optically reads data printed on paper, and the multi-function device 205 includes the functions both of the printer 202 and of the scanner 204 . A personal computer 206 creates documents and images, and manages personal data, such as mail and a schedule for the user.
The printer 202 , the scanner 204 , the multi-function device 205 , and the personal computer 206 can each serve as the client and the server described above.
FIG. 3 is a functional block diagram illustrating the printer 202 according to the embodiment.
In FIG. 3, a touch panel 301 is used to display a printer status and a menu screen for a user, who by touching the screen can select an item listed on the menu. The user can also enter characters by using a keyboard that is displayed on the screen. Instead of the touch panel 301 , an ordinary display unit and a keyboard can be prepared.
A CPU 302 executes various programs, to include procedures that will be described later while referring to the flowcharts, and controls the individual sections connected by a system bus 308 . A printing unit 303 prints data on paper, etc. A communication unit 304 exchanges data, to include commands and statuses, with a desktop or with a scanner, or with another printer connected across a network.
A ROM 305 is used to store fixed data and programs. A RAM 306 is used to temporarily store data and programs. A hard disk drive (HDD) 307 is used to permanently store programs and data, and is employed as the above described database 104 . The system bus 308 is used as a medium for connecting the above described sections, and for the exchange of data, addresses and control signals among these sections. The programs, including the procedures that will be described later while referring to the flowcharts, may be stored in the ROM 305 , or may be loaded from the HDD 307 into the RAM 306 , as needed, before the processing has begun or while it is in progress.
In FIG. 4 is shown an example initial menu screen. FIG. 5 is a flowchart showing the processing that begins with the initial menu screen. When jobs are present in a print queue, they are displayed as a list on the status screen. As information for each of the individual jobs, the name of the job and the name of the submitter are displayed.
At step S 501 a user selects a desired item from the initial menu. At step S 502 the selected item is identified and a corresponding new screen is displayed.
When “Device” is selected, at step S 503 the device status is displayed. When “Back” or “Forward” is selected, at step S 504 the screen that preceded or that succeeds the current screen is displayed. When “End” is selected, at step S 505 an end process is performed. When “New Interaction” is selected, at step S 506 a new process is performed. When “Help” is selected, at step S 507 the help screen for the current state is displayed.
“When Print URL” is selected, the screen is changed to a “Print URL” screen. When, at step S 515 , a URL is indirectly entered or is designated by a reference, and “Go” is selected, at step S 516 information is obtained and previewed. At step S 517 the contents of the information that have been confirmed are printed. The screen is thereafter returned to the initial menu screen.
When “Public Info (public information)” is selected, at step S 515 program control advances to the process for public information, and the screen is changed to a “public information process” screen. When “Goto Device (another device)” is selected, at step S 512 a setup screen for accessing another device is displayed, and the process for accessing another device is performed.
In addition, a job in a print queue can be selected on the initial screen. To select a job, a button displayed in front of the name of the desired job is touched. When a specific job is thus selected, at step S 513 a password input screen is displayed. A password is then entered, and when it matches the password for the selected job, a setup screen is displayed for a process that corresponds to the job that was selected from the print queue.
Following this, at step S 514 an action type is selected for the selected job, and at step S 515 an appropriate time for the action type is set. When “Print Later” is selected as an action type, at step S 517 the print time can be designated. When “Hold Here” is selected, at step S 518 the length of time for the holding period can be set.
When “Pause/Restart Printing” is selected, at step S 519 the printing is temporarily halted, and the screen is returned to the initial menu screen to wait for the selection of “Pause/Restart Printing” (for the depression of the same button). When “Cancel Printing” is selected, at step S 520 a print job is deleted from the print queue, and “Cancel” is recorded in the history as the action taken for this job. The screen is then returned to the initial screen.
FIG. 6 is a flowchart showing the login processing performed when a new process is selected on the initial menu. At step S 601 a “Login” screen is displayed, and the identifier that a user has entered is examined. When a login is permitted, at step S 602 a check is performed to determine whether there are any effective jobs (pending jobs) present for the user who has just logged in. If there are such unprocessed jobs, at step S 604 a list of them is displayed and an action for a selected job is performed. When there are no unprocessed jobs, at step S 603 the main menu is displayed to initiate the performance of the processing that begins with the main menu, which will be described later while referring to FIG. 8 .
FIG. 7 is a diagram showing an example main menu, and FIG. 8 is a flowchart showing the processing that begins with the main menu. In the flowchart, the shifting of the screen from the main menu and the flow of the process are shown. At step S 801 the main menu is displayed, and at step S 802 a process (action) is selected.
When “Logout” is selected at step S 802 , at step S 804 the logout process is performed. When “Help” is selected, at step S 805 the help process is performed. When “Search” is selected, at step S 806 the search process is performed. When “Print” is selected, at step S 807 the printing process is performed. When “Send” is selected, at step S 808 the transmission process is performed. When “Delete” is selected, at step S 809 the deletion process is performed. When “Set Instructions” is selected, at step S 810 the command setup process is performed. And when “Reschedule” is selected, at step S 811 the rescheduling process is performed.
When the addition of public information is selected, at step S 812 public information is added. When “Goto Device” is selected, at step S 813 another device is accessed. When “Goto My Desktop” is selected, at step S 814 the desktop is accessed. When “Device” is selected, at step S 815 the status of the apparatus is displayed. And when “End” is selected, at step S 816 the end process is performed that will be described in detail while referring to FIG. 9 .
FIG. 9 is a flowchart showing the end processing performed when the End button displayed in the upper right of each operating screen is selected.
When a user enters information on any operating screen displayed by the client, the client processing unit determines whether the operation selected by the user should be handled by the client or by the server.
In this embodiment, the operating buttons displayed on the operating screen are displayed on a screen holding an HTML page received by the server. When the user selects one of the buttons, in the client process the selected operation is converted into a corresponding HTML request, which is transmitted to the server. The server then performs a corresponding process.
The End button in the upper right of each operating screen is one that is written over the HTML page by the client side. When the user selects the End button, therefore, it is assumed that this process should be handled by the client, and the end process in FIG. 9 is initiated by the client.
When the end process is initiated, at step S 901 the end screen is displayed. FIG. 11 is a diagram showing an example end screen. At step S 902 the contents of the operation selected by the user are obtained and at step S 903 they are analyzed. At step S 904 program control branches in accordance with the operation type.
When a password is input by the user, at step S 905 “*” is displayed on the screen in order to affirm that the input by the operator was accepted. At step S 906 the operator input password data that are internally held are updated. Program control then returns to step S 902 to accept a new user operation.
When “Restart” is selected by the user, at step S 907 the client process that is currently being performed is terminated and is then restarted. The processing is thereafter terminated.
When “Shut Down” is selected by the user, at step S 908 the shutdown process in FIG. 10 is performed, and the processing is thereafter terminated.
FIG. 10 is a flowchart showing the shutdown processing. For this processing, a different operation is performed in accordance with a password entered by the user.
When the shutdown process is initiated, at step S 1001 program control branches in accordance with the password that is entered.
When the password entered by the user matches the password for a shutdown system that is set in advance by a manager, at step S 1002 the system is shut down, and the processing is terminated.
When the password entered by the user matches the password for “leave to OS” that is set in advance by the manager, at step S 1003 only the client process is terminated, and the control right is returned to the OS. The processing is thereafter terminated.
When the password entered by the user does not match either password that is set in advance by the manager, at step S 1004 an error message is displayed, and the processing is thereafter terminated. When “Cancel” is selected by the user, the processing is terminated without any further process being performed.
With this arrangement, for example, only the manger can shut down the system, and only a specific user can terminate the client process.
The present invention may be applied for an apparatus constituted by a single device, or for a system constituted by a plurality of apparatuses. For implementing the present invention, a storage medium on which is stored software program code for implementing the functions described in the above embodiment may be supplied to an apparatus or to a system, and the computer in the apparatus or in the system may read the program code from the storage medium.
In addition, the scope of the present invention includes not only a case where the functions in the embodiment can be performed when program code is read and executed by the computer, but also a case where, in accordance with an instruction contained in the program code, an OS running on the computer, etc., can perform the processing required to accomplish the functions included in the above embodiment.
The storage medium on which such program code is recorded constitutes the present invention.
Although the present invention has been described in its preferred form with a certain degree of particularity, many apparently widely different embodiments of the invention can be made without departing from the spirit and the scope thereof. It is to be understood that the invention is not limited to the specific embodiments described herein, except as defined in the appended claims.
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When termination of information processing is instructed, the entry of a password is requested and the password that is entered is identified. When the password that is input is a password for a manager, the system is shut down; when it is a password for a registered user, the client process is terminated; but when it is a password for a person other than those two, permission to end the processing is not granted. Thus, the type of end process that is performed can be controlled in accordance with the identity of a user. As for the client process, upon receiving an end instruction from a user the client internally performs a corresponding end process, instead of requesting that the process be performed by the server process.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of Invention
[0002] The invention relates to an organic electroluminescence device and, in particular, to an organic electroluminescence device with a low reflectivity.
[0003] 2. Related Art
[0004] The organic electroluminescence device which is also named organic light-emitting diode (OLED) has the advantages of both LCD and inorganic LED, such as thin, light-weight, high-resolution, power-saving, self-emission and high-response, etc. However, the conventional OLED needs to be deposited a metallic electrode, the contrast of OLED panel will greatly reduce due to the reflection of the ambient light. The legibility for a conventional OLED panel is thus relatively poor.
[0005] A conventional method so far is to attach a layer of circular polarizer (CP) on an OLED by changing the phase of the incident ambient light to reduce the reflection. As described in the U.S. Pat. Nos. 5,596,246 and 6,211,613, the CP is attached on the display. This method has been adopted in mass production for OLED. However, the use of CP will increase the production cost. One may also use optical absorption and optical interference to reduce the reflectivity of the metallic electrode. The U.S. Pat. Nos. 6,185,032, 6,558,820, 6,545,409, and the early disclosure No. 2002/0043928 proposed another method, which coats a thin layer of dark-colored or black light-absorbing material before the reflective metallic electrode of the OLED. This method reduces the reflectivity of the metallic electrode and increases the panel contrast. Moreover, one can also use the method of using optical absorption along with the destructive interference to reduce the device reflectivity, as disclosed in the U.S. Pat. Nos. 6,411,019, 6,545,409, 6,429,451, and 6,608,333. The device structure disclosed in the U.S. Pat. No. 6,411,019 is to insert an interference layer in the OLED. The interference layer is between the electrode and organic electroluminescence (OEL) layer of the device to reduce the reflectivity due to optical absorption and destructive interference. To excite the OEL layer between the anode and the cathode, the inserted interference layer has to be made of a conductive material. The work function difference between the interference layer and the electrode has to be extremely small in order not to reduce the carrier injection and increase the device operation voltage. This reduces the selection of the interference layer materials. In order to satisfy both the conductivity and the work function requirements, one usually selects indium tin oxide (ITO), indium zinc oxide (IZO), or a mixture of aluminum and silicon oxide as the interference layer. The device structure disclosed in the U.S. Pat. No. 6,545,409 is to use the thin cathode/light-absorbing layer/dielectric layer/metal layer structure in the OLED and the cathode and the metal layer are electrically connected. By controlling the conditions of the light-absorbing layer, the dielectric layer and the thin cathode, the reflectivity is also reduced due to the optical absorption and destructive interference. However, it is necessary to use the light-absorbing layer with an absorption coefficient greater than 10 4 cm −1 and the dielectric layer. Thus, it is limited for choosing materials, and it is also a little complicated in manufacturing and condition controls.
SUMMARY OF THE INVENTION
[0006] In view of the foregoing, the invention provides an organic electroluminescence (OEL) device to remove its reflection of the ambient light by inserting a transparent control layer with an appropriate thickness, thereby enhancing the contrast of the OEL device and panel. Through the device structure design, the control layer is not necessarily to be conductive and there is no need to adjust the work function of each adjacent layer. This enlarges the selection space of the control layer materials.
[0007] To achieve the above objective, the disclosed OLED device includes a transparent electrode, organic electroluminescence (OEL) layers, a thin metal layer, a transparent control layer, and an auxiliary electrode. The transparent electrode and the thin metal electrode are sited on both sides of the OEL layers in order to excite it to emit light. The control layer is transparent and adjacent to the thin metal electrode. The auxiliary electrode and the thin metal electrode are used to sandwich the control layer. Most of the region between the thin metal electrode and the auxiliary electrode is inserted with the transparent control layer with an appropriate thickness. However, the auxiliary electrode and the thin metal electrode are electrically connected at the other part of the sandwiched region without the control layer. By way of optical absorption and destructive interference, the invention can largely reduce the reflection caused by the ambient light, thus enhancing the contrast of the OLED display.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The invention will become more fully understood from the detailed description given hereinbelow illustration only, and thus are not limitative of the present invention, and wherein:
[0009] FIG. 1 is a schematic view of the structure in the first embodiment of the invention;
[0010] FIG. 2 is a schematic view of the structure in the second embodiment of the invention;
[0011] FIG. 3 is a schematic view of the structure in the third embodiment of the invention;
[0012] FIG. 4 is a schematic view of the structure in the fourth embodiment of the invention;
[0013] FIG. 5 shows the comparative reflectivity spectra of a standard device and the first test embodiment; and
[0014] FIG. 6 shows the comparative reflectivity spectra of the third test embodiment with ARC.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The invention can be applied to bottom-emission and top-emission organic electroluminescence (OEL) devices; only the coating order and device structures need to be modified.
[0016] The first embodiment shown in FIG. 1 belongs to the bottom-emission OLED device. The OLED device includes a transparent electrode 110 , OEL layers 120 , a thin metal layer 130 , a control layer 140 , and an auxiliary electrode 150 . The transparent electrode 110 is formed on the surface of a transparent substrate 100 . The OEL layers 120 are coated on the transparent electrode. The thin metal electrode 130 is formed on the OEL layers 120 . The thin metal electrode 130 is further formed with the control layer 140 and the auxiliary electrode 150 so that the control layer 140 is sandwiched between the thin metal electrode 130 and the auxiliary electrode 150 . The auxiliary electrode 150 and the thin metal electrode 130 are electrically connected via a conductive region 141 .
[0017] Since the conductive region 141 connecting the thin metal electrode 130 and the auxiliary electrode 150 does not contain the control layer, its reflectivity is higher. To reduce its local reflection, a black matrix 160 is installed on the region of the transparent electrode 110 corresponding to the conductive region, as shown in the second embodiment in FIG. 2 . The surface of the transparent substrate 100 is formed in sequence with a transparent electrode 110 , a black matrix 160 , OEL layers 120 , a thin metal electrode 130 , a control layer 140 , and an auxiliary electrode 150 . The black matrix 160 is coated on a part of the transparent electrode 110 . The OEL layers 120 are coated on both the transparent electrode 110 and the black matrix 160 . The thin metal electrode 130 is formed on the OEL layers 120 . The thin metal electrode 130 is further formed with the control layer 140 and the auxiliary electrode 150 so that the control layer 140 is sandwiched between the thin metal electrode 130 and the auxiliary electrode 150 . The auxiliary electrode 150 and the metal electrode 130 are electrically connected via a conductive region 141 , and the high reflection of the conductive region 141 will be reduced due to the black matrix 160 .
[0018] Reflections also occur at the interface between the substrate of the OLED device and the air, thus increasing the reflectivity. In order to reduce the overall reflectivity, an anti-reflection coating (ARC) is formed on the other surface of the substrate. As shown in FIG. 3 , one surface of the transparent substrate 100 is formed in sequence with a transparent electrode 110 , a black matrix 160 , OEL layers 120 , a thin metal layer 130 , a control layer 140 , and an auxiliary electrode 150 . The black matrix 160 is coated on a part of the transparent electrode 110 . The OEL layers 120 are coated on both the transparent electrode 110 and the black matrix 160 . The thin metal electrode 130 is formed on the OEL layers 120 . The thin metal electrode 130 is further formed with the control layer 140 and the auxiliary electrode 150 so that the control layer 140 is sandwiched between the thin metal electrode 130 and the auxiliary electrode 150 . The auxiliary electrode 150 and the thin metal electrode 130 are electrically connected via a conductive region 141 , and the high reflection of the conductive region 141 will be reduced due to the black matrix 160 . In addition, the other surface of the transparent substrate 100 is coated with an ARC 170 to further reduce the reflection between the substrate and the air.
[0019] Please refer to FIG. 4 for a top-emission OLED device, which is the fourth embodiment of the invention. The OLED device includes a transparent electrode 210 , OEL layers 220 , a thin metal layer 230 , a control layer 240 , and an auxiliary electrode 250 . The auxiliary electrode 250 is formed on the surface of a substrate 200 . The control layer 240 is formed on the auxiliary electrode 250 . The thin metal electrode 230 is formed on the control layer 240 . The control layer 240 is sandwiched between the thin metal electrode 230 and the auxiliary electrode 250 . The auxiliary electrode 250 and the thin metal electrode 230 are electrically connected via a conductive region 241 . The OEL layers 220 are coated on the thin metal electrode 230 . The transparent electrode 210 is formed on the OEL layers 220 . The top-emission OLED device uses the side with the transparent electrode 210 as the display surface.
[0020] Following the same principle, the top-emission OLED device can be formed with an ARC on its display surface to reduce reflections at the interface between the display surface and the air. One can also insert a black matrix formed in a region corresponding to the conductive region to reduce the local high reflection in the conductive region joining the thin metal electrode and the auxiliary electrode.
[0021] In the embodiments of the invention, the material of the transparent electrode is selected from transparent conductive substances such as indium tin oxide (ITO) and indium zinc oxide (IZO) or thin metal layer. The thin metal electrode is semi-transparent. Its material is selected from metals, alloys, or metal oxides. Its thickness is below 20 nanometers (nm). The control layer is a transparent material selected from inorganic insulating substances, inorganic semiconductor substances, organic insulating substances, organic semiconductor substances, or their combinations. Its thickness is above 30 nm and below 300 nm. The transparent material has an average absorption coefficient between 400 nm and 700 nm less than 10 4 cm −1 . The OEL layers can be a combination with different numbers of hole injection layer, hole transport layer, emission layer, electron transport layer, electron injection layer, and carrier generation layer.
[0022] To prove that the disclosed device can reduce reflections caused by the ambient light, we use the first embodiment structure with control layers made of different materials to test. The control layer materials are, respectively, LiF, NPB, and rubrene. The thickness can be adjusted according to the optical property of the material to achieve a lower reflection.
First Test Embodiment
[0023] A glass substrate with a transparent electrode is first precleaned by ultrasonic treatment in detergent, pure water and iso-propanol in sequence, followed by drying in an oven. Afterwards, the glass substrate is placed on a substrate holder in a cluster-type vacuum chamber. The surface of the transparent electrode is first processed by oxygen plasma. Afterwards, the transparent electrode is coated with 5 nm AlF 3 as the hole injection layer, 60 nm NPB as the hole transport layer, and 60 nm Alq 3 as the emission layer and the electron transport layer, thereby forming the OEL layers. It is further coated with 0.5 nm LiF and X1 nm aluminum as the thin metal electrode. The thin metal electrode is then coated with Y1 nm LiF as the control layer. Finally, 100 nm aluminum is coated as the auxiliary electrode. The conductive region between the thin metal electrode and the auxiliary electrode can be adjusted and controlled by tuning the angle of the metal mask and the evaporation angle. After packaging the OLED device, we measure the average reflectivity (400˜700 nm) of the OLED device. The test results of devices using X1 and Y1 are given in Table 1.
TABLE 1 Al = X1 nm LiF = Y1 nm Average reflectivity (%) 8 72 14.6 7.2 72 10.2 6.4 72 6.6 6.4 64 7.4 6.4 80 5.9 0 0 63.4
[0024] From the above results, the average reflectivity of the standard device without both a thin metal electrode and a control layer (X1=0, Y1=0) is 63.4%. After taping a circular polarizer (CP) on the standard device, we obtain an average reflectivity of 7.4%. The device in the first test embodiment has a reflectivity far lower than the standard device. The device in the first test embodiment (X1=6.4, Y1=80) has an average reflectivity of 5.9% only, even lower than the standard device attached with CP. The reflection spectra of these three devices are shown in FIG. 5 .
[0025] Moreover, the emission efficiency of the standard device will reduce to be 45% of its original efficiency after taping the CP. However, the device with a control layer can still maintain the emission efficiency above 50% of the standard device. The turn-on voltages of the device with a control layer and the standard device are both at 2.6 V. The voltage-current properties of both devices are very similar.
Second Test Embodiment
[0026] The control conditions of the manufacturing process and materials here are the same as in the first test embodiment. We only change the material of the control layer to NPB and set its thickness to be Y2. At the same time, the aluminum thickness of the thin metal electrode is X2. The test results for devices with different X2 and Y2 are given in Table 2. It clearly shows that the device in the second test embodiment has a reflectivity far lower than the standard device.
TABLE 2 Average Al = X2 nm NPB = Y2 nm reflectivity (%) 12.5 150 33.8 12.5 130 26.7 12.5 110 17.6 12.5 90 16.3 10 90 13.6 7.5 90 19.6
Third Test Embodiment
[0027] The control conditions of the manufacturing process and materials here are almost the same as in the first embodiments. We only change the material of the control layer to rubrene and set its thickness to be Y3. At the same time, the aluminum thickness of the thin metal electrode is X3. The test results for devices with different X3 and Y3 are given in Table 3. It clearly shows that the device in the third test embodiment has a reflectivity far lower than the standard device.
TABLE 3 Average Al = X3 nm Rubrene = Y3 nm reflectivity (%) 10 100 18.7 10 85 10.7 10 70 9.1 8 90 8.9 8 80 9.5 8 70 11.1
[0028] To further reduce the reflectivity, the device in the third test embodiment (X3=8, Y3=90) is coated with an ARC or taped with another piece of transparent substrate with an ARC on the other surface of the OLED device substrate to prevent reflections at the substrate-air interface. The average reflectivity of the OLED device can reduce from 8.9% to 5.8%. The reflection spectra of these two devices are shown in FIG. 6 .
[0029] From the test results of the first to third test embodiments, we learn that by tuning the thin metal electrode and the control layer and by coating an ARC, the reflectivity of the OLED device can be effective reduced. One may also adjust the ingredients of the auxiliary electrode (e.g. other metals or alloys) to achieve better effects.
[0030] In the above-mentioned test embodiments, the local junction between the thin metal electrode and the auxiliary electrode can be made using a metal mask with different coating angles. However, one can also employ other manufacturing processes such as shadow masks, ribs, collimators, dry etching, and laser processing.
[0031] Certain variations would be apparent to those skilled in the art, which variations are considered within the spirit and scope of the claimed invention.
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An organic electroluminescence device with a low reflectivity includes organic electroluminescence layers, a transparent electrode, a thin metal electrode, a control layer, and an auxiliary electrode. The transparent electrode and the thin metal electrode are sited on both sides of the OEL layer, respectively, in order to excite it to emit light. The auxiliary electrode and the thin metal electrode are mostly separated by a control layer. Both the auxiliary electrode and the thin metal electrode are locally connected to maintain electrically connected. Therefore, the control layer is not necessarily conductive and its material selection is not restricted by the requirement of work function matching with adjacent layers. The disclosed OLED device with a low reflectivity does not require a circular polarizer. It can be used for both active-matrix and passive-matrix OLED displays. The reflection of ambient light can be largely reduced to increase the contrast of the display panel.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of application Ser. No. 10/200,850, filed Jul. 22, 2002, now U.S. Pat. No. 6,676,845, issued Jan. 13, 2004, which is a continuation of application Ser. No. 09/482,187, filed Jan. 12, 2000, now U.S. Pat. No. 6,464,888, issued Oct. 15, 2002, which is a continuation of application Ser. No. 09/041,829, filed Mar. 12, 1998, now U.S. Pat. No. 6,051,149, issued Apr. 18, 2000.
GOVERNMENT LICENSE RIGHTS
This invention was made with government support under Contract No. DABT 63-97-C-0001 awarded by Advanced Research Projects Agency (ARPA). The Government has certain rights in this invention.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to methods for forming etch masks on substrates which are too large to efficiently employ photolithography techniques. Such etch masks may be used to form such structures as micropoint cathode emitters for field emission flat panel video displays, spacers for liquid crystal displays, quantum dots, or other features which may be randomly distributed on a surface.
2. State of the Art
For considerably more than half a century, the cathode ray tube (CRT) has been the principal device for electronically displaying visual information. Although CRTs have been endowed during that period with remarkable display characteristics in the areas of color, brightness, contrast and resolution, they have remained relatively bulky and power hungry. The advent of portable computers has created intense demand for displays which are lightweight, compact, and power efficient. Although liquid crystal displays (LCDs) are now used almost universally for laptop computers, contrast is poor in comparison to CRTs, only a limited range of viewing angles is possible, and battery life is still measured in hours rather than days. Power consumption for computers having a color LCD is even greater, and thus, operational times are shorter still, unless a heavier battery pack is incorporated into those machines. In addition, color screens tend to be far more costly than CRTs of equal screen size.
As a result of the drawbacks of liquid crystal display technology, field emission display technology has been receiving increasing attention by the industry. Flat panel displays utilizing such technology employ a matrix-addressable array of cold, pointed, field emission cathodes in combination with a luminescent phosphor screen.
Somewhat analogous to a cathode ray tube, individual field emission structures are sometimes referred to as vacuum microelectronic triodes. Each triode has the following elements: a cathode (emitter tip), a grid (also referred to as the gate), and an anode (typically, the phosphor-coated element to which emitted electrons are directed). The cathode and grid elements are generally located on a baseplate, while the anode elements are located on a transparent screen, or faceplate. The baseplate and faceplate are spaced apart from one another. As the space between the baseplate and faceplate must be evacuated, a hermetic seal joins the peripheral edges of the baseplate to those of the faceplate.
Although the phenomenon of field emission was discovered in the 1950's, it has been within only the last ten years that extensive research and development have been directed at commercializing the technology. As of this date, low-power, high-resolution, high-contrast, monochrome flat panel displays with a diagonal measurement of about 15 centimeters have been manufactured using field emission cathode array technology. Although useful for such applications as viewfinder displays in video cameras, their small size makes them unsuited for use as computer display screens.
Several engineering obstacles must be overcome before large screen field emission video displays become commercially viable. One such problem relates to the formation of load-bearing spacers which are required to maintain physical separation of the baseplate and the phosphor coated faceplate in the presence of external atmospheric pressure. Another problem relates to masking the baseplate in order to form the emitter tips. When the baseplate is no larger than the semiconductor wafers typically used for integrated circuit manufacture, the process disclosed in U.S. Pat. No. 5,391,259 to David Cathey, et al. works splendidly, as the mask particles can be formed from photoresist resin using a conventional photolithography process. However, when the baseplate is larger than those semiconductor wafers, conventional photolithographic techniques utilized in the integrated circuit manufacturing industry are much more difficult to apply. This disclosure is directed toward the problem of forming emitter tips on a large area baseplate.
Erie Knappenberger of Micron Display Technology, Inc. has proposed a new method for forming a mask pattern on a field emission display baseplate using beads or particles as the masking medium. As etch masks for a random pattern of similarly sized dots formed by dispensing glass or plastic beads suspended in a solution on an etchable surface are known to suffer from the problem of aggregation (i.e., multiple beads aggregating together on the surface), a nebulizer or atomizer is used to generate an aerosol containing particles. A monodispersed aerosol may be produced by utilizing a nebulizer or atomizer which produces droplets which are less than twice the size of the beads or particles within the mixture that is to be atomized. Alternatively, the mixture may be diluted so that the probability of two particles or beads being included within a single droplet is small. The aerosol thus created is then applied to a substrate, producing a uniform monolayer of particles having substantially no aggregation. The particles may be used as a micropoint mask pattern which, when subjected to an etch step, forms field emitter tips for a field emission display or other micro-type structures. An alternative method for minimizing aggregation is to use two types of particles, one of which functions as a masking particle, the other which functions as a spacer particle. Thus, even if aggregation of particles is intentionally generated, the spacer particles may be removed by various techniques such as a chemical dissolution or evaporation, thereby minimizing aggregation of the masking particles themselves.
Another masking technique taught by U.S. Pat. No. 5,676,853 to James J. Alwan, utilizes a mixture of mask particles and spacer particles. The spacer particles space the mask particles apart from one another, and the ratio of spacer particle size to mask particle size and the ratio of spacer particle quantity to mask particle quantity control the distance between mask particles and the uniformity of distribution of mask particles.
An additional masking technique taught by U.S. Pat. No. 5,510,156 to Yang Zhao utilizes latex spheres which are deposited in a monolayer on a surface, shrunk to reduce their diameters, and subsequently covered with an aluminum layer. When the reduced-diameter spheres are dissolved, apertures are formed in the aluminum layer, and the apertures are subsequently utilized to etch an underlying layer.
Still another masking technique is taught by U.S. Pat. No. 5,399,238 to Nalin Kumar. This technique relies on physical vapor deposition to place randomly distributed metal nuclei on a surface. The nuclei form a discontinuous etch mask on the surface of a layer to be etched.
Even under the best of circumstances, the use of the foregoing masking techniques will produce totally random patterns.
A more regular mosaic pattern may be produced by the process disclosed in U.S. Pat. No. 4,407,695 to Harry W. Deckman. Using this process, a monolayer film of spherical colloidal particles is deposited on a surface to be etched. A spinning step which applies centripetal force to the particles is employed to improve packing density. The packed monolayer is then ion etched to produce tapered columnar features. The tapering of the features results from continuing degradation of the colloidal particles during the ion etch step.
A masking technique similar to that patented by Deckman is disclosed in U.S. Pat. Nos. 5,220,725; 5,245,248 and 5,660,570 to Chung Chan, et al. This technique is disclosed in the context of fabricating an interconnection device having atomically sharp projections which can function as field emitters at voltages compatible with conventional integrated circuit structures. The projections are formed by creating a monolayer of latex microspheres on a surface to be etched by spraying or pouring a colloidal suspension of the microspheres on the surface and, then, subjecting the monolayer covered surface to either a wet etch or a reactive-ion etch.
What is needed is a simplified process for forming more regular mask patterns having no masking defects caused by two or more masking particles being too close to one another. The desired process should be capable of producing mask patterns which suffer little or no degradation during plasma etches. In addition, the process should be capable of forming masks which are usable for both reactive-ion etches and wet etches.
BRIEF SUMMARY OF THE INVENTION
The heretofore expressed needs are fulfilled by a new process for forming a mask pattern. Beads, each of which has a substantially unetchable core covered by a removable spacer coating are used to form a discontinuous, regular hexagonal mask pattern. Each of the beads is preferably both spherical and of a particular size, as is each of the cores. For a preferred embodiment of the process, a reactive-ion-etchable material layer (hereinafter “the target layer”) is coated with a thin thermo-adhesive layer. A bead confinement wall, or frame, is then secured to the peripheral edges of the target layer using one of several available techniques. For example, the confinement wall may be bonded to the thermo-adhesive layer, or it may be secured to the target layer with spring clips. In the former case, the confinement wall may be heated so that when it is placed on the thermo-adhesive layer, it bonds thereto. Beads are then dispensed onto the thermo-adhesive layer, in a quantity at least sufficient to form a hexagonally packed monolayer on the adhesive layer within the boundaries of the confinement wall. The bead-covered substrate is then subjected to vibration of a frequency and amplitude that will cause a settling of the beads to their lowest energy level, a state where optimum packing is achieved with a hexagonal monolayer bead pattern in contact with the thermo-adhesive layer.
Optimum hexagonal packing having been achieved, the resultant assembly is heated, causing the layer of beads directly in contact with the adhesive layer to adhere thereto. The beads which are not in contact with the adhesive layer do not adhere to it. The unadhered beads are then discarded. This is accomplished, most easily, by inverting the assembly. They may also be removed by washing them from the assembly, after which the assembly is dried.
Spacer shell material is then removed from each of the beads, leaving only the cores visible in a top plan view. At least two methods may be employed to remove the spacer shell material between the non-etchable bead cores. The bead-coated substrate may be subjected to a first reactive-ion etch which etches away all of the spacer material except that which is beneath the cores and which is in bonded contact with the adhesive layer overlaying the substrate. The first reactive-ion etch chemistry is preferably selected such that it selectively etches the spacer material, but does not significantly etch either the cores or the target layer. If the target layer is etched simultaneously with the spacer material, uneven etching of the target layer will occur, as the areas of the target layer between the beads will etch first. The regions of the target layer closest to the cores will be the last areas exposed to reactive ion bombardment. Alternatively, the spacer material on the beads may be sublimable at elevated temperatures. Thus, as the coating on the beads sublimates, each non-etchable bead core will settle until it is eventually in direct contact with the adhesive layer. The core-masked target layer is then subjected to a second reactive-ion etch, which etches the target layer and forms a column beneath each core. If the target layer is laminar and is etched clear through to an underlying layer, a circular island of target layer material remains beneath each core. The cores are then removed, as well as any remaining spacer material beneath them.
In the case where a laminar target layer is etched clear through to an underlying layer, the circular islands of target layer material that remain may be used as a secondary mask pattern during a wet isotropic etch of the underlying layer. Such a combination of a unidirectional reactive-ion etch using the bead cores as a primary mask and an omnidirectional wet etch using the islands formed by the plasma etch as a secondary mask may be used to form micropoint cathode emitter tips in an underlying conductive or semiconductive layer.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The following illustrative figures are not drawn to scale, and are meant to be merely representative of the disclosed process:
FIG. 1 is a cross-sectional view of a spherical bead having a spherical core covered with a spacer shell;
FIG. 2 is a cross-sectional side view of an in-process baseplate assembly, which includes a silicate glass plate, on which has been deposited a conductive layer, a silicon layer, a masking layer, and a thermo-adhesive layer;
FIG. 3A is a cross-sectional view of the in-process baseplate assembly of FIG. 2 following the affixing of a confinement wall to the periphery thereof;
FIG. 3B is a cross-sectional side view of an alternative structure for affixing the confinement wall to the substrate structure of FIG. 2 using spring clips;
FIG. 4 is a cross-sectional side view of the in-process baseplate assembly structure of FIG. 3A following the dispensing of beads within the boundaries of the confinement wall;
FIG. 5 is a cross-sectional side view of the in-process baseplate assembly of FIG. 4 during a vibrational step which promotes a continuous, even hexagonal packing pattern of a monolayer of beads on the surface of the thermo-adhesive layer;
FIG. 6 is a top plan view of an ideal arrangement of hexagonally packed beads;
FIG. 7 is a cross-sectional side view of the in-process baseplate assembly of FIG. 5 following an elevated temperature step which causes the lower layer of beads to adhere to the thermo-adhesive layer;
FIG. 8 is a cross-sectional side view of the in-process baseplate assembly of FIG. 7 following the discarding of unadhered beads;
FIG. 9 is a cross-sectional side view of the in-process baseplate assembly of FIG. 8 following removal of the confinement wall;
FIG. 10 is a cross-sectional side view of the in-process baseplate assembly of FIG. 9 following a first plasma etch step which removes all spacer material from the beads except that which is immediately beneath each core;
FIG. 11 is a cross-sectional side view of the in-process baseplate assembly of FIG. 10 following a second plasma etch step which anisotropically etches the masking layer to form a plurality of masking islands therefrom;
FIG. 12 is a cross-sectional side view of the in-process baseplate assembly of FIG. 11 following the removal of the cores, the spacer material which underlies each core, and remaining portions of the thermo-adhesive layer;
FIG. 13 is a cross-sectional side view of the in-process baseplate assembly of FIG. 12 following a first isotropic etch which forms dull micropoint cathode emitter tips within the silicon layer;
FIG. 14 is a cross-sectional side view of the in-process baseplate assembly of FIG. 13 following removal of the masking islands; and
FIG. 15 is a cross-sectional side view of the in-process baseplate assembly of FIG. 14 following a second isotropic etch which sharpens the existing dull micropoint cathode emitter tips.
DETAILED DESCRIPTION OF THE INVENTION
Although the masking process of the present invention may be utilized for nearly any masking application where an ordered array of circular features is desired, it is especially useful for the masking of substrates or coated substrates which are so expansive that conventional photolithography exposure equipment will not easily accommodate them. As a concrete example of the utility of the invention, it will be disclosed in the context of a process for fabricating an array of emitter tips for the microcathodes of a baseplate assembly for a field emission display.
As a matter of clarification, a brief description of etch technology is in order. An etch that is isotropic is omnidirectional. That is, it etches in all directions at substantially the same rate. As a general rule, solution etches (usually called “wet etches”) are isotropic. For example, hydrofluoric acid solutions are commonly used to isotropically etch silicon. Although the term anisotropic literally means not isotropic, in the integrated circuit manufacturing industry, it has come to connote substantial unidirectionality. Thus, an etch that is anisotropic etches in substantially a single direction (e.g., straight down). Plasma etches typically have both isotropic and anisotropic components. Plasma etches are normally performed within an etch chamber. A conventional etch chamber generally has an upper electrode and a lower electrode to which the target is affixed. During a plasma etch, ions accelerated by an electric field applied between the two electrodes impact the target. Upon impact, the ions react with atoms on the target surface to form gaseous reaction products which are removed from the etch chamber. It is this acceleration of reactive ions within the electric field that imparts substantial unidirectionality to a plasma etch. The anisotropic component of a plasma etch can be optimized through the careful selection of equipment, etch chemistries, power settings and positioning of the article to be etched within the etch chamber. In the context of this disclosure, the term isotropic means omnidirectional; the term anisotropic means downwardly unidirectional.
The emitter tips will be formed from a silicon layer by, first, creating an array of masking islands on the surface of the silicon layer and, then, performing an isotropic etch to form an emitter tip beneath each masking island. Although the materials utilized in the various layers of the representative process are presently considered to be the preferred materials for the desired application, the inventor wishes to emphasize that the process may be used for the same application, or for other applications, using a different combination of etchable and nonetchable materials.
Referring now to FIG. 1 , a spherical bead 100 is depicted in a cross-sectional view. The bead has a spherical core 101 covered with a spacer shell 102 . The materials from which the core 101 and the shell 102 are formed are selected such that during a particular anisotropic plasma etch, the material comprising the shell 102 may be etched selectively with respect to the material comprising the core 101 . In other words, during the plasma etch, the shell will etch, while the core will not. For example, the bead cores may be formed from glass, iron or many other plasma etch-resistant materials compatible with integrated circuit processing. The shell material, on the other hand, may be formed from polymers, glasses or many other materials which are compatible with integrated circuit processing, and which may be plasma etched selectively with respect to the core material. Alternatively, the shell 102 may be formed from a material that sublimates rapidly at elevated temperatures compatible with integrated circuit manufacture (i.e., those within a range of about 200–400° C.). Paradichlorobenzene and napthalene are two such common materials. The bead cores 101 are employed as elemental masking elements, while the shells 102 set or define the spacing between the bead cores 101 . Spacing between elemental masking elements (i.e., the cores 101 ) may be adjusted by varying thickness of the shells 102 . In the drawings appended to this disclosure, beads are depicted, for the sake of clarity, as though the cores 101 are opaque elements, while the shells 102 are depicted as though transparent. However, nothing should be inferred regarding the type of materials used from the adoption of this illustration convention.
Referring now to FIG. 2 , a conductive layer 202 is deposited on a silicate glass plate 201 . As conductive layer 202 must be fairly stable during subsequent elevated temperature steps, suicides of metals such as titanium, tungsten, cobalt, nickel, platinum, and paladium may be used. A silicon layer 203 (also referred to herein as “the cathodic layer”) is deposited over the conductive layer 202 . A masking layer 204 is then deposited over the silicon layer 203 . The masking layer 204 may be a nitrided material such as silicon nitride, titanium nitride, or titanium carbonitride, a silicide of a refractory metal such as titanium, platinum or tungsten, or an unreacted metal such as aluminum, titanium, or copper. The primary consideration during the selection of the material for masking layer 204 is that it be substantially unetchable during an anisotropic plasma etch of silicon layer 203 . Finally, a thermo-adhesive layer 205 is deposited on the upper surface of masking layer 204 . The thermo-adhesive layer 205 may be a wax or a polymer material which softens and becomes tacky when heated, and which preferably reversibly hardens when cooled. The wax may be, for example, an ester, a fatty acid, a long-chain alcohol, or a long-chain hydrocarbon. The polymer material may be, for example, a polyurethane resin, a polyester resin, or an epoxy resin. The silicate glass plate 201 with the additional layers deposited thereon shall now be referred to as the in-process baseplate assembly 206 .
Referring now to FIG. 3A , a bead confinement wall 301 A is attached to the periphery of the thermo-adhesive layer 205 of the in-process baseplate assembly 206 . The wall 301 A may be formed from nearly any rigid or semi-rigid material such as metal, glass, or high-temperature polymeric plastic. The wall 301 A may be attached by heating it to a temperature in excess of that which will cause the thermo-adhesive layer 205 to soften and become tacky, placing it on the thermo-adhesive layer 205 , and allowing the entire in-process baseplate/wall assembly 302 to cool. Alternatively, the wall 301 A may be attached by placing it on the thermo-adhesive layer 205 , heating the resulting in-process baseplate/wall assembly 302 to a temperature in excess of that which will cause the thermo-adhesive layer 205 to soften and become tacky, and allowing the entire assembly to cool.
FIG. 3B depicts an alternative method of affixing the confinement wall to the in-process baseplate assembly 206 . A bead confinement wall 301 B is clipped to the in-process baseplate assembly 206 with spring clips 303 . For the sake of simplification, and because the method by which the bead confinement wall ( 301 A or 301 B) is attached to the in-process baseplate assembly 206 insignificantly affects the remainder of the process, the in-process baseplate/wall assembly of FIG. 3B and that of FIG. 3A shall both be referred to, hereinafter, as item number 302 .
Referring now to FIG. 4 , a quantity of beads 100 , such as those depicted in FIG. 1 , has been dispensed onto the in-process baseplate/wall assembly 302 of FIG. 3A or FIG. 3B . The quantity of the dispensed beads 100 is at least sufficient to create a hexagonally packed monolayer of beads 100 on the entire surface of the thermo-adhesive layer enclosed by the confinement wall 301 A or 301 B. Confinement wall 301 A or 301 B prevents the dispensed beads 100 from rolling off the edge of the in-process baseplate/wall assembly 302 .
Referring now to FIG. 5 , a vibration step is performed which promotes continuous, even hexagonal packing pattern of a monolayer of beads 100 on the surface of the thermo-adhesive layer 205 . Ideally, the vibrational movement will include a vertical component that is just barely sufficient to dislodge improperly packed beads, but not those which are already properly packed in the bottom-most layer. FIG. 6 depicts an ideal arrangement of hexagonally packed beads.
Referring now to FIG. 7 , once a hexagonally packed monolayer 701 that is in contact with the thermo-adhesive layer 205 has been attained, the temperature of in-process baseplate/wall/bead assembly 702 is elevated, causing each of the beads in the lower bead layer 701 to adhere to the thermo-adhesive layer 205 .
Referring now to FIG. 8 , once the in-process baseplate/wall/bead assembly 702 has cooled, unadhered beads (i.e., those not in lower layer 701 ) are discarded. This is accomplished, most easily, by inverting the assembly. They may also be removed by washing them from the assembly 702 , after which the assembly 702 is dried.
Referring to FIGS. 8 and 9 , the bead confinement wall 301 A may be removed by applying heat to the upper edge 901 thereof, allowing the applied heat to transfer through the wall 301 A until the thermo-adhesive is softened along the lower edge 902 of the wall 301 A and the wall 301 A can be released from the thermo-adhesive layer 205 . Likewise, confinement wall 301 B may be removed by releasing the spring clips 303 (see FIG. 3B ).
Referring now to FIG. 10 , a first anisotropic etch is used to remove all spacer material of shell 102 from the beads 100 except that circular mask island 1101 which is beneath each core 101 . The first anisotropic etch chemistry is selected such that neither the cores 101 nor the masking layer 204 is etched by the first plasma etch.
Referring now to FIG. 11 , a second anisotropic etch is used to etch the masking layer 204 and stop on the silicon layer 203 , forming a circular mask island 1101 beneath each core 101 . An alternative embodiment of the process combines the first and second anisotropic etches so that the spacer material of shell 102 is etched from the beads 100 during the same step that etches the masking layer 204 . In this case, the etch chemistry should be carefully selected to stop on the upper surface of silicon layer 203 .
Referring now to FIG. 12 , the remaining portions of the silicon layer 203 , the cores 101 and spacer material of shell 102 beneath each core 101 have been removed by washing the entire in-process baseplate assembly 206 in a solvent in which the thermo-adhesive layer 205 dissolves. For wax-based thermo-adhesives, an appropriate solvent selected from the ether, alkane, alcohol and haloalkane groups may be used. For polymer resins, a ketone such as acetone may be used.
Referring now to FIG. 13 , an isotropic etch is used to form an array of dull micropoint cathode emitter tips 1301 from the silicon layer 203 . If the isotropic etch were continued until the tips 1301 became sharp pointed, the mask islands 1101 might become detached from the tips 1301 and interfere with etch rate uniformity.
Referring now to FIG. 14 , the circular mask islands 1101 are removed with an isotropic etch that is selective for the material from which the primary masking layer 204 was formed over the silicon layer 203 .
Referring now to FIG. 15 , the dull-pointed micropoint cathode emitter tips 1301 formed with the isotropic etch, the results of which are depicted in FIG. 13 , are sharpened with a subsequent isotropic etch to form an array of sharpened micropoint cathode emitter tips 1501 .
For those familiar with etching technology, it should be clear that a mask pattern formed by bead cores 101 adhered directly on the surface of the silicon layer 203 could not be used to form emitter tips, as an isotropic etch of such a structure would have resulted in a fairly constant material removal rate over the entire surface of silicon, as each core is supported (at least theoretically) by only a single point of silicon material having no area. If such a structure were isotropically etched, the cores would sink at a fairly constant rate as silicon material supporting each core was etched away. The sinking of the cores would eventually likely affect inter-core spacing. In any case, such non-differential removal rates would not produce a predictable pattern, much less an array of emitter tips. Thus, it is necessary to transfer the bead core pattern to an underlying laminar layer (i.e., masking layer 204 ). Each circular masking island 1101 formed from the masking layer 204 is in contact with the silicon layer 203 throughout its entire circumference. An isotropic etch of the silicon layer 203 will gradually undermine the silicon surrounding each masking island 1101 to form the pointed tip structures.
In this specification and in the appended claims, a layer which is etched using the bead cores 101 as masking elements during the etch may also be referred to as the target layer. Thus, for the previously disclosed process of forming emitter tips, the masking layer 204 is also the target layer. It is, however, conceivable that there may be a need for a final structure having a pattern such as the one which was etched into masking layer 204 . Thus, for the appended claims, the target layer could be a masking layer, such as layer 204 , to which the bead core pattern is transferred during a preliminary step, or it could be a layer from which a pattern of permanent structural elements such as columns or islands is anisotropically etched.
It should be evident that the heretofore described process is capable of forming an array of micropoint cathode emitter tips for a field emission display. Those having ordinary skill in the art will recognize that the process may have many other applications for creating regularly ordered mask patterns on surfaces which are so expansive that photolithography using a conventional stepper exposure apparatus is impractical.
Although only several variations of the basic process are described, it will be obvious to those having ordinary skill in the art that changes and modifications may be made thereto without departing from the scope and the spirit of the process and products manufactured using the process as hereinafter claimed.
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A process for forming an etch mask having a discontinuous regular pattern utilizes beads, each of which has a substantially unetchable core covered by a removable spacer coating. Beads are dispensed as a hexagonally packed monolayer onto a thermo-adhesive layer. Following a vibrational step which facilitates hexagonal packing of the beads, the resultant assembly is heated so that the beads adhere to the adhesive layer. Excess beads are then discarded. Spacer shell material is then removed from each of the beads, leaving core etch masks. The core-masked target layer is then plasma etched to form a column of target material directly beneath each core. The cores and any spacer material underneath the cores are removed. The resulting circular island of target material may be used as an etch mask during wet isotropic etching of an underlying layer.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a composition of matter containing a complex of an alkoxylated amine, hydrocarbylsulfonic acid and adenine and to a lubricating oil composition containing the complex and its use to reduce friction and improve fuel economy in an internal combustion engine.
2. Description of the Related Art
There are many instances, as is well known, particularly under "Boundary Lubrication" conditions where two rubbing surfaces must be lubricated, or otherwise protected, so as to prevent wear and to insure continued movement. Moreover, where, as in most cases, friction between the two surfaces will increase the power required to effect movement and where the movement is an integral part of an energy conversion system, it is most desirable to effect the lubrication in a manner which will minimize this friction. As is also well known, both wear and friction can be reduced, with various degress of success, through the addition of a suitable additive or combination thereof, to a natural or synthetic lubricant. Similarly, continued movement can be insured, again with varying degress of success, through the addition of one or more appropriate additives.
The primary oil additive for the past 40 years for providing antiwear and antioxidant properties has been zinc dialkyldithiophosphate (ZDDP). Oil formulations containing ZDDP, however, require friction modifiers in order to reduce energy losses in overcoming friction. Such energy losses result in lower fuel economy. Moreover, oil additive packages containing ZDDP have environmental drawbacks. ZDDP adds to engine deposits which can lead to increased oil consumption and emissions. Moreover, ZDDP is not ash-free. Various ashless oil additive packages have been developed recently due to such environmental concerns.
It would be desirable to have a lubricating oil composition which provides excellent friction reducing, fuel economy properties and environmentally beneficial (less fuel, i.e., less exhaust emission) properties.
SUMMARY OF THE INVENTION
This invention relates to a novel composition of matter containing a complex of alkoxylated amine, hydrocarbylsulfonic acid and adenine and to an improved lubricating oil composition having improved friction reducing properties which results in improved fuel economy in an internal combustion engine. The composition of matter has the formula (I) and is a complex comprising the reaction product of an alkoxylated amine, hydrocarbylsulfonic acid and adenine, said complex having the formula ##STR2## where R is a hydrocarbyl group of from 2 to 22 carbon atoms, R 1 is a hydrocarbyl group of from 2 to 30 carbon atoms, R 2 is hydrogen or a hydrocarbyl group of 1 to 20 carbon atoms, x and y are each independently integers of from 1 to 15 with the proviso that the sum of x+y is from 2 to 20, and a, b and c are independent numbers from 1.0 to 3.0 wherein the ratios between a:b, a:c and b:c range from 1.0:3.0 to 3.0:1.0. In another embodiment, there is provided a lubricant composition comprising a major amount of a lubricating oil basestock and a minor amount of complex having the formula (I), and a method for reducing friction in an internal combustion engine which comprises operating the engine with a lubricating oil basestock containing an amount effective to reduce friction of a complex having the formula (I).
DETAILED DESCRIPTION OF THE INVENTION
In the lubricating oil composition of the present invention, the lubricating oil will contain a major amount of a lubricating oil basestock. The lubricating oil basestock are well known in the art and can be derived from natural lubricating oils, synthetic lubricating oils, or mixtures thereof. In general, the lubricating oil basestock will have a kinematic viscosity ranging from about 5 to about 10,000 cSt at 40° C., although typical applications will require an oil having a viscosity ranging from about 10 to about 1,000 cSt at 40° C.
Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal and shale.
Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs thereof, and the like. Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids with a variety of alcohols. Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers.
Silicon-based oils (such as the polyakyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins, and the like.
The lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
In the oil soluble complexes of the present invention having the formula (I) above, R is preferably a hydrocarbyl group of from 6 to 18 carbon atoms, R 1 is preferably a hydrocarbyl group of from 2 to 26 carbon atoms and R 2 is preferably hydrogen or a hydrocarbyl group of from I to 16 carbon atoms, especially hydrogen. The hydrocarbyl groups include aliphatic (alkyl or alkenyl) and alicyclic group which may be substituted with hydroxy, amino, mercapto and the like and the hydrocarbyl group may be interrupted by oxygen, nitrogen and sulfur. The sum of x+y is preferably 2 to 15, especially 5 to 15.
The complexes of the invention are prepared from the reaction of alkoxylated, preferably propoxylated or ethoxylated, most preferably ethoxylated amines and adenine with alkylsulfonic acid. Ethoxylated and/or propoxylated amines are commercially available from Sherex Chemicals under the trade name Varonic and from Akzo Corporation under the trade names Ethomeen®, Ethoduomeen® and Propomeen®. Examples of preferred amines include ethoxylated (5) cocoalkylamine, ethoxylated (2) tallowalkylamine, ethoxylated (15) cocoalkylamine and ethoxylated (5) soyaalkylamine.
The present hydrocarbylsulfonic acids are commercially available or may be prepared by methods known in the art. Adenine is also commercially available and the secondary amine derivatives prepared by methods known in the art.
The complexes according to the invention are prepared by adding alkylsulfonic acid to a mixture of adenine and alkoxylated amine. Because of the exothermic nature of the reaction, the reaction mixture should be stirred during addition of alkylsulfonic acid.
The precise stoichiometry of the bonding in the complexes of the formula (I) is not known since each molecule in the complex may have several sites which can take part in the hydrogen bonding process either as an acceptor or donor. Because of the multipilicity of bonding possibilities, the molar ratios a:b:c can be varied over a wide range based on the donor/acceptor sites on each of the three molecules and therefore a, b and c in formula (I) are numbers which are not necessarily integral. There exist a total of thirty combinations of interaction sites between the three molecules comprising the complex of the formula (I). For example, a:b:c may be 1:2:1 or 1:1:3 which are just two of the thirty possible combinations.
The lubricant oil composition according to the invention comprises a major amount of lubricating oil basestock and an amount effective to increase fuel economy of the complex of formula (I). Typically, the amount of complex will be from about 0.001 wt % to about 5 wt %, based on oil basestock. Preferably, the amount of complex is from about 0.05 wt % to about 1.0 wt %.
If desired, other additives known in the art may be added to the lubricating oil basestock. Such additives include dispersants, antiwear agents, antioxidants, rust inhibitors, corrosion inhibitors, detergents, pour point depressants, extreme pressure additives, viscosity index improvers, other friction modifiers, hydrolytic stabilizers and the like. These additives are typically disclosed, for example, in "Lubricant Additives" by C. V. Smalhear and R. Kennedy Smith, 1967, pp. 1-11 and in U.S. Pat. No. 4,105,571, the disclosures of which are incorporated herein by reference.
The lubricating oil composition of this invention can be used in the lubrication system of essentially any internal combustion engine, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad engines, and the like. Also contemplated are lubricating oils for gas-fired engines, alcohol (e.g., methanol) powered engines, stationary powered engines, turbines, and the like.
This invention may be further understood by reference to the following example, which includes a preferred embodiment of this invention.
Example 1
This Example illustrates the preparation of a complex containing ethoxylated amine, alkylsulfonic acid and adenine according to the invention. 41 g of ethoxylated(2)tallowamine and 1 g of adenine were heated to 60° C. with stirring in a 3-neck round bottom flask fitted with a thermometer and a water cooled condenser. 58 g of alkylsulfonic acid having the formula ##STR3## was added gradually to the stirred amine/adenine solution. During addition, the temperature rose to 105° C. due to the exothermic reaction between acid and amine. The reaction mixture was maintained at 105° C. for 1.5 hours and then cooled to room temperature. The reaction mixture was a complex according to the invention and was used without further purification.
EXAMPLE 2
The complex containing ethoxylated amine, alkylsulfonic acid and adenine is an effective friction modifier as shown in this example. The Ball on Cylinder (BOC) friction tests were performed using the experimental procedure described by S. Jahanmir and M. Beltzer in ASLE Transactions, Vol. 29, No. 3, p. 425 (1985) using a force of 0.8 Newtons (1 Kg) applied to a 12.5 mm steel ball in contact with a rotating steel cylinder that has a 43.9 mm diameter. The cylinder rotates inside a cup containing a sufficient quantity of lubricating oil to cover 2 mm of the bottom of the cylinder. The cylinder was rotated at 0.25 RPM. The friction force was continuously monitored by means of a load transducer. In the tests conducted, friction coefficients attained steady state values after 7 to 10 turns of the cylinder. Friction experiments were conducted with an oil temperature of 100° C. Various amounts of complex prepared in Example 1 were added to solvent 150 N. The results of BOC friction tests are shown in Table 1.
TABLE 1______________________________________Wt % of Ethoxylated(2)Tallowamine,Alkylsulfonic Acid and Adenine Complex Coefficientin Solvent 150N* Of Friction______________________________________0.00 0.320.1 0.200.2 0.180.3 0.130.5 0.100.8 0.071.0 0.06______________________________________ *S150 is a solvent extracted, dewaxed, hydrofined neutral lube base stock obtained from approved paraffinic crudes (viscosity, 32 cSt at 40° C., 150 Saybolt seconds)
As can be seen from the results in Table 1, as little as 1.0 wt % of complex shows an 81% decrease in the coefficient of friction. These results demonstrate that the present complexes are capable of significant reductions in the coefficient of friction of a lubricant basestock which results in less friction and hence greater fuel economy when the lubricated oil is used in an internal combustion engine.
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A composition of matter having utility in lubricant formulations, said composition being the reaction product of adenine, alkoxylated amine and hydrocarbylsulfonic acid and having the formula ##STR1## where R is a hydrocarbyl group of from 2 to 22 carbon atoms, R 1 is a hydrocarbyl group of from 2 to 30 carbon atoms, R 2 is hydrogen or a hydrocarbyl group of from 1 to 20 carbon atoms, x and y are each independently integers of from 1 to 15 with the proviso that the sum of x+y is from 2 to 20, and a, b and c are independent numbers from 1.0 to 3.0 wherein the ratios between a:b, a:c and b:c range from 1.0:3.0 to 3.0:1.0.
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FIELD OF THE INVENTION
[0001] This invention relates to fastener accessories, more particularly to retainers used to prevent the undesired disengagement of nuts from spindles.
BACKGROUND OF THE INVENTION
[0002] Retaining nuts are used to secure devices, for example a hub, upon a spindle. Typically both the spindle and nut are threaded. Devices are secured upon the spindle before the nut is screwed onto the spindle, the nut abutting the exterior side of the device. Vibration, associated with the rotation of the spindle, may cause the nut to unscrew and disengage from the spindle. The device is no longer secured and may detach itself from the spindle.
[0003] Numerous devices have been used to secure the nut to the spindle. Simple versions of these devices include lock washers, jam nuts, self-locking nuts and slotted nuts used in conjunction with a cotter pin. More advanced versions of securing devices include the controlled axle nut system of U.S. Pat. No. 5,795,037 to Hagelthorn and the nut and bolt locking system of U.S. Pat. No. 5,967,723 to Duran. Hagelthorn provides a retainer member which must be threaded onto the spindle. The threading process can be difficult, especially in cases where the parts are being assembled by machine. Potential assembly difficulties are cross-threading and the need to protect the internal threads of the retainer from damage. Duran provides a nut and washer locking combination where the washer deforms to form an interference fit with flats on the face of the nut as the nut is tightened upon a bolt. Locking contact between the nut and washer occurs only at one end of the nut.
[0004] A system which can be easily assembled and which provides a strong locking connection between the spindle nut and the nut retainer is desired.
SUMMARY OF THE INVENTION
[0005] The present invention overcomes these and other disadvantages of the prior art by providing a spindle nut retainer which is easily attached to a spindle/nut system and which creates a strong connection between the nut and spindle.
[0006] The invention provides in one aspect a spindle nut retainer which prevents a nut from unthreading and becoming detached from a spindle. The spindle nut retainer includes both a base section and peripheral section which together form a cup shape. The base section includes a hole through which the spindle passes. The peripheral section provides a plurality of fingers which form windows within the peripheral section. The fingers also include nut engaging surfaces which engage the corners of the nut to provide a locking connection.
[0007] The invention provides in another aspect a spindle nut retainer which includes both a base section and peripheral section which together form a cup shape. The base section includes a hole through which the spindle passes, and the peripheral section includes a plurality of fingers which create one or more longitudinal windows therebetween, the fingers including a flared end bent towards the center of the spindle nut retainer.
[0008] The spindle nut retainer of the present invention may be easily attached over the nut without having to be threaded upon the spindle. Further, the spindle nut retainer creates a strong locking connection along the corners of the spindle nut. These and other aspects of the invention are herein described in particularized detail with reference to the accompanying Figures.
BRIEF DESCRIPTION OF THE FIGURES
[0009] [0009]FIG. 1 is a cutaway view of a spindle nut locking system;
[0010] [0010]FIG. 2 is a top view of a spindle nut retainer;
[0011] [0011]FIG. 3 is a side view of the spindle nut retainer; and
[0012] [0012]FIG. 4 is a perspective view of an alternate embodiment of the spindle nut retainer.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Referring to the drawings, FIG. 1 illustrates a preferred spindle assembly 10 according to the invention. The assembly 10 prevents a nut 60 from becoming disengaged from a spindle 50 . Disengagement typically occurs as a result of vibration of the spindle 50 . The spindle assembly 10 as described in more detail below, comprises a spindle nut retainer 20 , a nut 60 , and a spindle 50 . In the illustrated embodiment, the spindle assembly 10 also comprises a hub 70 , one or more bearings 90 and one or more washers 80 .
[0014] Embodiments of the spindle nut retainer 20 are shown in FIGS. 2, 3 and 4 and comprise an integral base section 22 and peripheral section 28 in a cup-shaped configuration. In separate embodiments the spindle nut retainer 20 is made from materials such as steel as shown in FIG. 4, or a polymer as shown in FIGS. 2 and 3. The base section 22 may be flat, having an interior face 24 and an exterior face 26 . The base section 22 includes a centrally located aperture 34 . The area of the base section 22 around the aperture 34 may be of increased thickness for structural reinforcement. In an embodiment wherein the spindle nut retainer is made of steel, the base section 22 may include a bent tab 25 . The bent tab 25 may be integrally formed with the base section 22 and bent to extend from the base section 22 perpendicularly. The aperture 34 may be D-shaped. A flat portion of the base section forming the flat section of the “D” is an interference surface 27 . The interference surface 27 is transverse to the interior face 24 and exterior face 26 of the base section 22 As a result, there is rotational interference when the retainer 20 is positioned upon an area of the spindle 50 having a D-shaped cross section. In an embodiment wherein the spindle nut retainer is made of steel, the surface of bent tab 25 may be the interference surface 27 . The base section 22 may include a manufacturer's brand name.
[0015] The peripheral section 28 comprises the walls of the cup-shaped configuration of the spindle nut retainer 20 . The peripheral section 28 includes an exterior surface 30 and an interior surface 32 . The exterior surface 28 may be circular in shape. A first end 31 of the peripheral section is integral with the base section 22 . The peripheral section 28 of the spindle nut retainer may include a series of longitudinal windows 36 aligned in an alternating manner with and defined by solid fingers 38 of the peripheral section 28 . The number of windows 36 on a spindle nut retainer 20 may be related to the number of corners on the nut 60 , for example two times the number of corners. This allows the spindle nut retainer 20 to be easily fit over the nut 60 , without having to rotate the nut 60 into a position of exact alignment. In any position upon the peripheral section 28 , an oversized window 37 may be created by removing a finger 38 . The windows 36 and fingers 38 allow for increased flexibility of the spindle nut retainer 20 and ease in the manufacturing process. The longitudinal windows 36 also allow the passage of one or more corners 64 of the nut through the spindle nut retainer 20 .
[0016] The longitudinal windows 36 may extend all the way to the first end 31 of the peripheral section, thus, creating notches 35 within the exterior surface 30 of the base section 22 . A second end 33 of the peripheral section, opposite the base section 22 , may be a continuous ring. The longitudinal windows 36 , when the ring is continuous do not extend completely to the second end 33 of the peripheral section 28 . In an embodiment wherein the spindle nut retainer is made of steel, the second end 33 of the peripheral section is not a ring but instead is comprised of the flared ends 39 of each individual finger 38 .
[0017] In an embodiment wherein the spindle nut retainer 20 is made of polymer, the second end 33 of the peripheral section 28 may have an internal diameter which is smaller than the internal diameter of the remainder of the peripheral section 28 . The second end 33 of the peripheral section 28 will then snap over the nut 60 and be locked in place as shown in FIG. 1. In an embodiment wherein the spindle nut retainer 20 is made of steel, the flared ends 39 of each finger 38 may be bent internally to create a locking function. Additionally or alternatively in either embodiment, the corners 64 of the nut 60 which pass through the longitudinal windows 36 may be locked in place by the end surfaces 46 of the windows.
[0018] In an embodiment wherein the spindle nut retainer is made of polymer, the peripheral section 28 defines a plurality of nut engaging surfaces 40 . Each nut engaging surface 40 is angled. Each finger 38 includes two adjacent nut engaging surfaces 40 angled to form a point on the interior surface 32 of the peripheral section 28 . The nut engaging surfaces 40 may extend along the entire length of the interior surface 32 of the peripheral section 28 . The nut engaging surfaces 40 create rotational interference between the nut 60 and retainer 20 when the retainer 20 is overlapping the nut 60 . In embodiments wherein the spindle nut retainer is made of polymer the end surfaces 46 of the longitudinal windows 36 work in conjunction with the nut engaging surfaces 40 to lock the nut 60 in place. The nut engaging surfaces 40 will interfere with the corners 64 of the nut 60 if the nut is rotated in relation to the spindle nut retainer 20 or vise versa. The end surface 46 of the longitudinal window 36 will interfere with the corner of the nut 60 when the spindle nut retainer 20 is moved axially. In an embodiment wherein the spindle nut retainer is made of steel, the nut 60 is locked in place by the window side surfaces 48 , as opposed to the nut engaging surfaces, as well as window end surfaces 46 .
[0019] Referring to FIG. 1, the spindle assembly 10 further comprises the nut 60 which includes exterior flats 62 and corners 64 . The nut 62 is commonly formed of steel. The nut 60 functions to hold a hub 70 upon the spindle 50 . The nut 60 is threadedly engaged to the spindle 50 . As previously described the nut 60 is locked in place by the spindle nut retainer 20 . The spindle assembly 10 may further comprise a hub 70 . The hub 70 circumscribes the spindle 50 and rotates freely about the spindle 80 . One or more bearings 90 are used between the hub 70 and spindle 50 to allow free rotational engagement. The hub 70 is located on the interior side of the nut 60 and is restrained from disengagement from the spindle 50 by the nut 60 . The spindle assembly 10 may further comprise one or more washers 80 . In an embodiment, a washer 80 is between the hub 70 and the nut 60 . The washer 80 is flat and provides a surface which abuts both the hub 70 and the nut 60 .
[0020] The spindle assembly 10 further comprises a spindle 50 . In an embodiment, the spindle 50 is part of an automobile. The spindle 50 has multiple sections around which components are circumscribed. In an embodiment, the sections of the spindle 50 have varying diameters. The spindle has two ends. In an embodiment, a section adjacent to one end 52 of the spindle 50 has a D-shaped cross section. This section allows a spindle nut retainer 20 having a D-shaped cross section to circumscribe the spindle 50 which resists rotational movement. One section of the spindle 50 is threaded, allowing engagement with a nut 60 which is similarly threaded.
[0021] Although the invention has been shown and described with reference to certain preferred and alternate embodiments, the invention is not limited to these specific embodiments. Minor variations and insubstantial differences in the various combinations of materials and methods of application may occur to those of ordinary skill in the art while remaining within the scope of the invention as claimed and equivalents.
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A spindle nut retainer is provided for preventing a nut threaded upon a spindle from unthreading and detaching from the spindle. The spindle nut retainer includes an integral base section and peripheral section maintaining a cup-shaped configuration. The base section includes an aperture through which the spindle may pass and the peripheral section includes a plurality of fingers which form windows therebetween used to form a locking connection between the spindle nut retainer and the nut.
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FIELD OF THE INVENTION
[0001] This invention relates to telecommunications equipment and services and, in particular, a method of reverse origination of a telephone call placed by a called party to a calling party via a non-signaling network, (a computer network, for example) instead of a packet switched signaling network (Signaling System 7 (SS7), for example).
BACKGROUND OF THE INVENTION
[0002] According to current prices and tariffs, an inbound U.S. telephone call from another country is more expensive than an outbound U.S. call to that country. This means that if a call is originated in the U.S. for termination in a foreign country, it is typically cheaper than the reversed call, i.e., the same call originated in the foreign country for termination in the U.S. This is particularly true in the emerging free market economies which have less advanced and fewer telecommunications networks than the U.S. Absence of competitive market forces, as well as considerable investment of capital required for entering the telecommunications market, contribute to the existing high cost of telecommunications equipment and services in those countries.
[0003] The significant difference in telephone rates between the U.S. inbound and outbound telephone calls has spawned a new industry of the so-called reverse call origination. The traditional, i.e. forward, origination of a telephone call is from a calling party to a called party. The calling party pays for the call charges with the exception of a collect call, 1-800 call, bill-to-third-party call, certain cellular services, special N00 services where N (2-9) is the first digit for an area code (Numbering Plan Area) of a telephone number, etc. In contrast to the forward call origination, the reverse telephone call is originated from the called party equipment at the request of the calling party. The signaling information associated with the call proceeds in the reverse direction: from a switching office (switch), connected to the called party station via a Private Branch Exchange (PBX), to a switch serving the calling party via another PBX, for example. As known in the art, a signaling network, being a part of a telecommunications network, provides for an exchange of information related to a telephone call for voice/data/video. Typically, such signaling messages carry information regarding call set-up or tear-down, card validation, number translation, and other data transactions associated with the telephone call. Utilizing the reverse call origination, the calling party pays for the call charges even though the call has been originated by the telecommunications equipment serving the called party station.
[0004] As stated above, a significant cost advantage exists in originating an international telephone call from the U.S. To capitalize on cheaper U.S. calling rates and non-trivial price difference, several companies have set up operations in the U.S. for providing reverse call origination services to people abroad who place calls to the U.S. In some cases, the telephone service using the reverse call origination can be used advantageously even for calls that do not terminate in the U.S. These are transitory calls—from one foreign country to another foreign country via the U.S.—that establish the U.S. as a point of origin for obtaining cheaper rates.
[0005] Typically, the providers of the reverse call origination service purchase volume discounted telephone service from major U.S. long distance carriers and then resell it to callers in other countries at a higher premium. By providing the reverse call origination to the callers abroad, the resellers may place inbound international calls at slightly higher U.S. rates than the major U.S. long distance carriers. Nevertheless, the cost of the call is still lower than the cost of an inbound international call originated outside the U.S.
[0006] One of the most widely used methods of the reverse call origination, also known as a call-back service, is based on automatic number identification (ANI) detecting means. For example, an overseas caller Pierre wishes to call Jimmy, a business acquaintance in the U.S. Pierre dials a telephone number of a U.S. based Company ABC which provides the reverse call origination service for international callers. Pierre rings the Company ABC's telephone, for example, several times and then hangs up. Since the call was not completed, Pierre does not incur any charges for it. Based on the transmitted signaling information, the Company ABC determines Pierre's telephone number with the use of the ANI detecting means. The Company ABC, using a “live” or automated operator, then calls Pierre and asks for the called party number, i.e., Jimmy's telephone number. After obtaining the requested number, the Company ABC places the call to Jimmy. If Jimmy answers, then both parties, i.e., Jimmy and Pierre, are held on line, and the operator bridges the call between them. Using this call-back service, Pierre pays the call charges which are based on the U.S. rates even though he initiated the call from outside the U.S.
[0007] The described method has two significant drawbacks. First, the calling party outside the U.S. evades payments to the foreign-based telephone carrier for the call expenses because the initiating call was not completed to the providers of the reverse call origination (Company ABC). The call was purposefully intended not to be completed. The foreign telephone carrier does not collect any money for the uncompleted call even though the telephone carrier incurs expenses for transmitting signaling information associated with the call alerting. Cumulative effect of lost revenues by the foreign carriers may negatively affect foreign relations between the U.S. and other countries, and possibly violate international telecommunications treaties to which the U.S. is a signatory country.
[0008] Adversely affected by this service, the international carriers could either apply pressure on the Company ABC to discourage the reverse call origination or deploy means to outright prevent it. For example, high volume unanswered calls to the U.S. could be easily detected and consequently blocked by the international carrier on a called or calling number basis.
[0009] Setting aside the above issue for a moment, the second disadvantage of the above method includes the need for additional hardware and human resources. Thus, this method requires two outbound U.S. calls (one call leg. is from the Company ABC to Jimmy, and the other call leg is from the Company ABC back to Pierre); the U.S. operator's involvement to set up the calls; and special ANI detecting equipment for determining the calling party's number. The required additional features contribute to the service complexity, and the attending higher cost for the reverse call origination service.
[0010] A more sophisticated method of the reverse call origination eliminates the need for the “live” operator and two phone calls, as disclosed in U.S. Pat. No. 5,027,387 to Moll. In the '387 patent, a system is described having a special REDIC (Reverse Direction Calling) equipment which serves calling and called stations. When a caller desires to cost effectively place a call to another country or to a different time zone within the U.S., the call is. sent to the caller's PBX and then to the REDIC equipment which includes a computer and a database. The computer uses the database to determine whether the call would be cheaper if it were originated by the called party. If so, the calling party's REDIC sends a packetized message via the public network to the called party's REDIC requesting reverse call origination. After the handshaking, screening and confirmation of the request between the two REDICs, the call is originated by the called party rather than the calling party.
[0011] The '387 patent has certain advantages over the previously described ANI-based service, and is well suited for situations in which cheaper calling rates vary based on time of the day that the call is placed and the calling zone within the U.S. Thus, taking into account a three hour difference between Los Angeles and New York, in accordance with the Moll's invention, a 7:00 a.m. call (Eastern Standard Time) between LA and NY will be originated from LA to take advantage of the off-peak telephone rates. On the other hand, a 7:00 p.m. call (Eastern Standard Time) will be originated from NY to save on long distance calls. It is apparent that the cost effectiveness of the calling rates alternates due to the time zone difference. Therefore, the additional expense of installing REDIC equipment will not cause the attending significant loss of revenue for different vendors and service providers, because the number of calls originated from either NY or LA will not, on average, increase or decrease disproportionately.
[0012] The '387 patent, however, does not suggest any incentive for installing the additional REDIC equipment by a common carrier if the calling rates of that carrier are always higher than the other carrier, as is the case with the U.S. and foreign carriers. If the calls always originate from the U.S., the foreign carrier will most certainly refuse to support the reverse call origination and may even lobby its govemment to prohibit the service via diplomatic channels.
[0013] To overcome the above disadvantages of the prior art, the present invention provides for reverse call origination via a non-signaling network without imposing any unfair burden on the foreign carrier for the call setup, tear down, etc. or requiring any additional specialized telephone equipment.
SUMMARY OF THE INVENTION
[0014] The present invention originates a telephone call from a country with low telephone rates to a country with high telephone rates using a non-signaling network, such as a global computer network, for example; originates a telephone call from a country with low telephone rates to a country with high telephone rates without additional specialized telephone equipment or any modifications to switches and databases in either country; originates a telephone call from a country with low telephone rates to a country with high telephone rates without any manipulation of signaling information transmitted by a carrier in the high tariff country; and provides flexible allocation of charges for originating a telephone call from a country with low telephone rates to a country with high telephone rates.
[0015] In accordance with one embodiment of the invention, a calling party in a foreign country sends a request message to an electronic mailbox requesting the reverse call origination service. The mailbox is located on a global computer network, such as the Internet for example, and maintained by a U.S. service provider. The message includes an electronically generated form, i.e., a pre-formatted message, which is prepared by the provider. It comprises the calling party number, the called party number, and various optional parameters. As one option, the message may be encrypted to transfer customer's confidential information across the network safely.
[0016] After the form is filled out and sent to the mailbox by the customer, a microprocessor executing an application program on the computer network parses the information fields of the form and sends the card number for verification to a database. If the card is valid, the microprocessor executing the application program notifies the U.S. service provider of the request and forwards the information provided by the calling party. If the card is not valid, the request for the reverse call origination is aborted.
[0017] The service provider places a call to the called party in the U.S., then to the calling party abroad, and finally connects or bridges the two calls. After the call is completed, the calling party is charged for the calls at the U.S. rates because the two calls were made from the U.S.
[0018] In accordance with another embodiment of the invention, the calling party may supply a calling card number belonging to a third party. With the previously obtained authorization, the call charges will be paid by the third party.
[0019] In accordance with yet another embodiment of the invention, the call may be billed to the calling party in accordance with a previously agreed upon arrangement.
[0020] The advantages of sending information via a non-signaling network are as follows. First, the international carrier does not have to expend its resources on an unbillable call. Second, such pertinent information as a billing number (customer number, credit card number, etc.), a called party number, a calling party number, etc. can be sent in an initial message, thereby avoiding a call-back to the customer for collecting this information. This translates into lower costs for providing the reverse call origination service and possible savings for customers. Third, a separate line is not required for each customer resulting in fewer lines required to be purchased by the customers. Fourth, a destination number can be checked to determine if it is available, i.e., the destination telephone is “off-hook,” the network is congested, etc. The call will be reverse originated only if the destination telephone is “on-hook,” which again translates into lower costs and possible customer savings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The above-mentioned as well as additional advantages and features of the present invention will be evident and more clearly understood when considered in conjunction with the accompanying drawings, in which:
[0022] FIG. 1 shows a block diagram of a telephone call from Pierre (a calling party in a foreign country) to Jimmy (a called party in the U.S.) using the reverse call origination via a computer network in accordance with one embodiment of the present invention.
[0023] FIG. 2 shows a block diagram of a telephone call from Ivan (a calling party located in the first foreign country) to Steffi (a called party in the second foreign country) via the U.S. using the reverse call origination in accordance with another embodiment of the present invention.
[0024] In all Figures, like reference numerals represent same or identical components of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] One embodiment of the disclosed invention includes a calling party located in a foreign country who desires to call a party in the U.S. using the reverse call origination. According to this embodiment of the present invention as shown in FIG. 1 , the calling party, i.e., Pierre, 100 has access to a non-signaling network, i.e., a global computer network such as the Internet 102 , for example. To take advantage of the U.S. telephone rates which are lower than telephone rates in most other countries, the calling party 100 accesses the computer network 102 and sends a request for the reverse call origination to an electronic mailbox on the on-line computer service. The mailbox may be a computer account which the operator of the computer network allocates to the owner of the account upon request and/or fee. The account may be set up with various privileges requested by the owner, such as the size, authorized access, etc. For example, the owner may require the users of the computer network 102 to enter a password or an access code for sending or receiving messages to and from the mailbox.
[0026] In accordance with the disclosed invention, a U.S. service provider, i.e., a U.S. long distance carrier 104 , maintains the mailbox on the computer network 102 , which is specifically allocated for processing reverse call origination requests. To access the mailbox and send a call origination request message, the U.S. provider 104 may require, for example, a password previously obtained by the calling party 100 . In the alternative, no password may be needed to request the reverse call origination. In either case, the calling party 100 sends a request message comprising the following information:
calling party's number; called party's number; billing information and data, which may include, for example, a credit card or calling card number to be charged for the service, etc. other optional parameters, such as a password, etc.
[0031] In the current example, the calling party's number is the foreign telephone number, and the called party's number is the destination number of the call to the U.S. The calling party 100 enters this information into an electronically pre-formatted message generated by a computer program on the network 102 . The message is specifically tailored to the reverse call origination and has fields assigned to this particular function. The calling party 100 fills in the requested information in the pre-formatted message via his computer or computer terminal connected to the computer network 102 .
[0032] As previously stated, the request message with the above information is directed to the mailbox operated by the U.S. service provider 104 . In accordance with FIG. 1 , the computer program directs a microprocessor in a computer operated by the U.S. long distance carrier 104 to poll the mailbox for new messages every 3-5 seconds, for example, to obtain a quick turnaround response. Not all electronic mail systems, however, perform the polling function. As known in the art. some e-mail systems do not have to poll a mailbox to receive a message. Instead, these systems are automatically notified as soon as the message arrives at its destination, i.e., the mailbox in the current example. Since data in the message is presented in a standard format as selected and specified by the service provider 104 , the microprocessor can easily interpret or “parse” the information fields without any assistance from the “live” operator.
[0033] Next, the microprocessor executing the application program verifies the calling party's card number by accessing a database for card authorizations. There is no need for a separate database to validate the credit card, such as Visa, Master Card, American Express, etc., as the same databases currently used by subscribing merchants may be used for the card authorization in the disclosed invention. In a case of a calling card owned by a different U.S. long distance carrier than the one operating the reverse call origination service, an agreement may be reached, for example, providing for the use of the competitor's card. As an alternative embodiment of the present invention, verification may not be performed for corporate or other users who established accounts with the service provider 104 .
[0034] Regardless of the type of card used by the calling party 100 to pay for the call, if the card is determined to be valid, the application program operated by the U.S. long distance carrier 104 notifies its U.S. telephone operator of the request to place a call. The U.S. telephone operator is also provided with the calling party's and the called party's telephone numbers via a record retrieved from the mailbox. The U.S. operator then places a call to a called party, i.e., Jimmy, 106 located in the U.S. as shown in FIG. 1 . If the call is successfully terminated, the U.S. operator then calls the calling party 100 in the foreign country via a telecommunications network 108 and a foreign carrier 110 as known in the art. Upon establishing a voice communication with Pierre 100 , the U.S. operator bridges the call between Pierre 100 and Jimmy 106 as also known in the art.
[0035] If Jimmy's telephone line is busy or the call cannot be terminated because the network is congested, etc., the attempt to reach the called party 106 may be repeated until the voice connection is established. Alternatively, a message may be returned to the calling party 100 indicating the current status.
[0036] The calling party's card is billed for the two call legs, i.e., one call from the U.S. telephone operator to Jimmy and the other from the U.S. telephone operator to Pierre. The duration of the call extends to the point when one of the call legs is terminated. Even though two calls, instead of one, are made by the calling party 100 , both calls are billed at the U.S. telephone rate. For several countries with high telephone rates, the combination of two U.S. calls is still cheaper than a forward originated call to the U.S.
[0037] As another feature of the present invention, the U.S. carrier 104 may contain a database comprising telephone rates for inbound and outbound calls between the U.S. and various countries. When the U.S. carrier 104 receives a request for reverse call origination, its computer access the database to determine whether the two U.S. calls are less expensive than a normally originated, i.e., forward, call to the U.S. If this is the case, then the reverse call origination proceeds as described above. If, however, the computer determines that the forward originated call is cheaper than the two U.S. originated calls, the computer then uses the computer network 102 to send a message to Pierre advising him of this situation. Another alternative may be for Pierre's computer to expect a reply and stop waiting (time out) after 30 seconds, for example: if no response message is received from the service provider's computer, then the reverse call origination will occur as requested by Pierre.
[0038] Another embodiment of the present invention is illustrated in FIG. 2 which shows a block diagram of a telephone call transiting, instead of terminating in, the U.S. According to FIG. 2 , Ivan 200 , i.e., a calling party located in the first foreign country, wishes to call Steffi 206 , i.e., a called party located in the second foreign country, and sends a data message from his computer. The data message is sent via an international non-signalling network 202 , such as a packet network, data network, computer network, etc. as known in the art.
[0039] The data message includes an address name and domain name as used on the Internet for example, and is directed to a Company X 214 which is the owner of this address on the network 202 . The Company X 214 is a provider of the reverse call origination in accordance with the present invention. The Ivan's message includes:
a calling party number, i.e., his number and extension if applicable; a called party number, i.e., Steffi's number, including a country code and a national number with an extension if applicable; billing information which indicates how to bill for this call (Ivan's calling card, third party card, Steffi's calling card, Ivan's or Steffi's credit card, etc.) and billing data (a card number, expiration date, etc.); password which may be optional; and other optional parameters which may include various instructions to the Company X 214 , such as keep calling until Steffi is reached, or retry the call in 5 minutes, etc.
[0045] All of the information must be encrypted if the network 202 is exposed to breaches by computer “hackers” or unauthorized users.
[0046] After reaching the Company X 214 , the Ivan's message is analyzed for accuracy and validation of the billing information and the billing data. The calling number and the password, if applicable, are. compared with the entries in a database maintained by the Company X 214 . If the calling number, i.e., Ivan's, is requested not to be billed, a credit card or calling card number is checked for validity.
[0047] At the completion of validation and/or verification, the Company X 214 calls Steffi 206 . As well known in the art, the call proceeds via a U.S. long distance carrier 204 , a telecommunications network 208 carrying signaling and voice information, and a foreign carrier 210 serving the Steffl's telephone. When Steffi 206 answers the call from the Company X 214 , another call is then placed to Ivan 200 via a foreign carrier 212 . The two calls are bridged or connected with each other, similar to a 3-party call. If Steffi 206 cannot be reached, i.e., a busy signal or no-answer is received, then the Company X 214 notifies Ivan 200 of this situation. Alternatively, the Company X 214 may not notify Ivan 200 based on the prior arrangement. In this case, Ivan 200 , after waiting for several minutes for example, will realize that Steffi cannot be reached.
[0048] The above embodiment may be also use a database comprising telephone rates for inbound and outbound calls between the U.S. and various countries, as mentioned above in connection with another embodiment of the present invention. By accessing the database, a computer calculates whether the two U.S. calls are less expensive than a normally originated, i.e., forward, call. Based on the outcome of this calculation, the appropriate action is taken as described above.
[0049] In another embodiment of the present invention, after completing the validation and/or verification of billing information, the Company X 214 calls Ivan 200 via the U.S. long distance carrier 204 , the telecommunications network 208 , and the foreign carrier 212 serving the Ivan's telephone. While keeping Ivan 200 on hold, the Company A 214 calls Steffi 206 as described above. Although more expensive for customers, this method is easier to implement in the telephone industry. When Steffi 206 answers the call, the two calls are bridged or connected which is similar to a 3-party call. If Steffl 206 cannot be reached, the Company X 214 may take various courses of action as described above.
[0050] Upon completion of their conversation, either Steffi 206 or Ivan 200 hangs up first, and both legs of the call are disconnected at the first indication of a party being disconnected from the call. Billing information is then generated for sending to a party responsible for call charges.
[0051] Next, several alternative embodiments will be described with respect to the disclosed invention. First, a service provider of the reverse call origination may want to confirm that a calling party wants to proceed with the call before the original attempt is made to reach a called party. In this scenario, after receiving the request message, the service provider may call the calling party for confirmation of the reverse call origination. After confirming the request, the service provider places the calling party on hold, calls the called party and bridges the two calls.
[0052] Confirmation request entails the economic risk on the part of the calling party that the called party is unavailable, and the call cannot be terminated as intended. In this case, the calling party must still pay for the confirmation call made by the service provider. Thus, even though the call could not be terminated to the called party, the calling party incurred the cost for the unsuccessful attempt.
[0053] Although filling out the electronic form may delay the voice connection between the calling and called parties, the form may be partially completed by the calling party prior to initiating the request. Such information as the calling party's number and the card number may be included in the form for faster processing. This partially completed form, i.e., a template, may then be stored as a record in a database and quickly retrieved prior to the reverse call origination request. To initiate the service request, the calling party would have to supply only the destination number and quickly transmit the fully completed form to the service provider.
[0054] Another alternative of the disclosed invention may use a corporate account. For U.S. companies and businessmen working and staying abroad, a corporate account may be established for billing services in connection with the reverse call origination. As previously stated, in this case no credit card or user verification would have to be performed resulting in a faster voice connection between the callers.
[0055] Yet another embodiment of the invention pertains to a third party billing. A party located in a foreign country wants to call a party in the U.S. and charge the call to a third party. The calling party accesses an electronic mailbox maintained by a U.S. long distance carrier on a computer network, for example. Similar to the previously described embodiment, the calling party fills out a form to request the reverse call origination service. The form includes the calling party's number, the called party's number, a third party's card number to be charged for the service and other optional parameters as stated above.
[0056] In a case of a credit card, such as Visa, Master Card, American Express, etc., standard information will be required which includes the card number and the expiration date. If a third party's calling card is used, then some uniquely identifying information will be required to verify the authenticity of the third party or the relationship between the calling party and the third party. For example, a U.S. college student studying abroad and having an easy access to the Internet via a college computer may use the parents' calling card and provide the mother's maiden name as the uniquely identifying information.
[0057] Validity of the card and authenticity of the calling party proceeds as described in the previous embodiments. Thus, the credit card verification is performed via an existing database used by many merchants in the U.S. and abroad. The calling card information is verified via a remote database typically maintained by many U.S. long distance carriers. In the alternative embodiment which will compromise the security of service for the ease of operation, no additional information may be requested by the long distance carrier except the calling card number.
[0058] There are two major advantages of the disclosed invention over the systems and methods described in the prior art. First, the disclosed invention does not require the installation of any additional or specialized equipment at the calling and/or called party's site. No need exists for any modifications of the switches or databases operated by the long distance carriers to provide an interface with the additional equipment for reverse call origination. Many telecommunications databases currently contain foreign telephone rates which are used for comparison according to one aspect of the present invention.
[0059] Furthermore, the disclosed invention cannot possibly violate any international agreements and does not place unfair burden on the foreign carriers for transmitting signaling information despite the absence of the actual call completion. The foreign carrier does not incur any expenses during the call origination for setting up and tearing down the call, as described in the prior art, because the call origination request does not use the ANI equipment and completely bypasses international telecommunications networks. It is clear that services of the foreign carrier are not unfairly manipulated by the disclosed invention in contrast to the prior art.
[0060] Since those skilled in the art can modify the disclosed specific embodiment without departing from the spirit of the invention, it is, therefore, intended that the claims be interpreted to cover such modifications and equivalents.
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An approach is provided for originating a telephone call from a country with low telephone rates to a country with high telephone rates using a non-signaling network, such as a global computer network. This can be accomplished without additional specialized telephone equipment or any modifications to switches and databases in either country. Also, the telephone call can be established without any manipulations of signaling information transmitted by a carrier in the high traffic country. Such an approach provides flexible allocation of charges for originating a telephone call from a country with low telephone rates to a country with high telephone rates.
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BACKGROUND OF THE INVENTION
The invention relates to a process for the production of a face-to-face carpet fabric on a double pile loom having at least two filling insertion planes, using filling yarns, stuffer warp yarns, and chain warp yarns to form the back cloths in the form of a bottom cloth and a top cloth, as well as frames of pile yarns per warp course to form the patterned pile layer between the two back cloths, whose respectively non-patterning pile yarns are tied into the back cloths of the top and/or bottom cloths largely under tension and whose respectively patterning pile yarns are stretched alternately between the filling yarns of the top cloth and the bottom cloth; whereby the filling yarns within a pattern repeat in both back cloths are inserted in at least two different filling insertion planes, at least once as a back filling outside the stuffer warp and at least once as an inner filling inside the stuffer warp; whereby in each back cloth, groups of chain warp yarns are fed according to a prescribed pattern repeat, forming weaving sheds, whereby the chain warp yarns of a group staggered within a pattern repeat in the warp direction, loop in harmonizing weaving sequences outside the back fillings and inner fillings with respect to a back cloth, whereby each chain warp yarn of a group—within a weaving sequence—between its respective last binding to an inner filling and the subsequent last binding to a back filling is guided over several filling insertion cycles behind the inner fillings, forming a holding length, and then inside an inner filling in a compensating length, forming a weaving shed, and whereby the pattern repeats of the chain warp yarns are designed so that the tie-in length of the chain warp yarns of a group within each pattern repeat is compensated for between them.
A process of this type is known from EP 628 649 A1. It shows, for example, the customary state of the art up to now. The chain warps are arranged regularly in groups of two chain warp yarns. Each group is assigned respectively to a warp course. Each warp course has respectively such a group of chain warp yarns, at least one stuffer warp yarn, and a frame of pile yarns.
A group of chain warp yarns is characterized in that it holds within its pattern repeat all the back fillings and all the inner fillings in its effective area on the stuffer warp, which is tied in under tension, and optionally on the dead piles, which are tied in under tension.
It is customary thereby to guide the individual chain warp yarns of a group within a pattern repeat of a specific weaving sequence by means of shafts during the formation of the weaving shed. Because only a single warp beam is available as a rule for the chain warp yarns on a double pile loom, the chain warp yarns have been woven in regularly according to a uniform weaving sequence, so that the tie-in length and thus the tension of all chain warp yarns of a group can be held constant within a pattern repeat.
Those skilled in the art regularly focus on not exceeding a certain pattern repeat size and a certain temporary difference in consumption in order to ensure that the tension of the chain warp yarns running from a single warp beam is uniform. In practice, a so-called two-course rib weave (cf. Hans Osswald, “Die Teppichindustrie” 1965, Melliand Textilberichte, Heidelberg, p. 112, FIGS. 176 and 177) was used regularly on face-to-face carpet looms for the two-shuttle production of the backing. In this two-shuttle three-shot weave with a pattern repeat of six filling insertion cycles, in one of the two back cloths a chain warp yarn regularly extended diagonally from one inner filling to a back filling inserted four courses later and from there back again to an inner filling in the two immediately succeeding courses.
With this type of tie-in, the intermediate pile binding point was drawn very tightly to the previously formed back cloth by means of the diagonal section, let us call it the “holding length”, of the chain warp yarn. The shorter section guided through the back cloth, which we call the “compensating length,” then fixed the position of the chain warp yarn in the back cloth, so that when the chain warp yarn tension slackened in the shed area, the finished fabric could not loosen again.
Such a weave already ensures that the quality of the tie-in of the pile legs will be serviceable. There are specific limits to the filling density, however.
The asymmetrically tied-in chain warp causes the fillings carrying and supporting the pile loops to be deflected in the warp direction along the stuffer warp or along the dead piles. The exit direction of the pile loops regularly deviates by up to 10° and more from the vertical to the back cloth. Such an inclined position of the pile legs is regularly the reason that certain required resilience properties can only be ensured by increasing the pile density and/or by raising the pile height. Both measures for ensuring the desired resilience properties require a considerable additional expense for pile material. The costs for a carpet produced in this manner are correspondingly high.
A further disadvantage of this asymmetrical weave of the back cloth is that the recovery power of the pile cover under partial severe loading—for example by the feet of pieces of furniture—is insufficient.
Intensive brushing processes and the like may be required to remove partial pressure points. Usually, however, such pressure points leave permanent and clearly visible deformations in the pile surface.
Due to the inclined position of the pile legs, carpets woven in this manner cannot be lined up next to one another for contract use. The differing reflection angles of the incident light, which are caused as a function of the respective weave direction, give an observer the impression that there are color defects.
In order to limit the inclination of the pile angles, attempts have already been made (cf. Osswald, p. 112) to increase the thickness of the back cloth by inserting intermediate fillings that separate the stuffer warp from the dead pile strand. It was also hoped that this would enable the deflection of the fillings on the back cloth to be reduced.
This measure, with a specific arrangement of the fillings inserted successively or simultaneously in the area of a pattern repeat, had only limited success as far as the orientation of the pile legs was concerned (cf. DE 574 920).
There was a distinct increase in the quantity of material used. The pile density was not increased further by these measures.
In EP 628 649 A1 referred to initially, a solution to this problem was attempted in that other filling yarn arrangements were used, while keeping the intermediate filling. The chain warp yarns were guided over the filling yarns in such a way that they loaded the filling yarns approximately symmetrically in the warp direction. The filling yarns—inserted as back filling, intermediate filling, or inner filling—are this held largely immobile in the warp direction. The size of the pattern repeat was maintained in the customary manner with four filling insertion cycles. This led to an increased yarn material requirement for chain warp yarns. The pile density, measured in the warp direction, also remained clearly limited in this case. Carpets produced in this manner frequently had to be placed in lower quality categories due to inadequate density.
For the said reasons, the production of very dense pile goods was normally previously reserved for the single-shuttle weaving technique, in which not every pile loop is tied to a back filling. Much lower productivity was accepted.
EP 922 799 A2 shows an attempt to increase pile density even using a two-shuttle method. In each back cloth. the top cloth and the bottom cloth, the pile loops in a warp course are stretched alternately on a back filling and then on an intermediate filling—which is inserted between the stuffer warp and the dead piles. The pattern repeat of the chain warp yarns extends over eight courses. The initially defined holding length is formed in each weaving direction in three successive courses.
The goods achievable using intermediate fillings and back fillings as pile carrying fillings are of lower quality. The appearance of the back of the carpet differs considerably from the appearance of the pile side. The pile loops at the borders of the pattern, which are only bound via an intermediate filling, have a distinctly lower pull-out resistance. During the usual care with a vacuum cleaner, these pile loops are gradually detached from their weave and removed. The final result of this is unclear pattern contours. A higher pile density is only achieved to a limited extent.
In Belgian Patent 675 494, an attempt was made to achieve a greater pile density even when all the pile loops are stretched over a back filling, using a similar basic weave of the chain warp. Here, the dead piles were guided under tension on the back of the bottom cloth and after the weaving procedure and the separation of the face-to-face carpet fabric, were scratched off from the back of the bottom cloth in the pile plane. These so-called “scratch-off goods” are known to be of unsatisfactory quality.
It is an object of the present invention to provide a process for fixing the back cloths with dead piles distributed in the top cloth and bottom cloth and tied in by means of chain warp yarns, which process on the one hand ensures a largely vertical tie-in of the pile legs in the back cloths, enables a carpet fabric to be produced with a high pile density, and ensures that the quantity of material used in the area of the back cloths can be distinctly reduced.
It is furthermore an object of the invention to ensure, by means of the measures found, that the resilience properties of the carpet are the same or better, the quantity of pile material used being reduced.
SUMMARY OF THE INVENTION
This objective is accomplished by a process in accordance with which the combination of the designated process steps prevents back fillings from being deflected in the warp direction relative to the inner fillings. It prevents the points of intersection of two chain warp yarns of two groups always being positioned in one and the same transversal area of the back cloth in adjacent warp courses during the shed treadle motion.
Surprisingly, the combination enables the pile density in the warp direction to be increased by up to 30%, depending on the weave variant selected and the thickness of the filling yarns used.
The pile loops project regularly from the back cloth largely vertically and are stable and securely supported in this position. This leads to excellent resilience properties in the finished carpets.
The recovery power of the pile surface after partial severe loading is optimized.
The varying reflectance of the colors as a function of weave direction is distinctly reduced. The use of pile carpet for contract carpeting is no longer generally excluded.
Depending on the weave selected in the scope of the invention, chain warp material can be saved in orders of magnitude of between 10 and 25%.
A saving of pile material results from the fact that a lower pile height can be selected to achieve the same resilience properties, due to the vertical pile tie-in.
In addition to said advantages, another embodiment has the additional advantage that the pile binding points on the carpet back are distributed uniformly and free of lines, especially when 4 chain warp yarns are used per group. The carpet back resembles the classical hand-knotted carpet and has the additional advantages of the taut stuffer warp.
In contrast to known basic weaves, the pile density was able to be increased with a relatively small pattern repeat by up to 15 pile rows/dm, and in variants with a substantially larger pattern repeat by up to more than 100 pile rows/dm.
Depending on the length of the pattern repeat, the modification according to a further embodiment enables a distinct saving (up to over 25%) of chain warp material while maintaining the classical back appearance of a carpet—analogous to the conventional 2/2 rib weave. Here too it is possible to increase the pile density considerably.
In accordance with an advantageous embodiment of the invention, a group of the chain warp yarns is suitably distributed over 3 to 4 warp courses. Again there is a high pile density and a distinct saving of chain warp material.
The advantages of the weave according to a further embodiment are that in addition to an attractive saving of chain warp material, improved pile position, and improved pile density, high wear resistance can be ensured, even in the unbound state.
In accordance with another embodiment, a variant is defined that is important in particular for working with three overlapping filling insertion planes. The most essential advantages are a high saving of chain warp material while maintaining high wear resistance of the carpet.
Yet a further advantageous embodiment describes a second basic method to achieve the object of the invention in a limited area of the pattern repeat, which has the same results as those described in relation to the initial embodiment described above.
A still further embodiment of the invention is directed to an almost equivalent method to the first embodiment described herein. The pile loops do not tie over a back filling in every case. The pattern of the front face of the carpet is not reproduced completely on the back, however. This weave is desirable where the demands on the quality of the carpet are not particularly high and the price is to be kept correspondingly low.
The invention is explained in greater detail below by means of examples with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view through a face-to-face carpet fabric along the warp direction;
FIG. 1 a is a top view of the face-to-face carpet fabric according to FIG. 1;
FIG. 2 is a schematic weave design of one of the back cloths, a top cloth, with an irregular weave pattern of the chain warp yarns;
FIG. 3 is a representation as in FIG. 2 with a regular pattern repeat;
FIG. 4 is a schematic weave design with chain warp yarns binding irregularly in long lengths in two adjacent warp courses,
FIG. 5 is a representation as in FIG. 2 with regularly symmetrically binding chain warp yarns arranged in pairs in two adjacent warp courses;
FIG. 6 is a representation as in FIG. 5 with back and inner fillings bound in pairs;
FIG. 7 is the representation of a weave pattern with alternating tabby weave over each three back- or inner fillings;
FIG. 8 is a representation as in FIG. 7 with an extended tabby weave in the area of the back- and inner fillings,
FIG. 9 is a representation of a top cloth with an additional intermediate filling and regular guiding of the chain warps and a distribution of the chain warps on two warp courses;
FIG. 10 is a representation according to FIG. 9 with a modified arrangement of the intermediate fillings;
FIG. 11 is a representation as in FIG. 9 with a third variant of the arrangement of the intermediate fillings, whereby the group of chain warp yarns consists of four chain warp yarns assigned to two warp courses;
FIG. 12 is a representation of a top cloth with the filling arrangement of FIG. 11, whereby the chain warp yarns loop around the back- and intermediate fillings in lengths in tabby weave and in the following length bind the intermediate and inner fillings;
FIG. 13 is a representation as in FIG. 7, whereby an additional intermediate filling is provided;
FIGS. 14 and 15 are modifications of the weave of FIG. 13;
FIG. 16 is a diagram of the paired filling weave for back fillings on a top cloth as in FIGS. 1 and 2;
FIG. 17 is a diagram when tabby weave is used on the back fillings on a top cloth;
FIG. 18 is a weave diagram with tie-in of the chain warp yarns asymmetrically under tension, using their gripping action in the finished fabric of a top cloth; and
FIGS. 19 to 22 show further weave examples with pile loops interlacing unevenly with back-, intermediate, or inner fillings.
DETAILED DESCRIPTION OF THE INVENTION
The face-to-face carpet fabric shown in FIG. 1 consists of a top and a bottom back. cloth, top cloth OW and bottom cloth UW, and of patterning pile yarns PM alternating regularly between the top and bottom back cloth, which pile yarns are separated in the riddle between top cloth OW and bottom cloth UW after the weaving procedure.
Each of back cloths OW, UW contains stuffer warp yarns FK running in the warp direction and non-patterning pile yarns oriented parallel to them that are designated below as dead piles PT or dead pile strand. These two yarn groups FK, PT are held on the outside by back fillings SR and on the inside by inner fillings SI. The position of the back fillings SR. and inner fillings SI is fixed by chain warp yarns B (B 1 , B 2 in FIG. 1 ). Chain warp yarns B are arranged in groups. The size of the group varies normally between two (e.g. B 1 , B 2 ) and four (e.g. B 13 to B 16 ) chain warp yarns B. The number of chain warp yarns B in a group is governed by the minimum number of yarns needed to bind all the back fillings SR and inner fillings SI to the back cloth once each within a pattern repeat R. (Adjacent groups can also augment one another with respect to one or more binding points.)
In one pattern repeat of chain warp yarns B we find as a rule at least one holding length Y and at least one compensating length Z.
The first holding length Y 1 of chain warp yarn B 1 of the B 1 , B 2 group shown in FIG. 1 begins after inner filling SI shown above left. It encloses upper left back filling SR 1 and then second back filling SR 2 . In the subsequent first compensating length Z 1 , this chain warp yarn B 1 is guided to subsequent inner filling SI and from there in the same plane to the next inner filling SI. If all chain warp yarns B 1 , B 2 of the group were to bind with the same tie-in length, the pattern repeat of a group. would already be ended here.
In the present case, however, second chain warp yarn B 2 binds differently. It alternates respectively from a filling yarn lying opposite the first-named filling yarn pair to the net filling yarn, which is inserted three filling insertions later. This chain warp yarn B 2 brings the necessary longitudinal tension to the backing by means of another holding length Y 2 and ensures that back fillings SR that carry pile loops and inner fillings SI that guide pile loops, are drawn against one another so tightly that the pile loops are prevented from lying at an angle.
In order to ensure that the tie-in length of both chain warp yarns B 1 , B 2 remains the same within a pattern repeat, both chain warp yarns B 1 , B 2 reciprocally change their weave twice within a pattern repeat R—optionally in a special change length W. As a result, each chain warp yarn B 1 , B 2 has two different holding lengths Y 1 , Y 2 and also two different compensating lengths Z 1 , Z 2 .
In both weaves, holding length Y 1 , Y 2 and also respective compensating length Z 1 , Z 2 extend over three filling insertion cycles. Because of change lengths W, the total pattern repeat amounts to e.g. 20 or 28 filling insertion cycles. After three or five fillings respectively, two chain warp yarns B 1 , B 2 change regularly from the back plane inwards or vice versa.
The size of pattern repeat R and individual binding lengths X 1 , X 2 (FIG. 2) should be selected thereby such that a temporary slackening of individual chain warp yarns B 1 , B 2 of a group while being doffed from the warp beam can also be avoided with certainty. The tension of chain warp yarns B should be monitored before entry into the shed-forming zone and must-not fall below a value of 2 to 4 N.
In the present case, chain warp yarns B 1 , B 2 of the group can be distributed over two adjacent warp courses K 1 , K 2 (FIG. 1 a , FIG. 5 and FIG. 6 ). In spite of this distribution, they hold the relatively voluminous back fillings SR against stuffer warp FK and inner fillings SI securely enough against dead pile strands PT in the respective back cloth OW or UW.
In FIGS. 2 to 8 below, weave designs are shown based on top cloths OW in which the back cloth only has back fillings SR and inner fillings SI.
FIGS. 9 to 15 , in contrast, show back cloths, for example of top cloths OW, that also have intermediate fillings SZ (SZ 1 , SZ 2 , SZ 3 ) between the taut stuffer warp FK and the voluminous dead piles PT.
FIG. 2 shows a weave as was also described in relation to FIG. 1 . Only change lengths W are positioned and formed somewhat differently here. Special change lengths W are provided in FIG. 2 in addition to holding lengths Y 1 , Y 2 and compensating lengths Z 1 , Z 2 . Change lengths W can also be assigned to compensating lengths Z 1 , Z 2 .
The weave variant of FIG. 3 shows a regular paired interlacing of back fillings SR and inner fillings SI. It achieves the object of the invention by very simple means. After the first tied-in back filling SR, chain warp yarns B 3 , B 4 in the first warp course maintain their position in the weaving shed until the second back filling of this pair is beaten up. Holding length Y 3 brought from the last inner filling SI before the paired binding of the back fillings is gripped in the already finished fabric such that no elastic component can become active in this yarn length and deflect the last inserted back filling SR laterally. The pile legs are not deflected and stand almost vertical in the back cloth. In the adjacent warp course, a further pair of chain warp yarns B 3 ′ and B 4 ′ of this group binds staggered with respect to the first pair by two courses.
The weave design of FIG. 4 shows larger lengths with different weave designs of chain warp yarns B 5 , B 6 , B 7 , B 8 . Two chain warp yarns B 5 , B 6 bind regularly in pairs over back fillings SR or inner fillings SI thereby.
Their holding lengths Y 4 and compensating lengths Z 4 each extend over five filling insertion cycles. The two chain warp yarns B 7 , B 8 each bind only over one filling, a back filling SR or an inner filling SI.
Holding length Y 4 ′ extends over five filling insertions, while compensating length Z 4 ′ includes seven filling insertions. It is advisable to alternate these weave designs reciprocally after certain lengths—as already mentioned in relation to FIG. 2 . If it is desired to avoid such changes W, the two differently binding pairs of chain warp yarns B 5 , B 6 or B 7 , B 8 respectively must be doffed from two different warp beams.
FIG. 5 shows a weave design in which individual chain warp yarns B 9 , B 10 , B 11 , B 12 are interlaced almost symmetrically and regularly according to a single weave design. A deflection of the pile legs in any direction is reliably avoided and individual chain warp yarns B 9 , B 10 , B 11 , B 12 of a group are preferably arranged in pairs in adjacent warp courses K 1 , K 2 . It is also possible to arrange these chain warp yarns B 9 , B 10 , B 11 , B 12 individually respectively in four adjacent warp courses.
Holding lengths Y 5 include five filling insertions, while compensating lengths Z 5 finish after three courses each.
The embodiment of FIG. 6 is essentially comparable to FIG. 5 . The difference is that chain warp yarns B 13 , B 14 , B 15 , B 16 bind over pairs of filling yarns instead of over individual fillings. In this embodiment a very high fabric density is achieved with an absolutely vertical orientation of the pile legs. At a pattern repeat size of 16 , there are nine courses in holding length Y 6 and seven courses in compensating length Z 6 . When suitable filling yarns are used, it is possible to reduce the need for chain warp yarns distinctly, if the individual chain warp yarns B of a group are distributed over several warp courses.
The weave of FIG. 7 differs from FIG. 6 in that the number of by a chain warp yarn B 17 , B 18 , B 19 , B 20 in the area of back fillings SR and inner fillings SI is further increased. In combination with other chain warp yarns B 17 , B 18 , B 19 , B 20 of a group, back fillings SR or inner fillings SI are respectively fixed separately in tabby weave. Holding length Y 7 and also compensating length Z 7 extend respectively over seven filling insertion cycles.
In FIG. 8 the number of filling yarns bound in this manner is increased to five fillings per filling yarn plane. Chain warp yarns B 21 , B 22 , B 23 , B 24 of a group are staggered so that on the one hand all back fillings SR and inner fillings SI are woven reliably and that back fillings SR are bound to inner fillings SI at regular intervals.
FIGS. 9 to 11 show the regular tie-in of filling yarns SR, SI, SZ by chain warp yarns B 25 , B 26 , B 27 , whereby the chain warp yarns in reciprocal alternation fix filling yarns SR, SI individually almost symmetrically according to a uniform weave design with the pattern repeat R 9 , R 10 , R 11 .
The differences between the individual FIGS. 9 to 11 consist only in the different position of the intermediate fillings SZ 1 (above the inner filling), SZ 2 (below the back filling), and SZ 3 (between the back filling and inner filling).
Chain warp yarns B 25 , B 26 , B 27 , B 28 of each of these back cloths can be arranged with respect to a group in one to four warp courses.
In FIG. 12, a pattern repeat R 12 of a chain warp yarn B 29 , B 30 consists of holding lengths Y 12 and compensating lengths Z 12 with different weave designs of the tabby weave type between inner filling SI and intermediate filling SZ 3 or between back filling SR and intermediate filling SZ 3 . All back fillings SR and all inner fillings SI are loaded symmetrically by chain warp yarns B 29 , B 30 . The tie-in length of chain warp yarns B 29 , B 30 of this group is compensated for by two change lengths W respectively, as in the Example of FIG. 2 .
The weave design of FIG. 13 is essentially comparable to the weave design of FIG. 7 . Change lengths W are shortened, however.
Holding lengths Y 13 extend over five filling insertion cycles; compensating lengths Z 13 likewise.
The additional intermediate fillings SZ 1 , which press stuffer warp FK against back fillings SR, ensure a slight curvature of stuffer warp FK that additionally prevents back fillings SR from sliding in the warp direction. Although individual back fillings SR are loaded unsymmetrically in the warp direction, they maintain their original position in combination with the adjacent fillings. Thus they enable an exact orientation of the pile legs vertical to the back cloth.
FIGS. 14 and 15 contain further modifications to FIGS. 7 and 8. Intermediate fillings SZ 2 , SZ 3 serve here to fix back fillings SR additionally, without chain warp yarns B 34 , B 35 , B 36 , or B 37 , B 38 , B 39 extending regularly over the entire cross section of back cloth OW.
With the embodiments described here, it is possible distinctly to reduce the number and incorporation of chain warp yarns B 34 , B 35 , B 36 , or B 37 , B 38 , B 39 . All the weave variants described have the effect of causing the pile legs to project vertically: from the back cloth—reliably and with feasible tolerances.
The reason for this varies in detail. The subject of FIGS. 16 to 18 is to represent the principles active thereby.
In the weave design of FIG. 16, the symmetrical loading of a pair of filling yarns by chain warp B 1 is utilized. Chain warp B 2 with its diagonally oriented holding length Y 2 and compensating length Z 2 deliver the necessary forces to hold filling yarn pair SR 1 and SR 2 against one another in the warp direction. The increase of inner tensions in chain warps B 1 , B 2 is avoided by the looping friction in combination with the friction caused by the gripping action within the finished fabric. Not only the density in the filling direction but also the density in the warp direction can be increased with the distribution of chain warp yarns B 1 and B 2 in adjacent warp courses. Laterally overlapping points of intersection of chain warp yarns B 1 , B 2 are avoided at the densest points in the fabric.
In the weave design according to FIG. 17, back fillings SR or inner fillings SI within holding lengths Y 17 (and also in compensating lengths 7 FIG. 7) are held against one another in their respective plane by means of tabby weave. All back fillings SR and also all inner fillings SI are held firmly against stuffer warp FK or dead piles PT respectively by means of at least one diagonal chain warp yarn length. In this manner the back cloth is very stable. Longitudinal forces (in the warp direction) in this system are additionally applied by the diagonal yarn length inside holding length Y 17 . Here too, the gripping forces have a favorable effect on this yarn length in the finished fabric. In the finished fabric, back fillings and inner fillings SR, SI remain where they are positioned during the beat-up (beat-up direction A).
FIG. 18 shows a weave design variant according to the invention that enables a vertical tie-in of the pile legs in spite of the asymmetry of the weave pattern. After being bound to inner filling S 14 within holding length Y 18 , chain warp yarn B 40 is guided over eight filling insertion cycles in the area of dead piles PT and stuffer warp FK. In this area it is stretched in the finished fabric and simultaneously gripped on all sides. The tensile force applied by it is exerted uniformly in beat-up direction A on all back fillings positioned in its effective area.
Although it appears in this weave that inner fillings SI are loaded in exactly the opposite direction, no deflection in this direction has been found in practice. It is highly probable that the reason for this is that the gripping forces on long holding length Y 18 within the finished fabric are so great that no deflection of the inner fillings takes place during a repeated filling beat-up. Even in this asymmetrical weave, the pile loops regularly project vertically from the back cloth.
The number of possible weaves is not yet exhausted with these Examples. It has been found that there must be certain numbers of filling insertion cycles in defining the sum of the lengths of holding lengths Y, chain warp yarns B of a group, and total pattern repeat length R of chain warp yarns B, if the desired effects are to be achieved regularly.
The density of the cross connections between back fillings SR and inner fillings SI ensures the necessary stability of the back cloth and the equally necessary friction of the fillings against the warp yarn strand (PT/FK).
Finally, we should mention that in particular the weave shown in FIG. 18 can also be woven in the opposite direction with similar effects. The asymmetrical tension on the back fillings will not be capable of changing the position of the back fillings during the repeated filling beat-ups, because of the stretched orientation of the compensating length (this would then be Z 18 ) between back fillings and inner fillings SR, SI. The gripping forces on chain warp yarns B building up within the finished fabric support this procedure. An almost vertical orientation of the pile yarn legs can also be achieved with this variant.
The results when a high pile density is achieved are similarly effective when a certain pattern repeat length is ensured. The saving of material for the chain warp overall is also fully effective in this variant.
The principles of the present invention can also be used in the weaving of face-to-face carpet fabrics in which not every patterning pile loop is stretched over a back filling. Examples of this are shown in FIGS. 19 and 20 for fabrics that have exclusively back fillings SR and inner fillings SI. Pile loops PM and PM′ are here bound alternately by back fillings SR and inner filling SI.
Chain warp B in FIG. 19 follows a pattern repeat R 19 that extends over 16 filling insertion cycles. The weave design is similar to that of FIG. 7 .
In FIG. 20 pattern repeat R 20 extends over 12 filling insertion cycles. It is similar to that of FIG. 6 .
FIGS. 21 and 22 show weave designs in which fillings SR, SI in top cloth OW are arranged in 3 planes respectively. Chain warp yarns B bind respectively over a pair of back fillings SR or inner fillings SI in the respective back cloth OW or UW. Pile loops PM, PM′ pass alternately once over a back filling SR and then over an intermediate filling SZ.
With these weave designs, a distinctly higher pile density and a saving of material for chain warp B are also achieved. The pile loops project sufficiently vertically from the back cloth here too.
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A process for the production of a face-to-face carpet fabric on a double pile loom having at least two filling insertion planes, uses filling yarns, stuffer warp yarns, and chain warp yarns to form two back cloths. The filling yarns are inserted into each back cloth as back fillings and inner fillings. Groups of chain warp yarns, individual yarns of which between their respective last binding to an inner filling and the succeeding last binding to a back filling form a holding length, are assigned to each back cloth. All patterning pile loops are stretched over back fillings. and the pattern repeat of a group of chain warp yarns is selected to be greater than six. The holding lengths of a chain warp yarn extend over at least three filling insertion cycles.
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FIELD OF THE INVENTION
The present invention relates to structural assemblies and, more particularly, relates to the joining of machined-sandwich assemblies by friction stir welding.
BACKGROUND OF THE INVENTION
Conventional structural assemblies as used in the manufacture of military and commercial aircraft are commonly fabricated using a bonded honeycomb-sandwich construction or a built-up structure. Conventional structural assemblies formed from these types of constructions generally include large numbers of parts and fasteners which can result in extensive tooling and increased labor costs during manufacture and assembly. The component parts of conventional structural assemblies are typically not welded because conventional welding techniques can distort the dimensions and/or shape of the component parts as well as create joints having defects such as porosity, micro-cracking, lack of fusion and poor ductility that can lead to cracking or failure of the joint when subjected to the severe cyclical stresses commonly associated with aeronautical applications.
Additionally, during use, aircraft structural assemblies are subjected to a variety of environmental conditions, temperature variations, severe acoustic and vibration environments, all of which create mechanical and thermal stresses. Over time, the application of cyclical stresses to bonded structural assemblies can lead to disbanding at the joints, and unless repaired, it can result in mechanical failure. Moisture entrapments also can occur during use of the aircraft which in combination with the extreme environmental conditions can result in corrosion which can also weaken the structural assembly. Due to the large number of parts and fasteners utilized in the construction of conventional structural assemblies, maintenance and repair can be time consuming and labor intensive which can be costly over the life of the assembly.
The number of total parts utilized in a bonded honeycomb or built-up structure can also increase the overall weight of the aircraft. Consequently, conventional structural assemblies are generally costly to build and maintain and can adversely affect the weight of the aircraft.
In seeking better structural assembly designs, other types of sandwich structures have been proposed. In particular, one such alternative design is an interlocking design concept such as the Grid-Lock® interlocking assembly of Tolo Incorporated which is described in U.S. Pat. No. 5,273,806 to Lockshaw et al. and which is shown in FIGS. 1 and 2. An interlocking structural assembly 10 includes first and second machined components 11, 12 which are typically fabricated from aluminum or titanium using a CNC milling machine. The components are machined to include generally planar surface portions 13, 14 having a plurality of integral ribs 15, 16 which extend outwardly from a respective surface portion and coincide with the ribs of the other component. The ribs 15 of the first component 11 are further machined to include grooves 17 for matingly receiving the distal ends of the corresponding ribs 16 of the second component 12. The grooves 17 are precisely machined so as to form a tongue and groove assembly which allows the ribs 15, 16 of the first and second components 11, 12 to be snapped together. Additionally, the interlock ribbing 15, 16 are adhesively bonded together with an adhesive 18 such as epoxy or urethane glue.
Interlocking ribs and grooves require extra stock material. Further, the ribs and grooves have to be machined with specific tolerances in order to obtain a secure fit of the interlocking assembly. The precise machining generally requires extra machining time which can increase the overall manufacturing costs and can result in material waste in cases of operator error.
The use of an adhesive to bond the structural assembly also creates the potential for disbonding of the joints due to degradation of the adhesive from heat exposure or environmental conditions and stress. An adhesive bond failure can accelerate corrosion damage or result in a catastrophic failure of the assembly. Although the use of the interlocking assembly assists the adhesive bond in joining the corresponding ribs, the mechanical strength of the joint remains well below that of the base material.
As a result, there remains a need for structural assemblies which can be manufactured and assembled with a minimum number of parts so as to reduce the costs associated with manufacture, assembly and maintenance of the structural assemblies, as well as to reduce the overall weight of the aircraft. The structural assembly must also be capable of providing high mechanical strength and structural rigidity.
SUMMARY OF THE INVENTION
The present invention provides a method of manufacturing a structural assembly including the steps of machining a work piece to form a first structural member having an outer and an inner surface. The first structural member may also be formed into a curvilinear geometry. A second work piece is machine into form a second structural member having a plurality of intermediate members disposed in a predetermined pattern, each of the plurality of intermediate members extends outwardly to corresponding distal ends. The distal ends are machined to form a pre-selected geometry. The inner surface of the first structural member is positioned adjacent to the distal ends of the plurality of intermediate members so that the plurality of intermediate members extend between the first and second structural members. The first and second structural members are secured so as to prevent movement of the first structural member relative to the second structural member and the plurality of intermediate members. The first structural member is then joined to the distal ends of each of the plurality of intermediate members by friction stir welding. The structural assembly is then secured to other structural assemblies to form the frame of an aircraft.
The present invention also provides a structural assembly including first and second structural members. It is particularly advantageous to have at least one of the first and second structural members formed of an unweldable material. The second structural member is spaced from the first structural member and has a plurality of intermediate members which extend outwardly in a predetermined pattern to corresponding distal ends. The distal ends are machined to form a pre-selected geometry. The plurality of intermediate members extend between the first structural member and the second structural member. The distal ends of each of the plurality of intermediate members are joined by means of a friction stir weld joint to the first structural member to form an integral structural assembly.
Accordingly, there has been provided a structural assembly and an associated method of manufacture allowing for the efficient construction of aircraft structural assemblies having a minimum number of component parts and which are joined together through a material bond substantially equal to the strength of the base materials. The resultant assembly requires less stock material and takes less time to machine.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other advantages and features of the invention, and the manner in which the same are accomplished, will become more readily apparent upon consideration of the following detailed description of the invention taken in conjunction with the accompanying drawings, which illustrate preferred and exemplary embodiments, and wherein:
FIG. 1 is a perspective view showing an interlocking structural assembly as known in the art;
FIG. 2 is a fragmentary cross-sectional view showing the tongue and groove joint of the interlocking structural assembly of FIG. 1;
FIG. 3 is a perspective view showing a partially assembled structural assembly according to the present invention;
FIG. 4A is a fragmentary cross-sectional view showing the joining of the first structural member to the distal end of an intermediate member of the structural assembly of FIG. 3;
FIG. 4B is a fragmentary cross-sectional view showing the joining of the first structural member to the distal end of an intermediate member having a straight tapered geometry;
FIG. 4C is a fragmentary cross-sectional view showing the joining of the first structural member to the distal end of an intermediate member having a "T" shaped geometry;
FIG. 4D is a fragmentary cross-sectional view showing the joining of the first structural member to the distal end of an intermediate member having an "L" shaped geometry;
FIG. 4E is a fragmentary cross-sectional view showing the joining of the first structural member to the distal end of an intermediate member having a curved tapered geometry; and
FIG. 5 is a flow chart showing the steps for manufacturing the structural assembly of FIG. 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which a preferred embodiment of the invention is shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, this embodiment is provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art. Like numbers refer to like elements throughout.
Referring now to the drawings, and in particular to FIG. 3, there is shown a structural assembly 20 according to the present invention. The structural assembly 20 includes a first structural member 21 which forms the outer skin of one side of the structural assembly. The first structural member 21 can be machined, through known manufacturing means, from a single work piece into a predetermined shape and thickness as required by the specific design loads and specifications. The first structural member 21 may also be formed, through known manufacturing means, into a curvilinear geometry. No extra material Dr machining time is required to machine interlocking grooves, as in the current adhesively bonded sandwich construction.
The structural assembly 20 also includes a second structural member 22 which preferably has a geometry that is evenly mated with the first structural member 21. The second structural member 22 includes a skin portion 23 and a plurality of intermediate members 24 which are formed integrally with the skin portion of the second structural member. Each of the intermediate members 24 extends outwardly from the skin portion 23 in a predetermined pattern to a corresponding distal end 25. The corresponding distal ends 25 are machined to form a pre-selected geometry. Again, the skin portion 23, the intermediate members 24 and the corresponding distal ends of the second structural member 22 can be machined, through known manufacturing means, from a single work piece into a predetermined shape and thickness as required by the specific design loads and specifications. For example, a CNC milling machine can be used to machine both the first and second structural members 21, 22.
The structural assembly 20 is constructed by positioning the first structural member 21 relative to the second structural member 22 such that the plurality of intermediate members 24 extend between the first structural member and the second structural member. In particular, the inner surface 26 of the first structural member 21 is adjacent to the distal ends 25 of the plurality of intermediate members 24. The first and second structural members 21, 22 are then secured so as to prevent motion of the first structural member relative to the second structural member and the plurality of intermediate members 24. For instance, the first and second structural members 21, 22 may be secured to each other by spot welding. Then, structural members 21, 22 may be secured to the work table by means of a conventional clamp (not shown).
The bottom surface 26 of the first outer member 21 is then joined to the distal ends 25 of the plurality of intermediate members 24 by friction stir welding. Specifically, a rotating friction stir welding probe 19 which is attached to a friction stir welding tool 27 is forced through the outer surface 28 of the first structural member 21, through the bottom surface 26 and into the distal ends 25 of the plurality of intermediate members 24. The frictional heat generated by the rotating tool 27 creates a plasticized region or joint 29 as shown in FIG. 4 which solidifies between the first structural member 21 and the distal ends of each of the plurality of intermediate members 24. Advantageously, the first structural member and the intermediate members are disposed in a substantially perpendicular relation. The rotating probe 19 is then moved along a path through the first structural member 21 that traces the respective intermediate member 24 to thereby form a continuous friction stir weld joint along the length of the intermediate member. This friction stir, welding process can then be repeated for each of the plurality of intermediate members 24. See U.S. Pat. No. 5,460,317 to Thomas et al. for a general discussion of friction stir welding, the contents of which are incorporated herein by reference.
In order to create the requisite bond between the plurality of intermediate members 24 and the first structural member 21, the thickness T of the first structural member and the thickness t of each of the intermediate members will depend upon the properties of the material used to form the first structural member and the second structural member 22, respectively. As illustrated in FIG. 4A, the probe 19 will preferably extend through the first structural member 21 and into the corresponding distal end 25 of each of the plurality of intermediate members 24 a distance d, which will again depend upon the material properties of the base materials as well as the thickness t of the intermediate members 24.
As shown in FIGS. 4A-E, the corresponding distal ends 25 of intermediate members 24 may be machined to form a variety of geometries. The geometry of the distal ends 25 are selected based on the geometry of the first structural member 24 as well as the particular load requirements of the joint between the first structural member and the distal end. In FIG. 4A the distal end 25 is machined to form a rectangular geometry. In FIG. 4B, the distal end is machined to form a tapered geometry. In FIG. 4C, the distal end is machined to form a "T" shaped geometry. In FIG. 4D, the distal end is machined to form an "L" shaped geometry, and in FIG. 4E, the distal end is machined to form a circular tapered geometry. Although specific geometries have been illustrated, the distal end can be machined to form other geometries that are also within the scope of the disclosed invention.
The method of the present invention is particularly advantageous to join first and second structural members 21, 22 that are formed of either similar or dissimilar metals which would be unweldable or uneconomical to join by any other means. Unweldable materials, when joined by conventional welding techniques, produce relatively weak weld joints because these materials possess high conductivity and quickly dissipate heat away from the weld joint. Such materials include aluminum and some aluminum alloys, particularly AA 2000 and AA 7000 series aluminum alloys. The method of the present invention permits first and second structural members formed of unweldable materials to be securely joined. The method of the present invention may also be used to securely join weldable materials to other weldable and to unweldable materials. Thus, the method of the present invention permits the materials which form the first and second structural members 21, 22 to be chosen from a wider variety of light weight, high strength metals and alloys, thereby facilitating reduction of the overall weight of the aircraft. Weight and strength are of critical concern in the aerospace industry.
Friction stir welding creates a severely deformed but highly refined grain structure at the weld interface. Further, friction stir welding results in a more narrow heat-affected zone compared to any fusion welding process and is not limited to selected alloys with properties that are suitable for conventional welding. Friction stir welding eliminates a number of defects related to conventional welding, such as micro-cracks, poor ductility, lack of fusion, porosity and most importantly, minimization of distortion which can adversely effect the shape and tolerances of the joined component members. In instances where the first and second structural members 21, 22 are formed of the same material, the joint 29 which consists of the plasticized material from the first structural member 21 and the corresponding distal end 25 of the intermediate member 24 will have substantially the same mechanical properties, including strength, as the base materials. Alternatively, if the materials used to form the first structural member 21 and the plurality of intermediate members 24 are dissimilar, then the joint 29 will have the strength of the weaker material so long as the first structural member and the plurality of intermediate members are each formed from a material, such as aluminum, aluminum alloys, titanium, titanium alloys or the like, which creates a full-strength metallurgical bond when joined through friction welding. Thus, the resulting join 29 in structural assembly 20 is of significantly greater strength than that provided by conventional structural assemblies, especially those utilizing adhesives.
Referring now to FIG. 5, there is illustrated the operations performed to manufacture a structural assembly according to one embodiment of the present invention. The first step includes machining a work piece to form a first structural member having inner and outer surfaces and may be performed simultaneously with the second step. The first structural member may also be formed into a curvilinear geometry. See block 30. The second step includes machining a second work piece to form a second structural member having a plurality of intermediate members, each of the plurality of intermediate members extending outwardly in a predetermined pattern to a corresponding distal end. See block 31.
Next, the inner surface of the first structural member is positioned adjacent to the distal ends of the plurality of intermediate members so that the plurality of intermediate members extend between the first and second structural members. See block 32. The first and second structural members must then be secured to each other by spot welding and then to the work table by clamping, so as to prevent movement of the first structural member relative to the second structural member and the plurality of intermediate members. See block 33.
The first structural member is then joined to the corresponding distal ends of each of the plurality of intermediate members by friction stir welding. See block 34. As described above, the friction stir welding is preformed by extending rotating friction stir welding probe through the first outer member into the distal end of the intermediate member. Thereafter, the structural assembly is secured to other structural assemblies to form the frame of an aircraft.
In the drawings and the specification, there has been set forth a preferred embodiment of the invention and, although specific terms are employed, the terms are used in a generic and descriptive sense only and not for purpose of limitation, the scope of the invention being set forth in the following claims.
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The machined-sandwich structural assembly has two components joined together with a joint of substantially the same strength as the weakest base material. More specifically, the structural assembly includes a first structural member and a second structural member. The first structural member is spaced from the second structural member through a plurality of intermediate members which extend between the first structural member and the second structural member. The plurality of intermediate members are friction stir welded to the first structural member. The resultant assembly requires less stock material, takes less time to machine and has a joint of improved strength.
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BACKGROUND OF THE INVENTION
The present invention is directed to the field of rubber mold centrifugal spin casting and more particularly to centrifugal spin casters used therefor.
Spin casting technology has been used for many years to produce costume jewelry, ornamental items, and has recently been employed to produce precision, high strength metal castings as well as thermoset plastic moldings, and wax investment casting patterns for engineered products. Spin casting offers the advantages of economical prototype and low volume production, short production lead time and low cost tooling. Further, it produces precision parts with close tolerances, smooth surfaces, and excellent detail at low per piece cost.
Basically, spin casting involves the use of a pair of complementary disc shaped rubber mold halves which are formed with a series of cavities therein. When the complementary rubber mold halves are placed together, a multi-cavity mold is formed. The multi-cavity rubber mold is clamped by air pressure between metal plates in a motor driven table. As the mold spins on the table, molten metal, liquid plastic or molten wax is poured into the center sprue of the mold, and the metal, plastic, or wax, forced outwardly through radial passageways or "runners" in the mold by centrifugal force, fills the mold cavities. Spin speeds typically range from 100 to 1000 RPM, depending on the size of the mold and the material being cast. The rotation may then be stopped, the mold opened, and the cast parts removed.
Heretofore, spin casters have been made such that access to the rotating turnable is from the top of the machine. The spin casters are typically provided with a horizontally disposed turntable having a plurality of vertically disposed clamp retainers. In one type of system for example, a central opening is provided in the turntable through which an hydraulic push rod is disposed. The push rod bears against a mold ram plate on top of and parallel to the turntable. The mold is adapted to be placed on top of the mold ram plate and a heavy metallic mold cover plate is placed on top of the mold. The mold coverplate is arranged such that clamp stays fixed thereto are placed underneath, and thus captive by, the clamp retainers attached to the turntable. After so adjusting the mold coverplate, the push rod may be actuated to thereby push the mold ram plate into firm engagement with the mold. In other systems, such as a "pancake" O-ring air clamping system, the pushrod is replaced by a hollow steel tube which allows the mold ram plate to be moved upwardly by forcing air directly against the bottom of the plate. In either case, the turntable, along with the mold and plates, are then rotated from the bottom of the machine. Molten metal, plastic, or wax material is poured through a central opening in the mold coverplate and thus delivered to the mold. After the spinning cycle is completed, the turntable, mold plates and the mold are brought to a stop, and the mold ram plate is separated from the mold coverplate. The mold coverplate is then released from the clamp retainers and lifted vertically from the machine by the operator to thus expose the mold. The mold is then removed by also lifting it vertically from the machine to complete the process.
There are many drawbacks associated with the above-described use of the prior art spin casting machines. The operator is burdened with several heavy lifting operations, specifically the vertical lifting into and from the machine of the mold and the heavy coverplate. Since two such operations (in the upward and downward directions) are required for both the mold and the coverplate, operation of the spin caster results in operator fatigue. Since the use of a heavy turntable and upstanding clamp retainers is required, the total spinning mass is high, resulting in slow startup and stopping times. This, coupled with the number of steps involved in placing the mold into and removing it from the spin caster result in very inefficient operation. Further, the upstanding clamp retainers present a serious hazard to the operator since speeds of up to 1000 RPM are not uncommon. Since the turntable, plates and the mold are turned from the bottom of the spin caster, the prior art spin casters are quite large in size and require an elaborate mold clamping/drive pulley mechanism for isolating the rotational movement of the apparatus from the hydraulic unit which provides the mold clamping pressure. Finally, since the mold and mold coverplate are hand loaded from the top of the machine, it is extremely difficult to utilize automatic liquid feeding devices.
OBJECTS AND SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide a spin caster which overcomes the difficulties associated with the prior art devices.
It is a further object of the invention to provide a front loading, top plate driven spin caster.
It is a further object of the invention to provide a spin caster which is of compact size and which can be table mounted.
It is a further object of the invention to provide a spin caster which is much more safe in operation than the prior art devices.
It is a further object of the invention to provide a spin caster which requires fewer operations and is thus more efficient than the prior art devices.
It is a further object of the invention to provide a spin caster which requires significantly less spinning mass than the prior art spin casters and is thus easier to stop and start than the prior art devices.
It is a further object of the invention to provide a spin caster which eliminates virtually all heavy lifting and thus greatly reduces operator fatigue.
It is a further object of the invention to provide a spin caster which readily lends itself to use with an automatic liquid feed system.
It is a further object of the invention to provide a highly efficient method of spin casting utilizing a front loading spin caster.
In accordance with the first aspect of the invention, a spin casting machine for spinning a mold includes a spin caster housing, a vertically stationary top plate disposed with the housing, a vertically movable bottom plate also in the housing, a loading door on a side of the housing, and means for applying a rotational force to the top plate. The vertically stationary top plate is adapted to rotate on a substantially vertical axis and has an aperture at the center thereof through which a liquid material is adapted to pass into the mold. The vertically movable bottom plate is adapted to rotate about the same substantially vertical axis. The loading door is adapted to allow the mold to be moved therethrough in a generally horizontal direction and placed on the bottom plate. The means for moving the bottom plate vertically upward causes the mold to contact the top plate such that the rotational force applied to the top plate propagates from the top plate through the mold to the bottom plate, the top plate, bottom plate and mold thus rotating together.
Preferably, the means for applying the rotational force to the top plate includes a pulley integral with the top plate and adapted to be engaged by a motor driven pulley belt. The means for moving the bottom plate vertically upward may comprise an air cylinder/piston assembly responsive to a control device, the control device selectively causing the cylinder/piston assembly to move the bottom plate up or down. Specifically, the control device may include a switch operatively connected to the loading door such that the bottom plate is moved up when the door is closed and down when the door is opened.
The top plate is preferably connected to the spin caster housing by way of a housing channel structure secured to the spin caster housing and by a first bearing for rotationally isolating the top plate from the channel structure and housing. The bottom plate is preferably connected to the spin caster housing by way of the cylinder/piston assembly which is in turn secured to, and suspended from the channel structure, and by a second bearing for rotationally isolating the bottom plate from the piston cylinder assembly.
Further, the bottom plate may be provided with a plurality of indexing pins and a greater number of indexing pin holes into which the pins are adapted to be disposed, such that molds of different sizes may be placed in the proper center locations on the bottom plate by placing the molds in abutment with the pins, the pins being movable to different pin holes to accommodate different size molds.
In accordance with the second aspect of the invention, a method for spin casting a mold in a spin caster includes the steps of loading the mold onto a vertically movable bottom plate and underneath a vertically stationary to plate, moving the bottom plate vertically upward to cause the mold to contact the top plate, applying a rotational force to the top plate, introducing a liquid material into the mold, terminating the rotational force, moving the bottom plate vertically downward, and removing the mold. The mold is loaded through a side of the spin caster housing onto the bottom plate. The top and bottom plates are adapted to rotate about a substantially vertical axis. The rotational force which is applied to the top plate propagates through the mold to the bottom plate to thus cause the top plate, the bottom plate and the mold to rotate together. The liquid material is introduced into the mold through an aperture in the top of the top plate.
Preferably, the step of loading comprises the steps of opening a loading door disposed on the side of the housing, thereby automatically moving the bottom plate vertically downward, moving the mold in a substantially horizontal direction onto the bottom plate, and closing the door to thereby automatically move the bottom plate vertically upward. The step of moving the mold onto the bottom plate may further comprise moving the mold into abutment with a plurality of indexing pins on the bottom plate.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects, aspects and embodiments of the invention will be described with reference to the following drawing figures of which:
FIG. 1 is a perspective and partial cross-sectional view of a prior art spin caster;
FIG. 2 is a perspective view of the front loading spin caster in accordance with the present invention;
FIG. 3 is a front cross-sectional view illustrating the details of the front loading spin caster in accordance with the present invention;
FIG. 4. is a top plan view of the top plate, motor and drive belt employed in the present invention; and
FIG. 5 is a top plan view of the bottom plate having indexing holes, indexing pins and a mold in abutment therewith in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
One example of a prior art spin caster 10 is illustrated in FIG. 1. Mounted on top of housing 12 is a rotatable turntable 14 which rotates on hollow shaft 16. Shaft 16 is fixed at its top to the bottom of the turntable 14 and fixed at the bottom to pulley 18. The pulley 18 is controlled by motor 20. Mounted within the hollow shaft 16 is a push rod 22 which is actuated by hydraulic ram 24 thereby moving the push rod up or down. The push rod is rotationally isolated from the ram 24 by means of a bearing coupler 26. The top of the push rod 22 bears against the mold ram plate 28 onto which the rubber molds 30 are placed. The mold coverplate 32 is then placed on top of the rubber molds 30 and positioned such that the stays 34 are disposed underneath the clamp retainers 36 which are secured to the bottom of the turntable. Finally, a metallic shield 38 is provided around the turntable, ram plate, molds and coverplate. A hinged cover, not shown, having a central opening, is included as well.
In operation, the operator places the rubber molds 30 and the coverplate 32 onto the mold ram plate 28, moves the stays 34 under the clamp retainers 36 and closes the hinged cover. The ram 24 is actuated to move the push rod and the ram plate 28 into abutment with the rubber molds 30. The motor 20 may then be actuated to turn shaft 16 and turntable 14, thus resulting in the rotation of the entire assembly of the turntable 14, plates 28 and 32 and the rubber molds 30. The liquid may then be ladled into the mold cavity 40 through a central sprue 42 provided in the mold coverplate 32 and the top rubber mold. The centrifugal force provided by the rotation forces the liquid material outwardly through channels or "runners" 44 into the mold cavities 40. After a short time, the motor 20 can be stopped and the operator waits until the entire assembly terminates its rotation, at which time the cover is opened, the ram is deactivated and the mold coverplate 32 is rotated to move the stays 34 out from under the clamp retainers 36. The mold coverplate must then be lifted vertically away from the rubber molds, and the rubber molds are subsequently lifted vertically off of the ram plate 28.
As will be appreciated by those skilled in the art, the foregoing series of steps is time consuming and causes a great deal of operator fatigue, especially since several of the steps involve bending over the machine and lifting the heavy coverplate 32 and molds 30 into and out of the spin caster. More specifically, the majority of operations do not involve the actual spin casting, but rather involve "set-up" steps, resulting in inefficient operation. Further, since the spin caster is rotated from the bottom by shaft 16 and the mold ram plate 28 is operated by ram 24 also from the bottom of the unit, the prior art spin caster must be provided rather elaborate apparatus such as the hollow shaft and pulley combination 16/18. This also leads to a rather big "stand alone" structure, certainly not the type of apparatus which could be conveniently disposed on a table top. Still further, since three relatively heavy metal plates 14, 28 and 32, in addition to the rubber molds 30, must rotate, the startup and stop times are undesirably high due to the high momentum and inertia produced by the massive apparatus. This also requires a substantial energy output by the machine. It is also readily apparent that even though a hinged cover is usually provided for the apparatus, the upwardly extending projections presented by the clamp retainers 36, represent a severe hazzard to the operator. Finally, it is extremely difficult to operate the prior art spin caster with an automatic feed device, which must be located above the spin caster, since access to the spin caster is from the top.
The front loading spin caster in accordance with the present invention avoids all of the above-mentioned difficulties inherent in the prior art devices. As shown in FIG. 2, the front loading spin caster 50 is of much more compact design and can be conveniently placed on a table top or virtually any other location as desired. The unit is provided with a flat and substantially unobstructed top surface 52 upon which an automatic liquid dispensing and metering system may be disposed. The top surface 52 can also be used as a table top upon which molds ready to be processed may be placed. As readily appreciated by those skilled in the art, such arrangements are difficult if not impossible with the top-loading prior art device.
Still with reference to FIG. 2, the front loading spin caster 50 is provided with an outwardly opening loading door 54 which may be opened and securely shut by means of spring loaded latch 56. Underneath the loading door 54 is a removable front access panel 58. A motor guard 60 is provided alongside the upper portion of the spin caster and is adapted to surround an electronic SCR motor 61 (FIG. 4) having an adjustable speed control from about 150 to 1,000 RPM. The top surface of the guard 60 can also be used as a table top for molds ready to be processed. A switch 62 for controlling the motor is provided at convenient location on the spin caster housing. The top surface 52 of the spin caster is provided with a heat resistant pad 64 made from transite, masonite or other suitable heat resistant materials. Centrally disposed on the top of the pad 64 is a pouring crucible 66 through which the liquid material is poured.
The details of the front loading spin caster in accordance with the present invention will now be discussed with further reference to FIG. 3. Secured to the housing of the spin caster by welding or other suitable means is channel 68. Suspended from the channel 68 is roller bearing assembly 70. A fixed position pulley/mold top plate 72 is connected to the roller bearing assembly by means of retainer plates 74 and bearing retainer 76 such that the fixed position pulley/top plate 72 can rotate in a horizontal plane relative to the fixed channel 68. The fixed position pulley/top plate 72 is preferably made out of aluminum or another light weight but strong metal or metal alloy. The bottom of the crucible 66 communicates with a hollow sprue 78 which is lined with a sprue insert 80 made of highly polished, hardened steel. As shown, a small gap is provided between the sprue insert 80 and the crucible 66, since the insert 80 rotates with the plate 72 while crucible 66 remains stationary.
Also secured to and suspended from the channel 68 is an air cylinder 82 having an air inlet 84 at the bottom thereof and a piston 86 at the top thereof. A movable bottom mold clamping plate 88 is connected to the piston 86 by means of a thrust bearing assembly 90 integral with the plate 88 and a block 92 between the thrust bearing 90 and the piston 86. The thrust bearing 90 allows rotation of the plate 88 in a horizontal plane relative to piston 86. Provided on the top of the clamping plate 88 are positioning means, such as a plurality of indexing pins (usually 3) which may be placed in different locations on the plate 88 for the proper location of different size molds. However, other means for positioning the plate may be employed as desired.
Also shown in FIG. 3 are the loading door 54 and the removable front panel 58. Operatively connected to the loading door 54 is a switch 94 which controls the air cylinder 82. Also provided is a collector tray 96 attached along one end to the channel and along the other end to the housing of the spin caster except for portion 98. The top surface 52 of the spin caster may be removed from the remaining portion of the spin caster housing at a location illustrated by the dashed lines 99 in FIGS. 2 and 3 in order to allow access to the top of the spin caster machinery for maintenance and the like. Although the top surface 52 will usually be connected to the remaining portion of the housing, the separation may be accomplished by removing a set of screws, or other fasteners. Finally, a support plate 100, fixed to the channel 68 is provided underneath the top surface 52 to allow for mounting of an automatic liquid feeding system.
As shown in FIG. 4, the motor 61 is connected to channel 68 by means of bracket 63 or other suitable means. A drive belt 65 is provided for rotating the top plate 72. An SCR motor control unit 67 is provided alongside the motor 61 and operates in a routine manner to provide any speed of rotation for the top plate 72 between about 150 and 1000 RPM. Associated with the SCR motor control unit 67 is a timer which functions in a well known manner to instruct the control unit that the spin cycle is complete. The motor control unit 67 provides dynamic braking of the motor upon termination of the spin cycle. The actual control dial for setting the speed of the motor 61 is disposed in a control panel separate from the spin caster. In fact, aside from the motor control 67, timer, push buttom 62 and switch 94, all other controls required for the spin caster are preferably disposed on a control panel separate from the spin caster, thus allowing the control panel to be mounted at a more convenient location, and thereby reducing still further the size of the spin caster.
In operation, the operator opens the loading door 54 to a horizontal position, thus deactivating the switch 94 which in turn causes piston 86 to retract within the air cylinder 82 to the position shown in solid lines in FIG. 3. With the loading door 54 opened to a horizontal position, it can be used as a tray to help facilitate the loading of the molds into the spin caster. The operator then places the molds 30 on the movable bottom mold clamping plate 88 such that the molds come into abutment with the indexing pins 89. As shown in FIG. 5, the indexing pins 89 are each disposed within one of a plurality of pin holes or slots 91 positioned on the plate 88 so as to allow the proper location of the molds 30 on the plate. Preferably, the pins are arranged in less than 180° of arc to facilitate the entry and removal of the molds 30 onto and from the plate. The positions of the pins can readily be changed by the operator depending upon the size of the molds currently being employed.
The operator may then close the loading door 54 thereby closing the switch 94 to cause activation of the air cylinder 82. The piston 86 rises to thereby clamp the molds 30 between the movable bottom plate 88 and the fixed position top plate 72, in the position indicated by the dashed lines. The operator may then push the switch 62 (FIG. 2) in order to start the motor 61. Alternatively, the micro switch 94 could also be used to start the motor if desired. The motor 61 functions to turn the entire assembly of the top plate 72, mold 30 and bottom plate 88 by means of the drive belt 65 driven about the pulley section of the plate 72. However, other means to provide the rotation, such as gears, and the like, may be employed if desired. Plate 72, along with the sprue insert 80, retainer plates 74 and bearing retainer 76 will rotate about the roller bearing assembly 70 in a horizontal plane relative to the channel 68 and the spin caster housing. The bottom plate 88 will rotate on the thrust bearing 90 parallel to, and through the same axis of rotation as the top plate 72. The operator can then either manually ladle the liquid material into the crucible 66 or can operate the automatic metal, plastic or wax dispensing and metering system if one is in use. The liquid material enters the mold 30 through the sprue 78 and is forced into each mold cavity by the centrifugal force exerted thereon. When the spin cycle is over, the motor control functions to dynamically brake the plates in response to a signal from the timer to quickly stop the rotation of the plates and molds. If however, the loading door 54 is opened during the spin cycle, the switch 94 provides to signal to the motor control to effect the dynamic braking and termination of the motor. Upon fully opening the loading door 54 the switch 94 will deactivate the air cylinder 82 to cause the piston 86 to retract to within the air cylinder 82 to the position illustrated in solid lines in FIG. 3. The operator may then simply slide the finished mold off the bottom plate 88 and out through the loading door 54 which acts as a tray in its horizontal position. The operator can then immediately repeat the process with another mold taken from the top "table" surface 52, the top of guard 60, or other convenient location.
The position of the top and bottom plates is designed such that approximately 7 inches clearance are provided between the two in the position illustrated in solid lines in FIG. 3, to thus allow any residual material within the sprue 78 to be cleared from the sprue upon retraction of the bottom plate 88. Any such residual material will be collected by collector tray 96 and deposited at the bottom of the spin caster housing underneath the gap 98 in the collector tray 96.
It will thus be appreciated that the front loading spin caster in accordance with the present invention provides an extremely efficient, simple and rapid spin casting technique. Since the only physical movement which need be employed by the operator is the placing and removing of the mold onto and from the bottom plate 88, a tremendous amount of effort is eliminated, since the operator is not required to vertically install and remove the mold and a heavy mold cover plate, as in the prior art. Since this is all that is required of the operator, the operation of the spin caster is much more efficient than the prior art spin casters, since fewer "set-up" operations are required. Since the plates and mold are driven from the top plate, separate from the piston/air cylinder assembly, the elaborate arrangement of the hollow shaft and push rod utilized in many of the prior art spin casters in not required. Since only the top and bottom plates 72 and 88 are involved in the spinning operation, rather than the three plates and the multiple clamp retainers employed in the prior art spin casters, less mass is turned in the present spin caster resulting in faster starts and stops and lower energy requirements. Since the present spin caster is driven from the top and is loaded from the front, rather than the top, it can be arranged with a very short profile allowing the unit to be used on a table top or on any other convenient support. Since the molds are loaded from the front, a relatively unobstructed top surface of the spin caster is provided, upon which an automatic dispensing and metering system can readily be installed. Finally, since none of the exposed protuberances such as the clamp retainers required on the prior art spin casters are required, the present spin caster is significantly safer to operate.
Although the present invention has been described with reference to the foregoing specification and drawings, many modifications, changes, additions and deletions to the invention may be made within scope and spirit thereof. For example, many different positioning means other than pins, and many different rotation means other than the pulley and belt arrangement, are within the purview of the invention. It is to be understood that the foregoing description of the invention is illustrative and not limiting, the scope of the invention being defined by the following claims.
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A front loading spin caster for spin casting a mold includes a vertically stationary top plate, a vertical movable bottom plate, a housing in which the top and bottom plates are disposed, a loading door disposed on one of the sides of the housing and adapted to allow the mold to be moved therethrough in a generally horizontal direction and placed on the bottom plate. The bottom plate can then be moved vertically upward to cause the mold to contact the top plate and a rotational force applied to the top plate propagates from the top plate through the mold to the bottom plate, the top plate, bottom plate and mold thus rotating together.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to a ball bearing that supports components in rotation, particularly in applications where axial thrust loads are present.
[0003] 2. Description of the Prior Art
[0004] To improve power density, there is a need to maximize ball fill and contact load capacity over that in regular single row deep groove ball bearings (DGBBs) using the standard Conrad design and method of assembly. Holding split bearing race segments together for both shipping and assembly present a problem.
[0005] Greater radial load capacity using additional balls can be achieved having a slot in one or both of the bearing races. This allows more radial capacity than the Conrad design but it severely reduces axial capacity, which is inappropriate for applications in which thrust loads can force the balls out of the slot.
[0006] An alternative is to use split-ring ball bearings, where one of the races is split in the middle to allow for more balls to be assembled in it. Unfortunately, handling and assembly suffer as the two halves of the split race are not retained together until installation. This also allows for more opportunity for mechanical damage and contamination until the whole open assembly is closed.
SUMMARY OF THE INVENTION
[0007] A bearing includes a first race including first and second segments, forming aligned pairs of first surfaces, spaced angularly about an axis; a second race including second surfaces, each second surface aligned with one of the pairs of first surfaces; balls, each ball contacting the surfaces of the first and second races; and a cage connecting each ball, engaging the first and second segments with a force that holds the segments in mutual contact.
[0008] Either the inner or outer race is formed in one piece; the other race is formed in two segments.
[0009] Contact between the ball and whole race can be at one central point, or at two points as with a Gothic arch bearing.
[0010] The ball may contact one or both of the segmented races when the segmented races are asymmetric.
[0011] The scope of applicability of the preferred embodiment will become apparent from the following detailed description, claims and drawings. It should be understood, that the description and specific examples, although indicating preferred embodiments of the invention, are given by way of illustration only. Various changes and modifications to the described embodiments and examples will become apparent to those skilled in the art.
DESCRIPTION OF THE DRAWINGS
[0012] The invention will be more readily understood by reference to the following description, taken with the accompanying drawings, in which:
[0013] FIG. 1 is an end view of a bearing with its component in spaced-apart relation;
[0014] FIG. 2 is a top view of a portion of the bearing of FIG. 1 ;
[0015] FIG. 3 is an end view of an alternate configuration of the bearing of FIG. 1 ;
[0016] FIG. 4 is an end view of an alternate configuration of the bearing of FIGS. 1 and 2 ;
[0017] FIG. 5 is an end view of the bearing configuration of FIG. 4 showing the split races spaced by unequal radial lengths from the ball;
[0018] FIG. 6 is an end view showing ball contact on the races, each over a single contact area; and
[0019] FIG. 7 is an end view showing ball contact on the solid race at multiple contact areas.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] FIG. 1 illustrates a bearing 10 that is symmetrical about an axis 12 . The bearing includes an outer race 14 , split inner races 16 , 18 and a cage 20 , formed with tabs 21 , 22 , which extend laterally. Cage tab 21 includes a leg 23 and cage tab 22 includes a leg 24 . Each of the legs 23 , 24 extends toward the axis 12 and overlaps the outer faces 26 , 28 of the split races 16 , 18 when the cage 20 is press-formed radially inward, thereby providing lateral continuity between races 16 , 18 .
[0021] The gap 30 between the races 16 , 18 is retained by press-forming the legs 23 , 24 of the tabs 21 , 22 such that the legs 23 , 24 bear with a running clearance to the outer faces 26 , 28 when the bearing 10 is in its assembled condition. The legs 23 and 24 are to have running clearance to the race surfaces, so as to retain the assembly in the uninstalled state, but minimize sliding friction in operation. A shaft/bore fastener may be used to close and/or preload the gap 30 , as with other bearings. The external shaft/bore fastener or some external device or preload would produce the axial force.
[0022] A spherical ball 32 enclosed by the races 14 , 16 , 18 , contacts at least a portion of the concave spherical inner surfaces 34 , 36 , 38 of races 14 , 16 , 18 .
[0023] FIG. 2 shows that the cage 20 is continuous about axis 12 and encircles each of the balls 32 . Each pair of tabs 21 , 22 is in a circumferential location between the balls 32 .
[0024] In the bearing configuration shown in FIG. 3 , split race 16 is formed with a rib 40 , which extends radially from the upper surface 42 of race 16 and along the circumference of surface 42 . Similarly, split race 18 is formed with a rib 44 that extends radially from the upper surface 46 of race 18 and along the circumference of race 18 .
[0025] The gap 30 between the races 16 , 18 is closed by press-forming the legs 23 , 24 of the tabs 21 , 22 such that the legs bear with a running clearance to the outer lateral faces of ribs 40 , 44 when the bearing 10 is in its assembled condition, thereby providing lateral continuity between races 16 , 18 .
[0026] In the bearing configuration shown in FIG. 4 , split race 16 is formed with a shoulder 50 , which extends along the circumference race 16 . Similarly, split race 18 is formed with a shoulder 52 , which extends along the circumference of race 18 .
[0027] The gap 30 between the races 16 , 18 is retained by press-forming the legs 23 , 24 of the tabs 21 , 22 such that the legs bear with a running clearance relative to the outer lateral faces of shoulder 50 , 52 when the bearing 10 is in its assembled condition, thereby providing lateral continuity between races 16 , 18 .
[0028] In the bearing configuration shown in FIG. 5 the split races 16 , 18 are spaced by unequal radial lengths from the ball 32 . The internal radius of curvature of concave spherical surface 36 is shorter than the internal radius of curvature of concave spherical surface 38 , thereby producing a gap g1 between the outer surface of ball 32 and surface 36 that is smaller than the gap g2 between the outer surface of ball 32 and surface 38 . The centerpoint of the internal radius of curvature of concave spherical surface 36 may also be axially and/or radially offset in space from the internal radius of curvature of concave spherical surface 38 , thereby aligning gap g1 differently than gap g2 to allow for asymmetric loading and contact stress characteristics between ball 32 and surfaces 34 , 36 , 38 .
[0029] Due to the asymmetric race profiles of surfaces 36 , 38 , pairs of bearings can be arranged such that greater radial and axial load capacity in one axial direction can be achieved in one member of the pair and greater radial and axial load capacity in the opposite axial direction can be achieved in the other member of the pair, thereby providing reactions bi-directional axial thrust loads at the bearing pair.
[0030] FIG. 6 is an end view showing contact between ball 32 and the races 14 , 16 , 18 . Because the radius of curvature of each concave spherical surface 34 , 36 , 38 is greater than the radius of the ball 32 , the range of contact on each race 14 , 16 , 18 occurs at a single contact area that is less than the entire area of each surface 34 , 36 , 38 .
[0031] FIG. 7 is an end view showing ball contact between ball 32 and the races 14 , 16 , 18 . Because the radius of curvature of each concave spherical surface 36 , 38 is greater than the radius of the ball 32 , the range of contact on races 16 , 18 occurs at a single contact area that is less than the entire area of surfaces 36 , 38 .
[0032] FIG. 7 shows that the inner surface of race 14 has the form of a Gothic arch. Because the inner surface of race 14 comprises two spherical surfaces 60 , 62 each having a center of curvature that is offset from the center of ball 32 and mutually non-coincident, the range of contact on race 14 occurs at multiple contact areas, the sum of the areas being less than the entire area of surfaces 60 , 62 .
[0033] In each of the configurations, the one piece race, such as race 14 , may be either the inner race or the outer race, and the other race may comprise two parts, such as the race portions 16 , 18 .
[0034] In accordance with the provisions of the patent statutes, the preferred embodiment has been described. However, it should be noted that the alternate embodiments can be practiced otherwise than as specifically illustrated and described.
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A bearing includes a first race including first and second segments, forming aligned pairs of first surfaces, spaced angularly about an axis; a second race including second surfaces, each second surface aligned with one of the pairs of first surfaces; balls, each ball contacting the surfaces of the first and second races; and a cage retaining each ball and engaging the first and second segments.
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This application is a continuation-in-part of U.S. Ser. No. 07/969,715 filed Oct. 27, 1992, now U.S. Pat. No. 5,230,365 issued Jul. 27, 1993.
The present invention generally relates to water valve apparatus and is more particularly directed to water valve apparatus with distal control.
Remote control water valves have heretofore found use in many medical and industrial applications in which the volume of water flow must be controlled independently from the user's hands.
Remotely operated water valves, controlled by, for example, knee motion or foot motion, are also particularly advantageous for many handicapped persons. Unfortunately, the installation of such remotely controlled valves has heretofore been expensive and complicated due to the necessity of special plumbing lines to and from remote disposed valves and the like.
Existing complicated and expensive plumbing configurations and the complex nature of heretofore proposed remote valve devices have inhibited the retrofitting of millions of existing wash basins and the like, which would be advantageous for both convenience and necessity to many handicapped individuals.
An additional deterrent to retrofit or after market devices for converting an existing faucet system into a remote control system is the typical lack of space in conventional cabinets housing the residential sink or basin.
Safety requirements are also a consideration, particularly if the adaptation of a conventional faucet system requires electrical connection for operation. Electrical requirements can add significant cost to such installations due to the necessary additional circuit outlets which should be of the ground fault type.
Hence, there is a need for a water valve apparatus with remote control which may be retrofitted to existing faucets in a safe, economical manner, without the additional complex running of plumbing lines to and from a remote switch and a requirement for electrical power.
The present invention satisfies that need in providing a water valve system which may be easily installed beneath an existing water basis or within a kitchen cabinet with only the use of short plumbing flex lines.
SUMMARY OF THE INVENTION
Water valve apparatus with distal control in accordance with the present invention generally includes valve means for controlling flow of water therethrough with the valve means including a movable actuator for starting and stopping the flow of water. A permanent magnet is provided and disposed proximate to the actuator for magnetic engagement therewith, which provides means for moving the actuator between a first position, stopping water flow through the valve, and a second position, allowing water flow through the valve.
In addition, a movable member is provided in order to alter the magnetic engagement between the permanent magnet and the actuator in order to move the actuator.
A cable having a distal and a proximal end is provided for moving the movable member with the cable proximal end being connected with the movable member and a manually operated lever connected to the cable means distal end provides a means for operating the cable in a manner causing movement of the permanent magnet and concomitant movement of the actuator as a result of magnet engagement alteration, in order to start and stop water flow through the valve.
Because there is only a mechanical link by way of the cable between the lever and the movable member, no electrical components are necessitated by the installation of the apparatus in accordance with the present invention.
A valve housing may be provided, which includes both hot and cold water inlets and outlets for cold water valve means for controlling the flow of cold water and hot water valve means for controlling the flow of hot water.
Flexible water lines provide a means for interconnecting the valve housing hot and cold water inlets and outlets to hot and cold water sources and to hot and cold water inlets of existing water faucets, without fixing the valve housing to any permanent structure.
In conjunction therewith, the cable may comprise a slidable center wire attached to the movable member and a sheath, surrounding this center wire and affixed to the valve housing, provides means for enabling the operation of the valve means through the cable means without stabilizing the valve housing.
This is important in that the valve housing need not be rigidly mounted to a structure beneath the basin, such as a wall or other rigid plumbing pipes or valves. Therefore, the housing in accordance with the present invention may be loosely arranged within a base and cabinet, around, under, or suspended through existing pipes and valves which greatly facilitates the installation thereof.
More particularly, the water valve apparatus in accordance with the present invention may include two hereinabove referenced valve means, one for hot and one for cold water, each including an actuator, coupled by a separate permanent magnet. In this instance, two movable members may be provided, each one associated with an actuator/permanent magnet arrangement.
Means may be provided for enabling simultaneously the two separate movable members by the cable means.
To ensure coupling of the permanent magnets with the actuators, the permanent magnets may have the shape of a doughnut and arranged so that the actuators are disposed for movement within a center hole of each of the doughnut-shaped magnets. Alteration of the magnetic engagement is effected by mounting the movable members for movement between an actuator and respective permanent magnets.
In order to facilitate use of the valve apparatus, the manually operated lever may include a releasable lock means for holding the movable members in a position maintaining the actuators in a position allowing continued water flow through the valves. In one embodiment of the present invention, manually operated lever means may comprise a foot pedal and, in another embodiment of the present invention, manually operated lever means may comprise a knee pedal.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages and features of the present invention will be better understood by the following description when considered in conjunction with the accompanying drawings in which:
FIG. 1 is a perspective view of the present invention as installed in a typical lavatory sink;
FIG. 2 is a perspective view of the present invention showing in particular doughnut-shaped magnets encircling valve actuators;
FIG. 3 is a cross-sectional view of the present invention showing a remote control and valves in a closed position;
FIG. 4 is a cross-sectional view of the present invention showing the remote contacts depressed and the valves in an open position;
FIG. 5 is a perspective view of an alternative embodiment of the present invention; and
FIG. 6 is a cross-sectional view of the embodiment shown in FIG. 5.
DETAILED DESCRIPTION
Turning now to FIG. 1, there is shown water valve apparatus 10 in accordance with the present invention as it may be installed beneath a conventional sink 16 or the like. FIG. 2 and FIG. 3 more particularly show the apparatus as generally including diaphragm type valves 12, 14, which provide a means for controlling hot and cold water therethrough, respectively.
The valves may be enclosed by housings 18, 20 and held in an abutting adjacent relationship by a plate 24, conventionally screwed or riveted to the housings 18, 20. Alternatively the valves 12, 14 may be enclosed in a unitary housing.
Diaphragm valves 12, 14, suitable for use in the present invention, are commercially available from the Horton Company of Pittsburgh, Pennsylvania, with specific utility of Model No. 525, produced by the Horton Company. These types of valves are well-known and are controlled by actuators 30, which are spring 36 biased within tubes 42, 44, interconnected with the housings 18, 20 through the plate 24. Valves of this type are typically utilized in laundry and dishwashing appliances (not shown), in which the actuators 30 are coupled to solenoids (not shown) for movement of the actuators 30 within tubes 42, 44 in order to open and close the diaphragm (not shown) in each valve 12, 14, in a conventional manner.
Flex lines 48, 50, coupled respectively to hot water inlets 54, 56 by means of threads 58, 60, provide a means for coupling the valves 12, 14 to hot and cold water sources 64, 66, respectively.
Outlet flex lines 72, 74, similarly connected to hot and cold water outlets 78, 80 by means of threads 84, 86, provide a means for connecting the valves 12, 14 to the hot and cold water inlets 90, 92, respectively, of a conventional faucet 96.
It is important to appreciate that the flex lines 48, 50, 72, 74, which may be reinforced plastic, contribute significantly to the present invention. These flex lines enable the valves 12, 14 to be positioned beneath the sink 16 and the faucet 96 in and around plumbing which includes a sink trap 98, without requiring rigid mounting of the valves 12, 14. Thus, depending upon the length of the flex lines 48, 50, 72, 74, the valves 12, 14 may be placed in any convenient position beneath the faucet 96 and, as hereinafter described, no interference with the operation of the valves 12, 14 is caused by such a "floating" configuration. Naturally, this drastically simplifies the installation of the apparatus 10 so that such installation may be accomplished by a homeowner.
Simultaneous operation of the valves 12, 14, as hereinafter described, enable the faucet lever 100 to be adjusted to a preselected position to control a desired temperature of water exiting from the faucet spout 102. Naturally, faucets with dual controls (not shown) may similarly be preset for use with the apparatus 10 in accordance with the present invention.
The presetting of the faucet lever 100 enables operation of the apparatus 10 to turn water on through the faucet spout 102 at a preselected volume and temperature, thus facilitating the use of the faucet by a handicapped person, incapable of controlling the lever 100 or separate turnable controls (not shown).
As more clearly shown in FIG. 2, ring magnets 104, 106 are disposed proximate and surrounding the actuators 30, 32 within actuator tubes 42, 44, respectively for magnet engagement therewith and for moving the actuator tubes 42, 44 between a first position (shown in solid line) stopping water flow through the valves 12, 14 and a second position, shown in FIG. 3, allowing water to flow through the valves 12, 14. As shown in FIG. 3, the spring 36 maintains the actuator 30 in an "off" position when the ring magnet 106 is in the first position. Movement of the ring magnets 104, 106 in the direction of arrows 114, 116 causes sufficient coupling between the magnets 104, 106 and the actuators 30 to move the actuators 30 in the direction of the arrow 118 and against the action of spring 36 to open the respective valves 12, 14.
Each of the ring magnets 104, 106 is held in position by arms 122, 124, respectively, which are pivotally mounted to the plate 24 by means of pins 126, 128 through pivot mounts 134, 136, respectively. Screws 138 may be used to secure the magnets 104, 106 to the arms 122, 124. A Bodin or bicycle-type cable 140 includes a proximal end 144, including a slidable wire 148 and a sheath 150 fixed to a bracket 152 attached to the valve housings 18, 20 through the plate 24.
Because the sheath is fixed to the valve housing, the slidable wire 148 is movable with respect thereto, which enables the valve housing 18, 20 to "float" while being attached to the hot and cold water sources 64, 66 and hot and cold water inlets 90, 92 by means of the flex lines 48, 50, 72, 74. A set screw 156 in a mounting bushing 158, attached to the bracket 152, enables a length adjustment of the cable 140 as hereinafter described in greater detail.
The slidable wire 148 is attached to a bar 162 with the bar 162 being loosely attached to the arms 122, 124 by means of bushings 166, 168, in order to provide a means for simultaneous movement of the two separate permanent magnets 104, 106 by the cable 140.
The embodiment as shown in the drawings, the cable 140 with slidable wire 148 therein, operates to open the valves upon pulling of the sliding wire 148 into the sheath 150, as shown by the arrow 172. (See FIG. 4.) Alternatively, the cable 140 and valve 12, 14 arrangement may be provided so that pushing of the slidable wire 148 out of the sheath 150 enables opening the valves. The slidable wire 148 may be guided through the valve housings 18, 20 through a bushing arrangement 176, and a clamp 178 fixed to the slidable wire 148 enables a spring 182, disposed between the clamp 178 and the bushing 158, to return the slidable wire 148 and magnets 104, 106 to a position (see FIG. 3) closing the valves 12, 14 when force pulling the slidable wire 148 is released.
In operation, a center hole 186, 188 in each of the magnets 104, 106 is sized to enable movement of the magnets in the direction of the arrows 114, 116 without binding contact with the actuator tubes 42, 44. The magnets, of course, are sized in width and pre-magnetized to ensure sufficient coupling with the actuators 130, 132. While other shaped magnets may be used, it has been found that the ring magnet 104, 106 configuration provides uniform coupling with the actuators 30 without causing detrimental resistance between the actuators 30 and the actuator tubes 42, 44, due to magnetic coupling between the magnets 104, 106 and actuators 30.
Turning now to FIGS. 3 and 4, in one embodiment of the present invention, the distal end 192 of the cable 140 is attached to a pedal 194 which includes a base 198 and a tread 200 pivotally attached to the base by a means of a pin 204. As shown in FIG. 1, dashed lines, the pedal may be mounted for operation by a knee (not shown). A distal end 206 of the slidable wire 148 is attached an arm 210 proximate a base pivot 212, so that movement of the tread 200 by a knee or foot (not shown) depressing and releasing the tread 200 in the directions indicated by the double-headed arrow 216 causes translational movement of the wire 148, as indicated by the arrow 218. With a distal end 220 of the sheath 150 attached to an end bracket 222 of the base, movement of the slidable wire 148 is not translated to the sheath 150 which is fixed to the brackets 152 and 222.
The arm 212 is pivotally mounted to the tread 200 by means of a pin 226, and a spring 230 causes the tread 200 to return to a spaced apart relationship with the base 198 after a depressing force applied thereto is released.
In order to lock the tread 200 in a depressed position, a wire 234 attached to the base 198 and extending through a hole 236 in the tread with a protruding head 138 is provided. The hole 236 having a keyhole shape enables the head 138 to fall into a slot portion 140 of the hole 236 to maintain the tread 200 in a depressed position. To release the tread 200, the head 138 is merely pushed into a circular portion 242 of the hole 236.
The pedal 194 may be installed at the base of a sink cabinet 248, shown in FIG. 1 (solid line), after interconnection of the flex lines 48, 50, 72, 74. During installation, the cable sheath 150 is released from the bushing 158 via the set screw 156 and the slidable wire 148 removed from the bar 162 for enabling installation of the cable 140 through the cabinet 248 without the necessity of cutting a large hole for the foot pedal 194. A small hole 250 drilled in the cabinet 248 enables passage of the cable which is thereafter interconnected with the valve housing 18, 20, as hereinabove described. After placement of the pedal, the set screw 156 allows a length adjustment of the sheath 150 to ensure that the pedal depression operates with the magnets 104, 106 through the arms 122, 124.
Turning now to FIGS. 5 and 6, there is shown an alternative embodiment 260 of a water valve apparatus in accordance with the present invention, which generally includes diaphragm valves 262, 264 identical to or similar to valves 12, 14, with the valves 262, 264 held in a spaced apart relationship by a mounting plate 266. Operation and connection of the valves 264, 266 is the same as hereinbefore described in connection with embodiment 10 of the present invention. Valves 262, 264 with actuator tubes 270, 272 for supporting actuators 274,276 operate in a manner identical to the actuators 30 and tubes 42, 44 hereinabove described.
One or more permanent magnets 278, 280, 282, 284 are fixed to the mounting plate 266 in a position surrounding the actuators 270, 272 respectively. This relationship provides for a magnetic engagement between the permanent magnets and the actuators similar to that hereinabove described in connection with embodiment 10 of the present invention. Spring 286, 288 mounted to the plate 266 bias a movable member 292 which provides a means for altering the magnetic engagement between the permanent magnets 278, 280, 282, 284 and the actuators 274, 276.
In that regard, depending cylinders 296, 298 are sized and configured for movement from an up position, shown in solid line in FIG. 6, to a down position, shown in phantom line in FIG. 6. When the depending cylinders 296, 298, as well as the member 292, are in the up position, full magnetic engagement is effected between the permanent magnets 278, 280, 282, 284 and the actuators 274, 276.
Preferably, the depending cylindrical members are formed of a ferromagnetic material and therefore the positioning between the permanent magnets 278, 280, 282, 284 and the actuators 274, 276 alters the magnetic engagement. The permanent magnets are sized and of proper strength such that when the depending cylindrical members are disposed between the permanent magnets and the actuators, the field is altered, or interrupted, sufficiently to enable the actuators to move in position, thus controlling flow of water through the valves 262, 264 as hereinbefore discussed.
The member 292 is stabilized by support rods 300, 302 and secured through the use of nuts 306, 308. Passing through an opening 400 in the plate 266 is a slidable wire 404 having a head 406 sized to pass through an opening 408 in the member 292 and engage the member 292 as shown by translational movement to a portion of the hole 408 smaller than the head 406. A cable 410 having a slidable wire 404 therein is interconnected to the foot pedal 194, as shown in FIG. 3 and hereinabove discussed. As also hereinabove described, the slidable wire 404 may be guided through the plate 266 by means of a bushing arrangement 414 with a set screw 416 for enabling a length adjustment of the cable 410 as hereinabove described and shown in FIG. 3.
Although there has been hereinabove described a specific water valve apparatus in accordance with the present invention, for the purpose of illustrating the manner in which the invention may be used to advantage, it should be appreciated that the invention is not limited thereto. Accordingly, any and all modifications, variations, or equivalent arrangements which may occur to those skilled in the art, should be considered to be within the scope of the present invention as defined in the appended claims.
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Water valve apparatus with distal control includes at least one valve for controlling flow of water therethrough and having a movable actuator for starting and stopping the flow of water. A permanent magnet, disposed proximate said actuator for magnetic engagement therewith, is provided for moving the actuator between a first position stopping water flow through the valve and a second position allowing water flow through the valve. A movable member is provided to alter the magnetic engagement between the permanent magnet and the actuator in order to move the actuator. A cable, having a slidable center wire attached to the movable member and a sheath attached to the valve is connected to a manually operable lever, for operating said cable in a manner causing movement of the movable member and concomitant movement of the actuator, as a result of magnetic engagement alteration, in order to start and stop water flow through the valve.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is based on provisional application Ser. No. 60/831,028, filed on Jul. 14, 2006.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
DESCRIPTION OF ATTACHED APPENDIX
[0003] Not Applicable
BACKGROUND OF THE INVENTION
[0004] This invention relates generally to the field of Enhanced Oil Recovery (EOR) and more specifically to an Oil Recovery Process employing mixtures of amphoteric surfactants. The amphoteric surfactants are betaines containing both saturated and unsaturated hydrophobic hydrocarbyl groups and are derived from naturally occurring oils and fatty acids rendering them green and biodegradable.
[0005] This invention also relates to the recovery of oil from subterranean oil reservoirs and more particularly to improved chemical flooding operations involving the use of certain mixtures of amphoteric surfactants that are suitable for use in brines containing relatively high concentrations of divalent metal ions and at high temperature ranges.
[0006] Crude oil is recovered from oil-bearing reservoirs generally by three processes designated primary, secondary and tertiary recovery. In primary recovery the oil is produced through a producing well by taking advantage of the pressure exerted on underground pools of oil by gas or water present with the oil. Approximately 20% of the original oil in place (OOIP) is recovered by this process. Once this pressure has been exhausted other means of recovering the remaining oil must be employed. In secondary recovery the well may be re-pressurized with gas or water injected through one or more injection wells to recover approximately an additional 20% of the OOIP. Other secondary recovery methods include acidizing and/or fracturing to create multiple channels through which the oil may flow. After secondary recovery means have been exhausted and fail to produce any additional oil, tertiary recovery can be employed to recover additional oil up to approximately 60% OOIP. Tertiary oil recovery processes include, but are not limited to, steam flooding, polymer flooding, microbiological flooding, and chemical flooding.
[0007] Chemical flooding includes the use of surfactants for lowering the interfacial tension (IFT) between the injection brine and the residual oil usually to an ultra-low value of below 1×10 −2 mN/m. Mobility control agents such as polymers are usually employed along with surfactants to adjust the mobility ratio between the oil and the injection brine. It has also been found that alkali, when included in the injection brine, can react with the acidic material present in the trapped oil to form surface-active salts that enhance the effectiveness of the injected surfactant. Alkali also is preferentially adsorbed onto the reservoir and therefore reduces the loss of surfactant and polymer through adsorption.
[0008] Alkaline-Surfactant-Polymer Flooding (ASP) has been the subject of numerous studies, papers and patents, for example U.S. Pat. No. 4,004,638 issued to Burdyn et al. in 1977 and U.S. Pat. No. 6,043,391 issued to Berger et al. in 2000. Several other tertiary chemical processes for enhanced oil recovery include Alkaline Surfactant (AS), Alkaline Polymer (AP), and Alkaline flooding. The alkali commonly used in these applications are inorganic alkali including, but are not limited to, sodium hydroxide, sodium carbonate, the combination of sodium hydroxide and sodium carbonate, and sodium silicates.
[0009] There are many examples of the prior art that discuss the use of different types of surfactants and/or surfactant formulations for EOR including amphoteric surfactants. As is known by those who are familiar with the art, amphoteric surfactants have the advantages of providing low IFT, tolerance to salt and di-valent cations and fair to low adsorption loss to the formation. U.S. Pat. No. 4,216,097 to Stournas, discloses a process for the recovery of oil from subterranean reservoirs employing an aqueous solution of an amphoteric surfactant. The amphoteric surfactant is used at a relatively low concentration within the range of 0.001 to 0.1 weight percent and is injected in a relatively large pore volume amount of at least 0.5 pore volume. U.S. Pat. No 4,554,974 to Kalpakei, et al. discloses a method for recovering petroleum using a surfactant slug comprising an aqueous solution containing about 0.001 to about 5% by weight of an amphoteric surfactant and an effective amount of high molecular weight homopolysaccharide gum thickener derived from the fungus strains of genus Schlerotium.
[0010] Although the prior art employ amphoteric surfactants as part of various formulations for the recovery of oil, we have unexpectedly found that the degree of unsaturation and the distribution of carbon chain lengths in the lipophilic base is of extreme importance to lower IFT for a wide range of different gravity oils and brines. Furthermore, relatively low pore volumes of the injection fluid including the mixture of the amphoteric surfactants is required for effective oil recovery. This present invention provides improved performance and economics over the prior art.
LIST OF FIGURES
[0011] None
BRIEF DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
[0012] The present invention provides a new and improved chemical flooding process for the recovery of oil from subterranean reservoirs that comprises injecting into one or more injection wells and recovering the oil from one or more production wells a composition containing:
[0013] a) a mixture of amphoteric surfactants each characterized by the formula:
[0000]
[0014] wherein:
[0015] R 1 is a hydrocarbyl group containing from 8 to 26 carbon atoms, the average of all hydrocarbyl groups having a ratio of Iodine Value (IV) to the Molecular Weight (MW) of the hydrocarbyl chain of at least 0.15 or R 1 is an alkyl amido group of the following structure
[0016] R—O—N—CH 2 CH 2 CH 2
[0017] Where R═R 1
[0018] R 2 and R 3 are each independently a hydrocarbyl group containing from 1 to 8 carbon atoms or an alkoxy group containing from 2 to 10 carbon atoms and having a ratio of carbon atoms to oxygen atoms within the range of 2 to 3,
[0019] R 4 is an aliphatic group containing from 1 to 6 carbon atoms, and
[0020] A is a sulfonate group or a carboxylate group; and,
[0021] b) optionally one or more alkali,
[0022] c) optionally one or more thickening agents,
[0023] d) optionally one or more co-solvents
[0024] e) an aqueous solvent; and;
[0025] recovering the oil from one or more production wells.
[0026] The injection and production well may be the same well. The aqueous solution may contain other ingredients, known to the art, as needed. These include alkali to reduce adsorption, thickening agents to provide an effective mobility ratio, and co-solvent to improve in product handling, dissolution and compatibility. Alkali may be used at levels of 0 to about 2 wt %. Thickening agents may be used at concentrations from 0 to about 5 wt % and co-solvents may be used at concentrations of from 0 to about 10 wt % of the injection fluid.
[0027] In this disclosure amphoteric surfactants and betaines are used interchangeably to identify the structure previously described above.
[0028] A preferred application of the amphoteric surfactants of the present invention is their use with brines or brines containing relatively high concentrations of salt and divalent metal ions. They are effective over a wide range of electrolyte concentrations and they can be used over a wide range of concentrations and still give ultra-low IFTs. Furthermore, the mixture of amphoteric surfactants of the present invention are derived from fatty acids and naturally occurring animal, vegetable or marine oils that are biodegradable and green in nature.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] Detailed descriptions of the preferred embodiment are provided herein. It is to be understood, however, that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in virtually any appropriately detailed system, structure or manner.
[0030] The present invention is an improvement over the prior art where amphoteric surfactants have been used to enhance the recovery of oil. The present invention involves a process for of recovery oil from a subterranean reservoir by injecting an aqueous liquid containing:
[0031] a) a mixture of amphoteric surfactants, each characterized by the formula:
[0000]
[0032] wherein:
[0033] R 1 is a hydrocarbyl group containing from 8 to 26 carbon atoms, the average of all hydrocarbyl groups having a ratio of Iodine Value to the Molecular Weight of the hydrocarbyl chain of at least 0.15 or R 1 is an alkyl amido group of the following structure R—O—N—CH 2 CH 2 CH 2
[0034] Where R═R 1
[0035] R 2 and R 3 are each independently a hydrocarbyl group containing from 1 to 8 carbon atoms or an alkoxy group containing from 2 to 10 carbon atoms and having a ratio of carbon atoms to oxygen atoms within the range of 2 to 3,
[0036] R 4 is an aliphatic group containing from 1 to 6 carbon atoms, and
[0037] A is a sulfonate group or a carboxylate group;
[0038] b) optionally one or more alkali,
[0039] c) optionally one or more thickening agents,
[0040] d) optionally one or more co-solvents
[0041] e) an aqueous solvent; and;
[0042] recovering the oil from one or more production wells.
[0043] The groups R 2 and R 3 may be the same or different and are selected from the group consisting of C1-C.8 hydrocarbyl groups or C2-C10 alkoxy groups having a ratio of carbon atoms to oxygen atoms within the range of 2 to 3. Stated otherwise, where R 2 or R 3 is an alkoxy group, it may be ethylene oxide, polyethylene oxide containing up to 5 ethylene oxide units, propylene oxide, polypropylene oxide containing up to 3 propylene oxide units, or oligimers of mixtures of ethylene oxide and propylene oxide containing no more than 10 carbon atoms. The nature of the R 2 and R 3 groups are, as noted previously, somewhat dependent upon the nature of the R 1 group or R group. Where R or R 1 comprises a relatively long chain aliphatic substitutent, R 2 and R 3 normally will be relatively short chain hydrocarbyl groups or ethylene oxide derivatives. For example, where R or R 1 is a C14-C.18 aliphatic radical, R 2 and R 3 normally will be methyl or ethyl groups or groups comprising ethylene oxide, propylene oxide, or polyethylene oxides.
[0044] Non-exclusive examples of suitable alkalis are sodium hydroxide, sodium carbonate, sodium silicate, potassium hydroxide, potassium carbonate, or potassium silicate. Non-exclusive examples of thickening agents include polymers such as xanthan gum, polyacrylamide or viscoelastic surfactants such as betaines and amine oxides. Non exclusive examples of suitable co-solvents include low molecular weight alcohols, glycols, polyglycols, and glycolethers such as propylene glycol, ethylene glycol, diethylene glycol, iso-propanol, butanol, iso-butanol, hexanol, 2-ethyl-hexanol, octanol, ethylene glycol monobutyl ether. The aqueous solvent may be water, an oilfield brine or a synthetic brine.
[0045] The amphoteric surfactant contains an inner quaternary ammonium group that is linked to a terminal sulfonate group or carboxylate group. The electrical charge on the inner quaternary group is electrically balanced by the terminal anionic group and such amphoteric surfactants may thus be characterized as dipolar ions or zwitter ions. The lipophilic base of the surfactant is linked to the terminal anionic group through the quaternary ammonium group and is provided by one or more hydrocarbyl groups.
[0046] The present invention has unexpectedly found the amount of unsaturation and the distribution of various carbon chain lengths of the lipophilic base within the amphoteric surfactants are very important for the performance of the amphoteric surfactants in the recovery of oil. The present invention also found that the optimum IFT and oil recovery, using relatively smaller pore volume than have been used in the past, may be obtained by using the proper mixture of the amphoteric surfactants with different amount of unsaturation and distribution of various carbon chain lengths of the lipophilic base within the amphoteric surfactants to improve the economics and the efficiency of the oil recovery process.
[0047] Non-exclusive examples of amphoteric surfactants which may be employed in carrying out the present invention include those having a lipophilic base derived from coconut oil, palm oil, palm kernel oil, tall oil, tallow, canola oil, rapeseed oil, herring oil, menhaden oil, soybean oil, corn oil, high erucyl acid rapeseed (HEAR) and other naturally occurring oils containing long chain fatty acids residues having a ratio of Iodine Value to the Molecular Weight of the hydrocarbyl chain of at least 0.15. Hydrogenated oils or those naturally containing a predominance of saturated lipophilic constituents have been found to perform poorly as components for recovering oil. Synthetic saturated and unsaturated derivatives having over 90% by weight of one component have also been found to perform less effectively than blends but can be used if two or more are blended to give the required MW and IV as will be described.
[0048] As is understood by those skilled in the art, surfactant molecules are characterized by an oil-soluble portion of the molecule that tends to partition into the oil phase of an oil-water interface and a water-soluble portion, that tends to partition into the water phase. In the amphoteric surfactants employed in the present invention, the sulfonate or carboxylate group is the water soluble portion. In addition, the ammonium quaternary group tends to impart water solubility to the surfactant molecule to a degree depending upon the characteristics of the substituents, R 2 and R 3 , defined previously. The greatest water solubility is observed when the R 2 and R 3 are methyl or ethyl radicals or ethylene oxide derivatives. Propylene oxide derivatives and mixtures of ethylene oxide and propylene oxide derivatives van be used to obtain greater oil solubility or intermediate solubility.
[0049] The aliphatic group, R 4 , defined previously, inking the quaternary ammonium and the sulfonate or carboxylate groups contains 1 to 6 carbon atoms and, in the case of R 4 containing 2 or more carbon atoms, may be saturated or unsaturated, and straight or branched chained. The R 4 radical may also be substituted with a group such as a hydroxy group, which tends to increase the water solubility of this portion of the surfactant molecule. Usually, however, the R 4 group will be unsubstituted hydrocarbyl radical. In a preferred embodiment of the invention, R 4 is an aliphatic group containing from 1 to 4 carbon atoms.
EXAMPLE 1
[0050] Analysis of various fatty acid and oils that we have used to synthesize the various betaines are shown in Table 1 in decreasing order of their Acid Value (AV). The AV is defined as the milligrams of potassium hydroxide necessary to neutralize the fatty acids in a 1 gram sample. The AV is a commonly accepted property used in the Fats, Oils and Surfactant Industries and can be determined using AOCS Official Method Te 1a-64 from the American Oil Chemists Society.
[0000]
TABLE 1
Composition of various fatty acids and oils
Acid or Oil
AV
<C12
C12
C14
C16
C16 1
C18
C18 1
C18 2
C18 3
C20
C20 1
C20 2
C22
C22 1
>C22
C-1299 a
279
1
99
0.5
C1216 a
263
1
61
25
11
0.5
1.5
Coconut Oil b
255
13
47
19
9.5
3
7
1.5
Palm Kernel Oil b
250
47
16
8.5
2
17
3
C-1495 a
245
2
97
1.5
Palmitic acid g
219
99%
C-1214 a
209
1
70
27
2
Emersol ® 6321NF c
201
3
5
6
79
6
1
Palm Oil b
200
1
45
3.8
40
10
0.2
Canola Oil d
200
4.2
1.9
58.8
21.2
10.2
0.6
1.7
0.3
1
0.1
Linoleic acid g
200
99.2
OL-600 a
199
0.3
5
0.3
2
61.3
20.4
6.2
2
2.5
Oleic acid g
197
99+
C18-20 e
197
2
4.5
2.4
23.4
30
19.5
1.5
13
1.3
2.4
Stearic acid g
197
96
Tallow, BFT
197
3
24
3.5
21
43
5
0.5
Emersol ® 153NF c
196
4
96
Soybean Oil d
192
0.8
0.5
0.5
10
4
22
54
8
0.2
Tall Oil fatty acid
180
2
59
37
1
1
HEAR Oil e
176
1.1
2.1
0.1
1.1
11.4
14.7
8.8
0.9
6.7
0.8
1.4
46.6
4.3
Hystrene ® 2290 f
165
0.6
1.8
94.1
3.5
Hystrene ® T-2802D f
160
2.2
16
79
1.3
a P&G Chemicals
b Huish Corporation
c Cognis Oleochemicals LLC
d Archer Daniels Midland
e VVF Ltd.
f Crompton
g Aldrich Chemical
[0051] Table 2 shows the effect of the unsaturation of the fatty acids and fatty oils on IFT and oil recovery. The un-saturation of fatty acids and fatty oils is determined by the IV as described in AOCS Official Method Tg 1a-64, and is expressed in terms of the number of centigrams (cg) of Iodine adsorbed per gram of sample or the % Iodine absorbed. The ratio of the IV to the MW gives an indication of the amount of unsaturation in a particular molecule. The higher the ratio of IV/MW, the more unsaturation in the molecule. The linear correlation coefficient for the relationship between IFT and degree of unsaturation for 164 tests run using the betaines derived from oils and acids listed in Table 1 was found to be 0.896.
[0052] The betaines were made using a process that is one of many that are well known by those familiar with the art by quaternization of a fatty amine derived from one of the oils or acids with sodium chloroacetate. Betaines where the hydrocarbyl group is R—O—N—CH 2 CH 2 CH 2 are synthesized from the corresponding fatty acid or oil by reaction with an amine such as dimethylaminopropyl amine (DMAPA) to form an amido amine and quaternizing the amido amine with sodium chloroacetate. Preferred betaines formed from amido amines are fatty alkylamidopropyldimethyl betaines. Multiple samples were made using the same fatty acids and fatty oils. The IFT listed in Table 2 is the average of minimum 5 repeating samples.
[0053] The IFT in Table 2 was measured using 0.1% betaine in a West Texas brine solution containing 4,250 ppm total dissolved solids and 150 ppm of divalent cations using a University of Texas Model 500 Spinning Drop Tensiometer after 30 minutes of contact between the various betaines solutions and the crude oil. It is known to the familiar of the art that a low IFT is conducive to higher oil recovery and that an IFT of less than 1×10 −2 mN/m is preferred to recover any significant oil after primary and secondary methods have been exhausted. The data in Table 2 show that the higher the degree of unsaturation, the lower the IFT. In studies of over 160 different combinations of crude oils having API Gravities of 10 to 40, brines having Total Dissolved Solids (TDS) of >200 to over 200,000 mg/L and the betaines based on the acids and oils listed in Table I, We have found that a IV/MW value of 0.15 or more is required to give low to ultra-low IFTs.
[0054] The percent original oil in place (OOIP) recovered was measured by preparing identical sand packed columns for each test as is commonly employed in the industry. Each of the sand packs were saturated with 32% oil and the brine was pumped through the bottom of each of the sand packed columns until all the free oil was removed from the sand pack. 0.3-pore volume of each injection fluid composition was then pumped through the bottom of the separate sand pack columns to determine the residual oil removed by each composition. 0.15% Flopaam™ 3630S polymer is used along with the amphoteric surfactants for the oil recovery experiments.
[0000]
TABLE 2
Relationship between IFT and Unsaturation at Constant MW
Crude oil: API gravity = 22
Temperature: 45° C.
Fatty Acids
Oil
or Fatty Oils
Recovery,
Used For Betaine
MW
AV
IV
IV/MW
IFT
% OOIP
Stearic acid
285
197
0.3
0.00
1.397
5.7
Behenyl
350
160
0.4
0.00
1.23
5.8
Tallow, BFT
285
197
48
0.17
0.0299
6.87
Palm oil
281
200
49
0.17
0.0153
7.01
HEAR acid
319
176
90
0.28
0.0367
10.6
Oleic acid
282
199
90
0.32
0.0056
12.6
OL-600
282
199
115
0.41
0.0046
12.8
Canola oil
281
200
115
0.41
0.0035
14.54
Soybean oil
292
192
130
0.44
0.0018
14.8
Tall Oil
311
180
165
0.53
0.0009
15.43
EXAMPLE 2
[0055] Table 3 shows the IFT values obtained using two betaines made from fatty acids having very similar molecular weight (Oleic=282, Stearic=285) but where oleic acid contains unsaturated hydrocarbyl groups and the stearic acid is completely saturated. The IV, IV/MW and the IFT data of the mixture of the two samples at various ratios are shown in Table 3. These results again demonstrate that the mixture of amphoteric surfactants containing un-saturation is an important property for lowering IFT. The optimum un-saturation is also dependent on the brine and crude oil composition, the temperature and the formation properties. Note also that the highest IV/MW values do not necessarily give the lowest IFT.
[0000]
TABLE 3
Effect Mixtures of Saturated and Unsaturated Betaines of Similar
MW on IFT
Oleyl Dimethyl
Stearyl Dimethyl
betaine, wt %
Betaine, wt %
IV
IV/MW
IFT, mN/m
100
0
90
0.317
0.0056
90
10
81
0.286
0.0042
80
20
72
0.254
0.0019
70
30
63
0.222
0.0034
60
40
54
0.19
0.0017
50
50
45
0.159
0.0083
40
60
36
0.127
0.023
30
70
27
0.095
0.087
20
80
18
0.063
0.019
10
90
9
0.032
0.201
0
100
0.3
0.001
1.397
EXAMPLE 3
[0056] Table 4 show the effect of various concentrations of mixture of amphoteric surfactants made from fatty oils and fatty acids containing un-saturation on the IFT. The tests were run using brine containing 5 wt % sodium chloride as the aqueous solvent for the various concentrations of amphoteric surfactant. The data from Table 4 shows that the betaine mixtures made with unsaturated oleic acid and tallow BFT fatty acid provided low IFT over wide ranges of surfactant concentrations. This is important for oil recovery since the surfactant concentrations is continuously changing as the injection fluid propagates through the reservoir due to the adsorption and dilution. This is an improvement over the prior art such as Example S-2 from Table I of U.S. Pat. No. 4,216,097 that shows ultra-low IFTs below 1×10 −2 can only be obtained using concentrations of 0.00075 wt % or less. This may be a disadvantage since the adsorption may easily exhaust the low concentration of surfactants. U.S. Pat. No. 4,216,097 shows that extremely low concentrations of surfactant can give extremely low IFT values. A surfactant with a much wider range of useful concentrations giving ultra-low IFT is required to insure enough surfactant will reach the oil. Generally 0.02 to 5.0 wt % is used depending on the amount required to obtained the desired results.
[0000]
TABLE 5
Effect Of Surfactant Concentration On IFT
Tallow BFT Dimethyl
Surfactant
Oleic Dimethyl Betaine
Betaine
Conc., wt %
IFT, mN/m
0.5
0.0178
0.0589
0.3
0.0067
0.0236
0.2
0.0031
0.0193
0.1
0.0012
0.0299
0.05
0.0011
0.0076
0.01
0.0007
0.0034
0.005
0.00028
0.0021
EXAMPLE 4
[0057] Table 5 shows the data obtained by measuring IFTs for various dimethylbetaines at 0.1 wt % in various salt solutions against the same crude oil. The data from Table 5 shows that the un-saturated betaines derived from oleyl and erucic acids are more effective in lowering IFT over a wider range of salt concentrations than their less unsaturated counterparts derived from tall oil fatty acid and behenic acid. Note that at higher salt concentrations the behenyl betaines becomes insoluble. This is another advantage of betaines having some degree of unsaturation in that they are soluble over a wider range of salt concentrations than their unsaturated counterparts.
[0058] While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
[0000]
TABLE 5
Effect Of Salt Concentration On IFT
Oleyl
Stearic
Erucyl
Behenyl
Dimethyl
Dimethyl
Dimethyl
Dimethyl
Betaine
Betaine
Betaine
Betaine
NaCl, wt %
IFT, mN/m @ 65 C., 30 Minutes Reading
0.5
0.0252
0.0678
0.0032
0.8320
1.0
0.0199
0.0356
0.0046
0.8550
2.0
0.0122
0.0199
0.0060
0.8870
3.0
0.0099
0.0105
0.0090
0.9340
5.0
0.0012
0.076
0.0378
Insoluble
10.0
0.0037
0.0548
0.0567
Insoluble
15.0
0.0079
0.0234
0.0866
Insoluble
20.0
0.0095
0.0789
0.0999
Insoluble
|
An oil recovery method employing amphoteric surfactants with the steps of: a) Injecting into one or more injection wells an aqueous solution containing a mixture of amphoteric surfactants containing mixture of amphoteric surfactants having a hydrocarbyl chain length between 8 and 26 and certain degree of unsaturation, and b) recovering the oil from one or more producing wells. The aqueous injection fluid may also contain one or more of the following: a thickening agent, an alkali, a co-solvent.
| 2
|
FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0001] Not applicable.
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER LISTING APPENDIX
[0002] Not applicable.
COPYRIGHT NOTICE
[0003] A portion of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or patent disclosure as it appears in the Patent and Trademark Office, patent file or records, but otherwise reserves all copyright rights whatsoever.
FIELD OF THE INVENTION
[0004] The present invention relates to devices for personal health monitoring and management, for example, without limitation, the tracking of a user's health indicators and contextual data, emergency response systems, and the storing and dispensing of medication.
BACKGROUND OF THE INVENTION
[0005] Interviews with physicians and people aging in place indicate that aging people have a difficult time managing their health when living alone. Most of the current technology to address this problem is in the area of pill dispensing devices. One of these devices is a medicine dispenser where medicines are stored in different chambers and a dispensing hole on one of the chambers is used to dispense medication. Another is a medicine dispenser where medicines are stored in bottles.
[0006] Another medicine dispenser known in the art is a dispenser where medicines are stored in small spaces and the unit is rotated to allow a proper dose to be picked up and dispensed. Another current dispensing system sorts medication on a day-to-day basis and has a logging system for missed medications. These solutions only deal with medicine and dosage and do not monitor any aspects of the user's health status.
[0007] Other current solutions for personal health management involve health compliance. One known solution relies on the device being connected to a container, from which the device receives information such as, but not limited to, cap openings and dispensed count. Another known solution connects a medication dispensing device to a controller that tells the user how to use medication. However, this solution does not track usage of the medication. Another current solution uses a pager connected to a carriage and a medication dispensing system. This device relies on the remote commands of a pager to dispense medication and is prone to failures in communication systems. Also, these solutions cannot react to emergencies.
[0008] Yet other current solutions for personal health management relate to health indicators and wellness tracking. One of these solutions comprises a server controlled by the health care provider that downloads a script to the patient client. The server monitors the patient health condition by asking the patient questions. Another health management solution is an apparatus that comprises a device with two sensors that gather two data parameters of a user's status and communicate this information to a computing device that derives additional data from these two parameters. However, these devices do not aid in the usage of medication.
[0009] In view of the foregoing, there is a need for an improved system for personal health management that can monitor and record the user's health status, aid the user with medication usage, and respond in an emergency.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:
[0011] FIGS. 1A and 1B illustrate an exemplary personal health management device with an automatic medicine dispenser, in accordance with an embodiment of the present invention. FIG. 1A is a front perspective view of the device, and FIG. 1B is a front perspective view of an exemplary pill dispenser housed within the device;
[0012] FIG. 2 illustrates an exemplary personal health management device with a light-guided, self-service medicine dispenser, in accordance with an embodiment of the present invention;
[0013] FIG. 3 shows the an exemplary typical network for a personal health management device, in accordance with an embodiment of the present invention;
[0014] FIG. 4 is a flowchart illustrating an exemplary function of a typical personal health management device, in accordance with an embodiment of the present invention; and
[0015] FIG. 5 illustrates a typical computer system that, when appropriately configured or designed, can serve as a computer system in which the invention may be embodied.
[0016] Unless otherwise indicated illustrations in the figures are not necessarily drawn to scale.
SUMMARY OF THE INVENTION
[0017] To achieve the forgoing and other objects and in accordance with the purpose of the invention, an apparatus, method and system for dispensing medication in a personal health management system are described.
[0018] In one embodiment of the invention, an apparatus for dispensing medication is shown. The apparatus includes one or more storage compartments for storing one or more medications, an input device for inputting data related to the medications, a data storage device configured to store at least the data, an output device operable to message information related to the medications, and a computing device configured to respond to the data, select one or more of the storage compartments for dispensing of the medication, provide information for the output device, and record quantity and frequency of the dispensing in the data storage device. In an embodiment the data comprises a prescription regimen for a user and quantities and types of medication in the one or more storage compartments. The computing device can be further configured to monitor quantities of the medication and message medication refills. In another embodiment the apparatus further comprises a reminder device operable to alert the user of a time for dispensing according to the prescription regimen. In another embodiment the computing device is further configured to message the user with guidance regarding the medication during the dispensing. In another embodiment the computing device is further configured to respond to data corresponding to a plurality of users and record quantity and frequency of dispensing for the users. In yet another embodiment the input device and the output device are further configured to communicate to a remote computing device. In another embodiment the input device is further configured to accept data from a user input means. In yet another embodiment the input device is further configured to accept data from one or more biometric measuring devices for a user. The computing device is further configured to use data from biometric measuring devices to track effectiveness of the prescription regimen, in another embodiment. In another embodiment the computing device is further configured to query the user about health status and store the user's responses to the query. In another embodiment the input device is further configured to accept data from an identification means associated with one or more of the medications. In various other embodiments the computing device is further configured to transmit data for one of more users to the remote computing device and the computing device is further configured to receive data regarding medications from the remote computing device. In another the output device is further configured to message an emergency service. In still another embodiment the apparatus further includes a selection device operable to automatically dispense the medication from the one or more storage compartments according to the prescription regimen. In another embodiment the data storage device is further configured to prevent loss of data during a power failure.
[0019] Means for implementing any of the foregoing functions are also provided.
[0020] A method is also provided for dispensing medication. In an embodiment the method comprises the steps of providing initial data for a user of a medication dispensing apparatus, storing medicine in the medication dispensing apparatus, providing a schedule for dispensing the medication for the user, waiting for a scheduled time for dispensing the medication or a user input, alerting the user at the scheduled time, waiting for the user to respond to the alerting, determining if to dispense the medication upon the user responding to the alerting, dispensing the medication upon the determination to dispense, recording the dispensing, obtaining user data from the user, recording the user data, returning to waiting for a scheduled time for dispensing the medication or a user input upon recording the user data, recording a missed medication upon a failure of the user to respond to the alerting, returning to waiting for a scheduled time for dispensing the medication or a user input if a number of recorded missed medications is less than or equal to a preset value, issuing an emergency alert when the number of recorded missed medications exceeds the preset value, determining if the user input is a setup change, returning to providing initial data for a user of a medication dispensing apparatus upon the determination of the setup change, and performing a requested task from the user input. In various other embodiments the method includes transmitting to a remote computing device the dispensing upon recording the dispensing and transmitting to the remote computing device the user input upon recording the user input.
[0021] A system is also provided for personal health management utilizing a medication dispensing apparatus. In one embodiment thereof the system provides for one or more biometric measuring devices for a user, and a health management device configured to accept one or more readings from the measuring devices, recording user data, and storing the one or more readings and the user data in a database. The health management device comprises a medication dispenser, a means for connecting to a remote server, a means for transferring the database to the remote server and a means for alerting the remote server of a medical emergency wherein the remote server responds to the alerting or an emergency situation determined from data in the database by contacting an appropriate emergency responder. In other embodiments the health management device further comprises a means for storing the database to prevent loss of data due to power interruptions and the health management device is further configured to receive messages from the remote server and present the messages to the user. In another embodiment the messages are intended to solicit one or more responses from the user and the health management device is further configured to send the one or more responses to the remote server. In various other embodiments the health management device is further configured to generate a one or more refill requests based upon the amount of medication in the medication dispensing apparatus and is further configured to support multiple users. In another embodiment the medication dispenser comprises an automatic dispenser for the medication.
[0022] An apparatus for automatic medication dispensing is also provided. In one embodiment the apparatus comprises a cylindrical pill cabinet comprising a hollow central channel, a plurality of pill compartments arranged circumferentially about the hollow central channel and flanked by poles positioned parallel to the central channel. A first motor is provided for rotating the pill cabinet about an axis of the central channel. The apparatus includes a dispensing arm comprising a lead screw parallel to the axis and exterior to the pill cabinet, a push nut in operation with the lead screw for traversing a length of the lead screw when the lead screw is rotated, and a plurality of pins arranged in a column perpendicular to the axis and positioned for contacting the push nut. A second motor is included for rotating the lead screw to move the push nut to contact a one of the push pins wherein the one push pin is pushed interior to a one of the pill compartments and a pill contained therein is pushed into the hollow channel. The apparatus includes a processor configured to control the first motor and second motor for selecting a pill to be dispensed via the hollow central channel.
[0023] Other features, advantages, and object of the present invention will become more apparent and be more readily understood from the following detailed description, which should be read in conjunction with the accompanying drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] The present invention is best understood by reference to the detailed figures and description set forth herein.
[0025] Embodiments of the invention are discussed below with reference to the Figures. However, those skilled in the art will readily appreciate that the detailed description given herein with respect to these figures is for explanatory purposes as the invention extends beyond these limited embodiments. For example, it should be appreciated that those skilled in the art will, in light of the teachings of the present invention, recognized a multiplicity of alternate and suitable approaches, depending upon the needs of the particular application, to implement the functionality of any given detail described herein, beyond the particular implementation choices in the following embodiments described and shown. That is, there are numerous modifications and variations of the invention that are too numerous to be listed but that all fit within the scope of the invention. Also, singular words should be read as plural and vice versa and masculine as feminine and vice versa, where appropriate, and alternatives embodiments do not necessarily imply that the two are mutually exclusive.
[0026] The present invention will now be described in detail with reference to embodiments thereof as illustrated in the accompanying drawings.
[0027] Research shows that many seniors aging in place live disadvantaged because of the lack of timely and intelligent personal care that, so far, is believed to be only possible from a human caregiver for example, without limitation, a nurse or a family member. The present invention strives to be an electronics replacement that can intelligently manage the user's health. Exemplary functions of embodiments of the present invention are, without limitation, monitoring the user's health status, prompting and guiding the user to correctly administer medications, charting the user's medical history, responding with appropriate actions in pre-emergency and emergency, and keeping the user's health status available to remote users.
[0028] Embodiments of the present invention comprise a central control unit (CCU) with a centralized persistent database. This forms the brains to which is interfaced any or all of the following elements without limitation: peripherals such as, but not limited to, a display, a keypad, and speakers, a pill storage-and-dispensing unit, devices for reading health status through standard or specialized ports, and standard communications ports to connect by internet or phone to a server.
[0029] By striving to be an effective electronic replacement for traditional care giving, embodiments of the present invention focus on preventive care. This includes, without limitation, drug compliance, which has always been difficult for seniors to take care of alone as prescriptions, the constituent drugs and regimen are complicated to understand and remember. The preferred embodiment of the present invention guides and dispenses the correct combination of drugs, also known as a “cocktail”, according to the regimen. Embodiments of the present invention also take biometric readings indicative of the state of health and answers to medical queries, also referred to as an interview, and use this, data to determine an action pre-emergency or post-emergency to prevent or notify the worsening of the user's health. All medical events are recorded in memory persistent across power failures. This medical history is made available to remote caregivers or physicians, periodically or on-deniand, as desired by the user.
[0030] An aspect of the present invention is to provide means for intelligent personal health care and management. Embodiments of the present invention dispense pills and monitor the user's health status by indictors given by prescription compliance and biometric readings. The tracking and services performed by the preferred embodiment are carried out partly within the device client; however, these services are mostly carried out by a remote server.
[0031] In typical operation, embodiments of the present invention may be used for the following applications, without limitation. Some embodiments enable a user to take medications with guidance correctly according to prescriptions, thus eliminating human error to a large degree. Some embodiments also have electronic voice and/or visual guidance to warn the user of general side effects and cross-medication side effects. Some embodiments record the medical history of the user including, without limitation, prescription regimen compliance, prescribed and non-prescribed drug consumption statistics, and health indicators. Some embodiments function as a overseer to notify when emergency and pre-emergency care are needed for the user. Some embodiments function as a means for caregivers to access the user's health status via the server.
[0032] FIGS. 1A and 1B illustrate an exemplary personal health management device with an automatic medicine dispenser, in accordance with an embodiment of the present invention. FIG. 1A is a front perspective view of the device, and FIG. 1B is a front perspective view of an exemplary pill dispenser housed within the device. In the present embodiment, the device comprises an external cabinet 101 to which the following elements, without limitation, are attached: a speaker 106 for voice instructions, a display 103 , and a keypad 102 . These elements are connected to a board with a central control unit (CCU) 121 that comprises a processor, memory RAM and ROM, access ports, and a sensor. The processor can connect to a PC or a server through the, access ports via means such as, but not limited to, phone lines, Ethernet, or wireless means.
[0033] In the present embodiment, display 103 enables the user to interact with the device through a menu and a graphic or character display prompter for data output, and keypad 102 enables the user to input data. Alternate embodiments may not include a display, and the user may be informed of information such as, but not limited to medication times by an audio alarm or other audio notification, for example without limitation, a recorded voice message. The reminder system in some embodiments may remind the user of medication times and other events through alternate means such as, but not limited to, a telephone call, a cellular phone call, or email. Alternate embodiments may not include a keypad, and users may be able to input data through alternate means such as, but not limited to, a full keyboard, a voice recognition system, barcode readers, or by downloading from a remote computing device or the Internet. In the present embodiment, the device also comprises a door 104 to load medicine into compartments 115 of the medicine dispenser housed inside cabinet 101 and shown by way of example in FIG. 1B . Some embodiments may also include security features such as, but not limited to, physical locks or password protection.
[0034] In the present embodiment, the automatic medicine dispenser inside cabinet 101 comprises a motor 113 coupled to a cylindrical pill cabinet 111 with a central hollow channel 112 . Cylindrical pill cabinet 111 rotates by commands from the processor to every position in which a column flanked by poles 114 lines up against a dispensing arm 116 . Once cylindrical pill cabinet 111 reaches the desired column, cylindrical pill cabinet 111 stops, and a motor 120 and a lead screw 118 of dispensing arm 116 push a nut 119 through pins 117 one by one. As nut 119 passes through pins 117 , each pin pops out the pills in compartments 115 through central hollow channel 112 . The pills are dispensed at the bottom where they are collected in a dispensing tray 105 , which can be removed from the dispenser.
[0035] FIG. 2 illustrates an exemplary personal health management device with a light-guided, self-service medicine dispenser, in accordance with an embodiment of the present invention. Unlike the embodiment shown by way of example in FIG. 1A , the present embodiment has a prescription-guided dispenser instead of an automatic dispenser. This dispenser guides the user by lighting the compartments of the pills to be consumed as opposed to the automatic dispenser that dispenses the group of medications directly. In the present embodiment, a device cabinet 201 has a primary door 202 that is opened to enable pills to be loaded into shelves 203 . Each shelf 203 has a guide light 204 . The device also comprises a display 205 , a keypad 206 , a speaker 207 , and extra storage 208 . Inside cabinet 201 is a CCU that functions similarly to CCU 121 shown by way of example in FIG. 1B with a processor, access ports, memory RAM and ROM, and sensors. The present embodiment may be considered a generic version of a personal health management device, and those skilled in the art, in light of the present teachings, will recognize that many features may be added to or removed from this embodiment while maintaining the function of the device
[0036] For example, without limitation, alternate embodiments may include, without limitation, any version of a pillbox or reminder device with automatic prescription-guided dispensing and/or visual and/or voice-guidance for prescription medications, with or without applications to track consumption of medication, prescribed or not, and to gather health indicators by interviewing the user or using biometric readings. Biometric readings that may be gathered through means such as, but not limited to, user input, sensors, monitors, or meters include, without limitation, weight, blood glucose levels, and blood pressure. Some embodiments may have a database, where this data is gathered, designed in such a way that it resists failures as if the copy is always up to date even after a power failure. The information in this database may be transferred to a remote computing device in some embodiments via a connection such as, but not limited to, a telecom system, the Internet, or a wired or wireless network. This transfer of information can move both ways, sending user information to the remote computing device and receiving information from the remote computing device such as, but not limited to, additional data, scripts, responses to questions, or instructions to the user. In some embodiments the remote computing device is able to use information such as, but not limited to, the data received, information contained in databases, and external information from the web to make deductions about the user's health.
[0037] Some embodiments may connect to a server to transmit drug compliance data and health indicators to the server. Some embodiments may also have sensors on the doors or latches or compartments to monitor the removal or addition of pills. Some embodiments may also support multiple users. Some embodiments may also have video-conferencing and messaging built in to talk with a caregiver or physician.
[0038] FIG. 3 shows an exemplary network for a personal health management device 301 , in accordance with an embodiment of the present invention. In the present embodiment, at the time of dispensing pills 302 , the user may also input biometric readings from a meter 303 into device 301 manually, for example, without limitation, through a keypad or keyboard, or automatically, for example, without limitation, through a wired or wireless connection. The user may also participate in a diagnosis interview set by the device where simple queries are put through to assess the health-status of the user. An exemplary question is, without limitation, “Do you feel all right?” This data is recorded and saved in memory, both temporary and retentive memory in the present embodiment. This record is transmitted periodically, and sometimes as soon as possible, to a server 306 . Data is sent by wireless or wired means, for example, without limitation, phone lines, Ethernet or a wireless network, to a point 304 , and then the data goes over an internet or telecom system backbone 305 to server 306 . Server 306 uses this data as well as contextual data, for example, without limitation, atmospheric temperature, to create derived data that is published periodically for the user's physician and/or caregiver by means such as, but not limited to ordinary mail, web or email, or a telephone. If device 301 or server 306 deduces that user needs emergency care, corresponding action is taken. The emergency can be several levels, for example, without limitation, contacting the caregivers, neighbors, or a call to a Personal Emergency Response 307 such as, but not limited to 911.
[0039] One of the features of the present embodiment is a centralized database. There are two parts to the database, the accumulating database in device 301 and the periodically updated copy in server 306 . The database in server 306 , however, also contains more derived data. Remote caregivers can access this database through means such as, but not limited to the Internet, email, or phone to monitor the user's health status. In the present embodiment, the database in device 301 enables the data to be saved consistently in non-volatile memory to prevent loss of data during power failures. This involves a careful write where the old value of parameters is written first followed by the change requested to their values. An example of a parameter value being, without limitation, the amount of medication taken After a power-up from a power failure, device 301 can reconstruct the actual value by looking up the careful write parameters and asking the user to fill any other parameter not available or performing a certain action.
[0040] The preferred embodiment enables the device to track cross-effects between prescribed and non-prescribed drugs. The FDA has a database that can be indexed with the National Drug Code (NDC) of the medication to obtain instructions and side effects. The server gets the NDC for every medication and crosschecks the medication with every other medication in the database contained in the device. This information is sent back to the device to wam the user and to caregivers if dangerous cross-effects may occur.
[0041] The preferred embodiment also has an application to track effectiveness of pills by tracking the specific health status improvement of the user, positive or negative, with the regimen. An example is, without limitation, a diet regimen to lose weight in three months. The preferred embodiment tracks the progress and makes predictions on whether the user is on track or not. In some embodiments, the device may also graphically chart the progress.
[0042] In some embodiments, the device can also request auto-refill when a medication is running low at the correct time so the medication is available not too late and not too soon. Some embodiments are able to support multiple users. In these embodiments, two or more users can use the same device even when they have common medications. A software logical layer partitions the physical resources into multiple domains, one for each user.
[0043] A basic implementation of the present invention includes a pillbox with one or more compartments where medications are stored in different compartments that takes a prescription by typing it on the keypad and guides the user to take the constituent medications according to the prescription schedule by using a queue, e.g., without limitation, LED, text, sound, voice guidance, etc. For example, without limitation, if the prescription says 2 mg of medication A which is in compartment #1, 4 mg of medication B in compartment #2, and 6 mg of Medication C in compartment #3. If each pill of medication A, B, and C is 2 mg: then the following is outputted at the time of dispensing assuming a voice guidance: 1 pills from Compartment #1, 2 pills from Compartment #2, 3 pills from Compartment #3. An exemplary physical system supporting this basic embodiment includes a box with one or more compartments: medications are stored in separate compartments, an LED for each compartment, a keypad to input prescription and/or drug information, an LCD character or screen or LEDs or character LED to display information, a computing device that computes a medicine dispensing result based on the prescription input, the medications, and the number of pills to be taken by the user at every interval. The present embodiment would guide the user with the LED's and any other information it may display on the screen. Volatile (RAM) and/or non-volatile (ROM) memory could be used in the device to store and process data.
[0044] FIG. 4 is a flowchart illustrating an exemplary function of a typical personal health management device, in accordance with an embodiment of the present invention. In the present embodiment, the process begins at a start point, step 401 . The user then sets up the CCU with information such as, but not limited to, personal and emergency information and contacts as well as connecting biometric meters such as, but not limited to, glucose or blood pressure to the device in step 402 . In step 403 , the user loads the medication according to the manner prescribed by the particular embodiment being used. The user also enters the medication's NDC number or name through the keypad in step 403 . In alternate embodiments, the NDC number can be input using a barcode reader using a barcode on the medication container. In the present embodiment, the user also enters the prescription either manually or by typing in the prescription access number in step 403 .
[0045] In step 404 , the process is interrupted by an alarm or by the user. This interruption may be caused by medication time or user input. In step 405 the device determines if it is currently a medication time. If it is a medication time, the device then determines if the user is absent in step 406 . If the user is absent, a missed medication is logged in step 407 . Missed medications can be a sign of trouble and, after a certain number, may require an emergency response. In the present embodiment, after the missed medication is logged, the device determines if the user has missed more than a preset number of medication times, and emergency response is activated in step 409 . If the user has not missed more than the preset number of medication times, the process waits for another interruption to occur at step 404 .
[0046] If the user is present in step 406 , the device determines whether to dispense the medication in step 411 . If the device decides to dispense the medication, the medication is dispensed and a message is transmitted to the server in step 412 . The device guides the user when taking a medication cocktail or a single medication by identifying the constituent drugs and their individual dosages. Guidance may be audio or visual. Biometric readings are taken and transmitted to the server in step 413 . If the device decides to not dispense medication in step 411 , the process continues to step 413 .
[0047] If it is not a medication time that caused the interruption as determined in step 405 , the device determines if the user requested an interrupt in step 410 . If the user has requested an interrupt, in step 414 , the user can choose to change the setup of the device or perform an alternate task such as, but not limited to, instantly dispense medication, or take readings. If the user wants to change the setup of the device, the process returns to step 402 where the user may edit the setup information. If the user wants to perform an alternate task, the device performs that task in step 415 .
[0048] Those skilled in the art will readily recognize, in accordance with the teachings of the present invention, that any of the foregoing steps and/or system modules may be suitably replaced, reordered, removed and additional steps and/or system modules may be inserted depending upon the needs of the particular application, and that the systems of the foregoing embodiments may be implemented using any of a wide variety of suitable processes and system modules, and is not limited to any particular computer hardware, software, middleware, firmware, microcode and the like.
[0049] Some embodiments of the invention provide the option of instant and/or vacation dispensing to the user. Instant dispensing is shown by way of example in FIG. 4 in step 415 where a user may input a task for the device to perform. The user can instantly dispense medication in advance for a short trip or a longer trip. For longer trips, when the device is not being transported with the user, some embodiments enable a related application called vacation dispensing where medications are dispensed for each session with instructions. The medicines can be put into a mobile pillbox. Also, the instructions can be provided to the user or caregiver for example, without limitation, by being written down or downloaded to a cell phone or a PDA. In some embodiments the device may be able to notify the user of medication times while on vacation through means such as, but not limited to, email or a phone call.
[0050] FIG. 5 illustrates a typical computer system that, when appropriately configured or designed, can serve as a computer system in which the invention may be embodied. The computer system 500 includes any number of processors 502 (also referred to as central processing units, or CPUs) that are coupled to storage devices including primary storage 506 (typically a random access memory, or RAM), primary storage 504 (typically a read only memory, or ROM). CPU 502 may be of various types including microcontrollers and microprocessors such as programmable devices (e.g., CPLDs and FPGAs) and non-programmable devices such as gate array ASICs or general purpose microprocessors. As is well known in the art, primary storage 504 acts to transfer data and instructions uni-directionally to the CPU and primary storage 506 is used typically to transfer data and instructions in a bi-directional manner. Both of these primary storage devices may include any suitable computer-readable media such as those described above. A mass storage device 508 may also be coupled bi-directionally to CPU 502 and provides additional data storage capacity and may include any of the computer-readable media described above. Mass storage device 508 may be used to store programs, data and the like and is typically a secondary storage medium such as a hard disk. It will be appreciated that the information retained within the mass storage device 508 , may, in appropriate cases, be incorporated in standard fashion as part of primary storage 506 as virtual memory. A specific mass storage device such as a CD-ROM 514 may also pass data uni-directionally to the CPU.
[0051] CPU 502 may also be coupled to an interface 510 that connects to one or more input/output devices such as such as video monitors, track balls, mice, keyboards, microphones, touch-sensitive displays, transducer card readers, magnetic or paper tape readers, tablets, styluses, voice or handwriting recognizers, or other well-known input devices such as, of course, other computers. Finally, CPU 502 optionally may be coupled to an external device such as a database or a computer or telecommunications or internet network using an external connection as shown generally at 512 , which may be implemented as a hardwired or wireless communications link using suitable conventional technologies. With such a connection, it is contemplated that the CPU might receive information from the network, or might output information to the network in the course of performing the method steps described in the teachings of the present invention.
[0052] Having fully described at least one embodiment of the present invention, other equivalent or alternative means for implementing a personal health management system according to the present invention will be apparent to those skilled in the art. The invention has been described above by way of illustration, and the specific embodiments disclosed are not intended to limit the invention to the particular forms disclosed. The invention is thus to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the following claims.
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An apparatus, method and system for dispensing medication in a personal health management system are described. The apparatus for dispensing medication is shown. The apparatus includes one or more storage compartments for storing-one or more medications, an input device for inputting data related to the medications, a data storage device configured to store at least the data, an output device operable to message information related to the medications, and a computing device configured to respond to the data, select one or more of the storage compartments for dispensing of the medication, provide information for the output device, and record quantity and frequency of the dispensing in the data storage device. A method is also provided for dispensing medication in accordance with an aspect of the invention. A system utilizing the apparatus in a personal health management system is also shown.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing ultrafine particles, and more particularly, it relates to a process for producing ultrafine particles of ceramics or metal without using the melting and pulverizing processes.
2. Description of the Prior Art
A remarkable progress has recently been made in the micromachining technology typified by the LSI (large scale integration) technology in electronics. The microforming and machining technology is necessary to produce extremely small components which are essential for the miniaturization of electronics machines and equipment with high performance and high reliability. Thus the development of this technology is urgently required. Such developmental works will be supported by the technology of producing ultrafine particles of ceramics or metal. For example, ultrafine particles permit the reduction of the thickness of the paste layer used as the thick film resistor which is one element on the circuit board of hybrid IC. The paste for this application is produced from a powder of ruthenium oxide or metallic ruthenium.
According to the conventional technology, ruthenium oxide is produced by heating ruthenium or ruthenium sulfide in an oxygen stream or oxidizing atmosphere, and metallic ruthenium is obtained by electrorefining. Ruthenium oxide produced by the dry method has to undergo a process for size reduction (below 1 μm) which consumes a great deal of time and energy. In addition, with the conventional pulverizing process it is difficult to produce ruthenium oxide powder of narrow particle size distribution and high purity. This is true of metallic ruthenium powders. In other words, there has been no process for producing a high-performance material for micromachining.
In the case of ceramics as an electronics material, it is necessary to sinter ultrafine particles of ruthenium oxide, ferrite, barium titanate, or the like so that the raw material powder does not lose its characteristic properties. This is accomplished by using a very active assistant which is as fine as the ceramics. To be more specific, a low-melting glass powder of ultrafine particles of about 100 A in size is favourably used as this kind of assistant. This glass powder is conventionally produced by mixing, melting and crushing a low-melting glass. Therefore, the conventional process requires a great deal of time and energy for melting oxides at high temperature and crushing glass. Moreover, the glass powder thus obtained is not good in particle properties.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for producing a ceramic powder and/or metal powder of ultrafine particles without using the melting and pulverizing steps, said powder being an electronics raw material or a sintering assistant.
It is another object of the invention to provide a process for producing ruthenium oxide powder and metallic ruthenium powder of high purity and ultrafine particles without using the melting and pulverizing steps.
It is another object of the invention to provide a process for producing a low-melting glass powder as a sintering assistant or easy-to-sinter powder which can be incorporated into a ceramic powder or metal powder of ultrafine particles without any adverse effect on the properties of the raw material.
The gist of the invention resides in a process for producing ultrafine particles which comprises the first step of preparing one or more than one kind of alkoxide of a metal which is a component of the desired ultrafine particles, and the second step of hydrolyzing said alkoxide to give precipitates and separating the precipitates, or the second step of heating said alkoxide.
According to the process of this invention, it is possible to obtain ultrafine particles in a short time with a small amount of energy by the liquid phase reaction, without using the melting and pulverizing steps.
One embodiment of this invention relates to a process for producing ruthenium oxide powder and metallic ruthenium powder by the steps of reacting a ruthenium compound with an alkali metal alkoxide and hydrolyzing the reaction product. According to this embodiment, it is possible to produce ultrafine particles of ruthenium oxide and/or metallic ruthenium having any desired purity.
Another embodiment of this invention relates to a process for producing a low-melting glass containing lead oxide by the steps of reacting at least three compounds including a lead alkoxide selected from alkoxides or sols derived from said alkoxides and hydrolyzing the reaction product. According to this embodiment, it is possible to produce an ultrafine glass powder of good particle properties (particle size, shape, and distribution) having a desired low melting point. The low-melting glass powder thus obtained is mixed with ceramic powder such as ruthenium oxide, ferrite and barium titanate to achieve sintering at low temperatures. If the low-melting glass powder is produced in the same vessel as used for producing ceramic powder by the hydrolysis of an alkoxide, the resulting hydrolyzate can be used as such for low-temperature sintering.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the flowsheet of the process in Examples 1 and 2 of this invention.
FIGS. 2(a) to 2(c) show the relation between the X-ray diffraction analysis and the heat treatment temperature observed in the powder obtained in Example 1.
FIG. 3 shows X-ray diffraction patterns of the powder obtained in Example 2 that methanol is used as alcohol.
FIG. 4 shows X-ray diffraction patterns of the powder obtained in Example 2 that ethanol is used as alcohol.
FIG. 5 shows X-ray diffraction patterns of the powder obtained in Example 2 that n-butanol is used as alcohol.
FIG. 6 shows X-ray diffraction patterns of the powder obtained in Example 2 that isopropanol is used as alcohol.
FIG. 7 shows X-ray diffraction patterns of the powder obtained in Example 2 that t-butanol is used as alcohol.
FIG. 8 shows the result of thermal analysis of the powder obtained in Example 2.
FIG. 9 shows the flowsheet of the process in Example 3 of this invention.
FIG. 10 shows the vitrification of a three-component compound of PbO-B 2 O 3 -SiO 2 .
FIG. 11 shows the flowsheet of the process in Example 4 of this invention.
FIG. 12 shows the relationship between the melting point and the amount of Al in a glass composed of Pb/B/Si (3/1/1 by mole).
FIG. 13 shows the flowsheet of the process in Example 5 of this invention.
DETAILED DESCRIPTION OF THE INVENTION
According to one embodiment of this invention, ruthenium oxide powder and/or metallic ruthenium powder are obtained in the following manner.
The ruthenium compound as the starting material is a ruthenium halide such as ruthenium chloride. The alcohol to prepare an alkoxide is methanol, ethanol, propanol, butanol, and the like. The alkali metal to prepare an alkoxide is sodium, lithium, and potassium.
A ruthenium compound is reacted with an alkali metal alkoxide to give a ruthenium alkoxide, which is then hydrolyzed or thermally decomposed to give ruthenium oxide powder and/or metallic ruthenium powder. This powder is composed of ultrafine particles ranging from 100 to 200 A in size and has a narrow particle size distribution. This powder can be obtained by either hydrolysis or thermal decompositon.
The hydrolysis can be accomplished by adding decarbonated distilled water to the reaction product at 0° to 100° C., preferably 25° to 100° C., at which the alkoxide does not decompose and the reactants are easy to handle.
The thermal decomposition may be accomplished at any temperature from room temperature to 1000° C. In other words, the reaction product forms ruthenium oxide or metallic ruthenium at room temperature. Either ruthenium oxide or metallic ruthenium is obtained depending on the type of alcohol used and the heating temperature.
Since the reactions are performed in liquid phase, it is rather simple to raise the purity of the product by refining, for example, extracting the by-product with an organic solvent (such as alcohol and benzene).
According to another embodiment of this invention, a low-melting glass powder (including lead oxide powder) used as a sintering assistant or easy-to-sinter powder is obtained in the following manner.
(By "alkoxide" is meant a compound formed by replacing the hydrogen atom of the hydroxyl group of an alcohol by a metal element such as boron, aluminum, and silicon; and by "glass" is meant an amorphous solid of an inorganic compound.)
The starting materials in this embodiment are at least three kinds of alkoxides including a lead alkoxide and sols derived from the alkoxides. Alkoxides other than lead alkoxide include, for example, silicon alkoxide, boron alkoxide, and aluminum alkoxide; and the sols include silica sol derived from a silicon alkoxide and alumina sol derived from an aluminum alkoxide.
In this embodiment, the starting materials are a lead alkoxide and two or more other alkoxides selected from the above-mentioned alkoxides and sols derived from the alkoxides. Typical combinations are shown below, although other combinations are also possible.
(1) Pb(OR) 2 , B(OR) 3 , and SiO 2 sol derived from Si(OR) 4
(2) Pb(OR) 2 , B(OR) 3 , Si(OR) 4 , and Al(OR) 3
(3) Pb(OR) 2 , B(OR) 3 , Si(OR) 4 , and Al 2 O 3 sol derived from Al(OR) 3
These alkoxides and sols are mixed and reacted with one another at a desired ratio. The mixing and reaction should preferably be performed in an organic solvent to facilitate mixing and promote reaction. In addition, the reaction product obtained in an organic solvent affords, upon hydrolysis, precipitates having the same composition as the reactants used. Suitable examples of the organic solvent include benzene, alcohol, toluene, and xylene, and the most suitable one is benzene because of its high solvency. The reaction temperature is not critical so long as it is lower than the decomposition temperature of alkoxides used. For the ease of operation, however, it should be 0° to 100° C., preferably from room temperature to 100° C.
The reaction product obtained in the above-mentioned step is then hydrolyzed. The hydrolysis is carried out by adding decarbonated distilled water directly to the reaction solution, or by bringing the reaction product into contact with steam spouting out of a pressurized vessel. The hydrolysis temperature is not critical. Where no pressure is applied, it is 0° to 100° C. preferably 25° to 100° C., at which the alkoxides used do not decompose. Where pressure is applied or steam is used, it is 100° to 200° C.
The hydrolysis forms powdery precipitates. The precipitates are separated from the mother liquor by centrifugation or filtration, followed by vacuum drying as required. In this way, there is obtained a low-melting glass powder.
The precipitates thus obtained are identified as low-melting glass by X-ray diffractometry, thermal analysis, and electron microscopic examination. The precipitates are amorphous regardless of the composition of the alkoxides used. In addition, no crystallization takes place when they are heated up to their melting point.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The invention is now described in more detail with reference to the following examples.
EXAMPLE 1
Vacuum-dried, completely water-free ruthenium chloride, alcohol (methanol, ethanol, isopropanol, n-butanol, or t-butanol), and a stoichiometric amount of sodium alkoxide (methoxide, ethoxide, isopropoxide, n-butoxide, or t-butoxide) were heated and reacted with one another under reflux. There were obtained black reaction products which are solid at normal temperature and difficulty soluble in alcohol and benzene. The reaction products were washed with methanol to remove sodium chloride, a by-product, which is barely soluble or insoluble in alcohols other than methanol. The flowsheet of the above-mentioned steps is shown in FIG. 1.
The resulting ruthenium alkoxide was dried at room temperature or 70° C., or heated at 200° C. or 600° C. in order to perform thermal decomposition. The resulting powders were examined by X-ray diffractometry and thermal analysis. The results of the X-ray diffractometry are shown in Table 1 and FIG. 2.
It is noted that metallic ruthenium is obtained in the case of heating up to 600° C. and ruthenium oxide is obtained in case of heating above 600° C.
TABLE 1______________________________________ Results of X-ray DiffractometryAlcohol Room Temp. 70° C. 200° C. 600° C.______________________________________Methanol Crystalline Ru Ru RuO.sub.2Ethanol Amorphous Amorphous Ru RuO.sub.2Isopropanol Ru Ru Amorphous RuO.sub.2 (Ru)n-Butanol Amorphous Amorphous Amorphous RuO.sub.2 (Ru) (Ru) (Ru)t-Butanol Amorphous Amorphous RuO.sub.2 RuO.sub.2______________________________________
EXAMPLE 2
Vacuum-dried, completely water-free ruthenium chloride, alcohol (methanol, ethanol, isopropanol, n-butanol, or t-butanol), and a stoichiometric amount of sodium alkoxide (methoxide, ethoxide, isopropoxide, n-butoxide, or t-butoxide) were heated and reacted with one another under reflux. There were obtained black reaction products which are solid at normal temperature and difficulty soluble in alcohol and benzene. The reaction products were washed with water to remove sodium chloride, a by-product.
The flowsheet of the above-mentioned steps is shown in FIG. 1.
The resulting precipitates were dried at room temperature, and further dried at 70° C. or heat treated at 200° C., 400° C. and 600° C., respectively. The resulting powders were examined by X-ray diffractometry and thermal analysis. The results of the X-ray diffractometry are shown in Table 2 and FIG. 3 to FIG. 7, and the results of the thermal analysis are shown in FIG. 8.
TABLE 2__________________________________________________________________________Result of X-ray DiffractometryRu(OR).sub.3 Room Temp. 70° C. 200° C. 400° C. 600-1000° C.__________________________________________________________________________Ru(OMe).sub.3 Ru(OMe).sub.3 Ru(OMe).sub.3 Ru Ru RuO.sub.2 Ru RuO.sub.2Ru(OEt).sub.3 Amorphous Ru Amorphous Ru RuO.sub.2 (Ru)Ru(OPr).sup.i.sub.3 Ru Ru Amorphous RuO.sub.2 RuO.sub.2 (Ru)Ru(OBu.sup.n).sub.3 Amorphous Amorphous Amorphous Ru RuO.sub.2 (Ru) (Ru) (Ru)Ru(Bu.sup.t).sub.3 Amorphous Amorphous RuO.sub.2 RuO.sub.2 RuO.sub.2Ru(OAm.sup.i).sub.3 Amorphous Amorphous Amorphous Ru RuO.sub.2 (Ru) (Ru)__________________________________________________________________________
According to the results of X-ray diffractometry and thermal analysis, the resulting powders obtained by using ethanol, isopropanol and n-butanol are metallic ruthenium, and the resulting powders obtained by using t-butanol are ruthenium oxide. They all afforded ruthenium oxide upon calcining.
EXAMPLE 3
Experiments were carried out according to the flowsheet shown in FIG. 9. At first, silicon ethoxide Si(OEt) 4 was hydrolyzed under reflux to give a silica hydrosol. The hydrosol was converted into an organosol by replacing the aqueous medium with xylene by azeotropic distillation. The organosol was mixed with lead ethoxide Pb(OEt) 2 and boron ethoxide B(OEt) 2 at varied ratios. They were reacted with one another under reflux at 80° C. in benzene. The reaction product was hydrolyzed by adding dropwise decarbonated distilled water at 80° C. There were obtained powdery precipitates. The precipiates were centrifugally separated and washed, followed by vacuum drying at 70° C. for 12 hours.
The resulting powders were heated at 100° C. to 1000° C. to see if crystallization takes place before they melt. Crystallization was examined by X-ray diffractometry and the melting point was measured by thermal analysis. FIGS. 10(a) and 10(b) show the results, the former indicating the temperaure at which melting starts and the latter indicating the temperature at which complete vitrification takes place.
According to the results of X-ray diffractometry and thermal analysis, the products in this example were identified as amorphous solids having a composition of PbO-SiO 2 -B 2 O 3 regardless of the composition of the starting materials. They did not crystallize when heated up to their respective melting points. It is noted from FIG. 10 that the greater the amount of SiO 2 , the higher the melting point, and the greater the amount of PbO, the lower the melting point. The melting point is further lowered when the composition contains B 2 O 3 .
Those products having the molar ratios marked with ⊚, ○, Δ, □, , , and , shown in FIG. 10(a) began to melt at 400° C., 500° C., 600° C., 700° C., 800° C., 900° C. and 1000° C., respectively. Those products having the molar ratios marked with ○, Δ, □, , , and , shown in FIG. 10 (b) began to melt at 500° C., 600° C., 700° C., 800° C., 900° C., and 1000° C., respectively. The mark □ indicates a composition that does not vitrify at 1000° C. or above. The composition Pb/B/Si (3/1/1 by mole) formed a good glass at the lowest temperature of 500° C.
EXAMPLE 4
Experiments were carried out according to the flowsheet shown in FIG. 11. At first, silicon ethoxide Si(OEt) 4 was hydrolyzed under reflux to give a silica hydrosol. The hydrosol was converted into an organosol by replacing the aqueous medium with xylene by azeotropic distillation. The organosol was mixed with lead ethoxide Pb(OEt) 2 and boron ethoxide B(OEt) 3 to give a composition of Pb-B-Si (3/1/1 by mole) that vitrifies at the lowest temperature. Aluminum isopropoxide Al(Oi-Pr) 3 was added in an amount corresponding to 0.43 or 1.67 mol of Al. They were reacted with one another under reflux at 80° C. in benzene. The reaction product was hydrolyzed by adding dropwise decarbonated distilled water at 80° C. There were obtained powdery precipitates. The precipitates were centrifugally separated and washed, followed by vacuum drying at 70° C. for 12 hours.
The resulting powders were heated at 100° C. to 1000° C. to see if crystallization takes place before they melt. Crystallization was examined by X-ray diffractometry and the melting point was measured by thermal analysis. FIG. 12 shows the relationship between the amount of Al and the vitrification temperature. It is noted that as the amount of Al increases, the vitrification temperature also rises. All of the powders obtained were amorphous according to X-ray diffractometry.
EXAMPLE 5
Experiments were carried out according to the flowsheet shown in FIG. 13. At first, aluminum isopropoxide Al(Oi-Pr) 3 was hydrolyzed with hydrochloric acid of pH 2, and the resulting product was deflocculated by further adding hydrochloric acid to give an alumina sol. The alumina sol was converted into alumina-silica hydrosol by adding silicon ethoxide under reflux. The hydrosol was converted into alumina-silica organosol by replacing the aqueous medium with xylene by azeotropic distillation. The organosol was mixed with lead ethoxide and boron ethoxide to give a composition of Pb-B-Si-Al (55/9.9/30/5.1 by wt %). They were reacted with one another under reflux at 80° C. in benzene. The reaction product was hydrolyzed by adding dropwise decarbonated distilled water at 80° C. There were obtained powdery precipitates. The precipitates were centrifugally separated and washed, followed by vacuum drying at 70° C. for 12 hours.
The resulting powders were heated at 100° C. to 1000° C. to see if crystallization takes place before they melt. They turned into a uniform clear glass at 800° C.
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There is provided a process for producing ultrafine particles by preparing one or more than one kind of alkoxide of a metal which is a component of the desired ultrafine particles, and subsequently hydrolyzing or heating said alkoxide. For the production of ultrafine particles of ruthenium oxide and/or metallic ruthenium, which are used as a raw material of thick film resistors, a ruthenium compound is reacted with an alkali metal alkoxide to give a ruthenium alkoxide and it is hydrolyzed or heated. For the production of a low-melting glass (including lead oxide), which is used as a sintering assistant or easy-to-sinter powder, at least three kinds of compounds (alkoxides or sols) including a lead alkoxide are reacted with one another and the resulting reaction product is hydrolyzed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
The present application claims priority to U.S. Provisional Ser. No. 61/777,933, filed Mar. 12, 2013, U.S. Provisional Ser. No. 61/777, 955, filed Mar. 12, 2013, and is a Continuation-In-Part of U.S. Ser. No. 13/162,344, filed Jun. 16, 2011 which claims priority to U.S. Provisional Ser. No. 61/355,859, filed Jun. 17, 2010, and U.S. Provisional Ser. No. 61/370,588, filed Aug. 4, 2010, all of which are incorporated by reference herein.
FIELD OF THE INVENTION
The invention relates generally to the field of medical diagnoses and more particularly to methods and materials used for the detection of entry of gastrointestinal contents into the respiratory tract, with special attention to the diagnosis for the purpose of prevention and treatment of disease.
BACKGROUND OF THE INVENTION
Gastro esophageal reflux disease (GERD) is a condition in which some of the stomach contents (solid and/or liquid) move backwards from the stomach into the esophagus (the tube from the mouth to the stomach). This action can irritate the esophagus, causing heartburn and other symptoms.
Gastroesophageal reflux disease (GERD), gastro-oesophageal reflux disease (GORD), gastric reflux disease, or acid reflux disease is defined as chronic symptoms or mucosal damage produced by the abnormal reflux of stomach acid to the esophagus. A typical symptom is heartburn.
This is commonly due to transient or permanent changes in the barrier between the esophagus and the stomach. This can be due to incompetence of the lower esophageal sphincter, transient lower esophageal sphincter relaxation, impaired expulsion of gastric reflux from the esophagus, or a hiatal hernia.
A different type of acid reflux which produces respiratory and laryngeal manifestations is laryngopharyngeal reflux (LPR), also called extraesophageal reflux disease (EERD). Unlike GERD, LPR is unlikely to produce heartburn, and is thus sometimes called silent reflux.
The gastrointestinal contents may thus also enter the respiratory tract as a result of any condition that causes the backward movement of the gastrointestinal contents from the stomach to esophagus. The gastrointestinal contents contain many substances that are likely to be harmful to the respiratory tract: acid, digestive enzymes, microorganisms, allergens, proinflammatory subtances and so on. There is increasing evidence that gastro esophageal reflux disease (GERD) is the underlying mechanism behind many disease conditions of the respiratory tract, such as infections and high morbidity in subjects with lung transplants, asthma, bronchitis, bronchiectasis, pulmonary fibrosis and so on. At present, there are no acceptable methods to detect the entry of gastrointestinal (GI) contents into the respiratory tract.
SUMMARY OF THE INVENTION
Diagnostic formulations for use in diagnosing and treating entry of gastrointestinal contents into the respiratory tract (“aspiration”) in subjects, with special attention to the diagnosis for the purpose of prevention and treatment of diseases associated with aspiration. The subjects that may be diagnosed and/or treated using such methods are animals, prefereably mammals, including humans.
In a first embodiment, the concentration of the gastrointestinal contents entering the respiratory tract can be estimated by adding a detectable non-toxic label that is not absorbed from the gastrointestinal tract or from the respiratory tract. The label should be in a form that is biocompatible with the respiratory tract and the gastrointestinal tract. The label also should not be destroyed in the gastrointestinal or respiratory tract. If the contents of the gastrointestinal tract enters the respiratory tract, the respiratory fluid can be sampled (e.g., by bronchoscopy) and the concentration of the label in the respiratory tract can be measured, thus estimating the concentration of the gastrointestinal contents that entered the respiratory tract.
For example, the diagnostic formulation may be comprised of an ingestible liquid; and a plurality of particles comprised of a biocompatible polymer such as carnauba wax and a non-radioactive label such as fluorescein.
Accordingly, a first embodiment provides a method of diagnosing respiratory fluid in a subject, comprising orally administering to a subject a diagnostic formulation comprising a plurality of particles, wherein the particles comprise a biocompatible material that is not destroyed in the gastrointestinal or respiratory tracts and a detectable label, allowing the formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract, accessing respiratory fluid from the subject, and analyzing the respiratory fluid to determine if the fluid contains the detectable label. The formulation optionally comprises an aqueous carrier.
In certain aspects, the biocompatible material comprises carnauba wax. In other aspects, the biocompatible material is associated with a detectable label, e.g. a fluorescent label, a radioactive label, a magnetic label and a UV label. In a specific aspect, the detectable label is an optically fluorescent label, e.g. fluorescein. The label is preferably encapsulated in a material which is not degraded in the respiratory and gastrointestinal tracts. In a specific aspect, the label is encapsulated in carnauba wax.
The the respiratory fluid n the methods of the invention used is accessed in any manner that allows analysis of fluid from the respiratory tract of the subject. In preferred aspects, the body fluid analyzed is fluid collected, e.g., using bronchoscopy, spontaneous sputum collection or induced sputum production. In some aspects, the analyzing of the detectable label in the collected respiratory fluid comprises determining a number of labels per unit volume of respiratory fluid obtained from the subject.
In certain embodiments, the methods of the invention further comprise the administration of a control formulation to a subject to establish a level of the agent for analysis of the presence and/or concentration of gastric contents in the respiratory fluid of a subject either before or following administration of the diagnostic formulation. The control formulation may be administered by inhalation, e.g., to establish levels of an agent that may be present should the agent be aspirated. The control formulation also may be administered by ingestion to establish a baseline for the agent should it not be aspirated. For the latter aspect, the control formulation is preferably administered during a period of time when the subject is not expected to experience aspiration of gastrointestinal contents into the respiratory tract.
In a specific aspect, detection of the level of the agent or detectable label indicative of aspiration of gastrointestinal contents into the respiratory tract requiring medical intervention is based on a comparison of the level observed following administration of the diagnostic formulation and the level observed following administration of the control formulation. In the case of administration of the control formulation to establish a negative baseline, the level of agent or detectable label determined for administering to the subject a medical treatment to reduce or prevent such aspiration is determined as an increased level of agent over that seen following the control administration. In the case of the control administration establishing the level in a bodily fluid, the level of agent or detectable label determined for administering to the subject a medical treatment to reduce or prevent such aspiration is determined by comparison to the levels produced using the control formulation.
In another aspect, detection of the level of the agent or detectable label indicative of aspiration of gastrointestinal contents into the respiratory tract requiring medical intervention is based on ranges established through clinical practice. This can be based on the levels of aspiration detected in a range of previous patients or a range based on a simlulation of predicted values of agent and/or detectable label.
In specific aspects, the invention provides a method of diagnosing respiratory fluid in a subject suffering from gastroesophageal reflux disease (GERD), comprising orally administering to a subject suspected of suffering from gastro esophageal reflux disease (GERD) a formulation comprised of a plurality of particles comprised of fluorescein and carnauba wax. allowing the formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract, accessing respiratory fluid from the subject, and analyzing the respiratory fluid to determine the presence of fluorescein, thereb determining if the subject aspirates gastrointestinal contents into the respiratory tract.
The invention further comprises a method of determining the respiratory fluid contains a concentration of gastric contents indicative of aspiration of gastrointestinal contents into the respiratory tract and administering to the subject a medical treatment to reduce or prevent such aspirations. Such medical treatments can include pharmacological intervention or surgical intervention.
In specific embodiments, the invention provides a diagnostic formulation, comprising an ingestible liquid carrier; and a plurality of particles comprised of carnauba wax and a detectable label. The formulation prefereably comprises an aqueous carrier. The detectable labe can be, e.g., a fluorescent label, a radioactive label, a magnetic label and a UV label. In a specific aspect, the particles comprise fluorescein encapsulated in carnauba wax. A preferred label is flourescein. In another specific aspect, the particles comprise a radioactive material encapsulated in carnauba wax. In a preferred aspect, the label is encapsulated in a material which is not degraded in the respiratory and gastrointestinal tracts.
In other embodiments, the invention provides a method of treating a subject suffering from entry of gastrointestinal contents orally administering to a subject a formulation comprising a plurality of particles, wherein the particles comprise a biocompatible material that is not destroyed in the gastrointestinal or respiratory tracts and a detectable label, allowing the formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract; accessing respiratory fluid from the subject, and analyzing the respiratory fluid to determine the concentration of detectable label in the respiratory fluid; determining if the concentration of detectable label in the respiratory fluid is indicative of aspiration of gastrointestinal contents into the respiratory tract requiring pharmacological treatment, and administering to the subject a pharmacological treatment to reduce or prevent such aspirations.
In preferred aspects, the the respiratory fluid is accessed by collecting fluid from lungs of the subject. In certain aspects, the analyzing comprises determining a number of fluorescein particles per unit volume of respiratory fluid obtained from the subject.
In certain embodiments, the invention provides for dual use of an agent that is not absorbed from the gastrointestinal tract of a subject but is absorbed from the respiratory tract for estimating the amount of the gastrointestinal contents that entered the respiratory tract, and particles of a biocompatible material that is not destroyed in the gastrointestinal or respiratory tracts and a detectable label to estimate the concentration of gastrointestinal contents that entered the respiratory tract. In certain aspects, these agents and particles can be used in the same formulation. The administered agent could then be detected using a bodily fluid (e.g., blood, a blood product or urine) and the particles detected in, e.g., the sputum or bronchial fluid of a subject. Using both approaches of the method of the invention will allow the determination of both the amount of gastric contents that has aspirated into a subject's respiratory system, and the concentration of the gastric contents in the bodily fluid.
For example, a formulation containing both particles of label-encapsulated carnauba wax and an agent such as a cromolyn salt may be administered to a subject. Following administration, the analysis of the cromolyn salt in the subject, e.g., through analysis of blood or urine, can be used to determine the amount of gastric contents aspirated into the respiratory system while the analysis of the detectable label in the bodily fluid of the subject, e.g. through detection of the label in sputum, can determine the concentration of the gastric contents in the bodily fluid.
The present invention also provides a method of determining the amount and concentration of gastric contents in the respiratory fluid of a subject, comprising orally administering to a subject a formulation comprising a plurality of particles, wherein the particles comprise a biocompatible material that is not destroyed in the gastrointestinal or respiratory tracts and a detectable label, and an agent that is not absorbed from the gastrointestinal tract of a subject but is absorbed from the respiratory tract of the subject, allowing the formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract, accessing the respiratory fluid from the subject, analyzing the respiratory fluid to determine the concentration of the detectable label in the respiratory fluid, accessing a body fluid other than respiratory fluid from the subject, and analyzing the body fluid to determine if the fluid contains a level of the agent indicative of the amount of aspiration of gastrointestinal contents into the respiratory tract. The body fluid other than respiratory fluid can be urine, blood or blood products.
The invention also futher provides determining the respiratory fluid contains a concentration of gastric contents in the respiratory tract indicative of aspiration of gastrointestinal contents into the respiratory tract, and administering to the subject a medical treatment to reduce or prevent such aspirations. Such medical treatments can include pharmacological intervention or surgical intervention.
Alternatively, the diagnostic methods of the invention may employ an agent that is not absorbed from the gastrointestinal tract, but is absorbed from the respiratory tract. Levels of this agent in a subject's bodily fluid, e.g., blood, plasma, serum or urine, can be detected and used to estimate the amount of the gastrointestinal contents that entered the respiratory tract. This is done by measuring the amount of the agent that has entered the circulation (from the respiratory tract) by taking samples of blood, plasma, serum or urine, and quantifying the amount of the label in those fluids. If the drug is excreted also into saliva, then the saliva samples may be the most convenient method. For example, cromolyn sodium (sodium cromoglycate) is a harmless substance that is soluble in water, is not destroyed in the gastrointestinal tract or the respiratory tract, is not absorbed from the gastrointestinal tract but is absorbed from the respiratory tract. A water solution of cromolyn sodium can therefore be swallowed and the concentrations of cromolyn in blood and urine samples can be used to estimate the amount of gastrointestinal contents that entered the respiratory tract. Cromolynic acid and other salts of cromolyn can be used instead of sodium cromolyn, or substances that are structurally similar such as nedocromil sodium. Another class of substances that have members that are poorly absorbed from the gastrointestinal tract but are well absorbed from the lung are anticholinergic drugs also known as muscarinic acid receptor antagonists such as tiotropium bromide.
Accordingly, the invention provides a method of diagnosing respiratory fluid in a subject, comprising orally administering to a subject a diagnostic formulation comprising an agent that is not absorbed from the gastrointestinal tract of a mammal but is absorbed from the respiratory tract of a mammal, allowing the formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract, accessing a body fluid from the subject, and analyzing the body fluid to determine if the fluid contains a level of the agent indicative of aspiration of gastrointestinal contents into the respiratory tract.
In a more specific aspect, the invention provides a method of diagnosing respiratory fluid in a subject, comprising orally administering to a subject a diagnostic formulation comprising a cromolyn salt, allowing the diagnostic formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract, accessing a body fluid from the subject; and analyzing the body fluid to determine if the fluid contains a level of the cromolyn salt indicative of aspiration of gastrointestinal contents into the respiratory tract.
The invention also provides methods of treating subjects in need of medical intervention due to aspiration of gastic contents into repiratory fluid. Accordingly, the invention provides a method of treating a subject suffering from entry of gastrointestinal contents into the respiratory tract, comprising orally administering to a subject a diagnostic formulation comprising an agent that is not absorbed from the gastrointestinal tract of a mammal but is absorbed from the respiratory tract of a mammal, allowing the formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract, accessing a body fluid from the subject wherein the body fluid, analyzing the body fluid to determine the level of the agent in the body fluid, determining the fluid contains a level of the agent salt indicative of aspiration of gastrointestinal contents into the respiratory tract, and administering to the subject a pharmacological or surgical treatment to reduce or prevent such aspirations, or advising the subject to change their diet, timing of meals, body posture at night and so on to minimize or prevent the aspiration of gastrointestinal fluid into the respiratory tract. One or both of the diagnostic agengs, such as fluorescein encapsulated in carnauba wax particles or cromolyn solution, either individually, or as a mixture, can be subsequently administered to probe the effectiveness of the intervention to treat the condition of aspiration of gastro-intestinal fluid into the respiratory tract.
The invention also provides a method of treatment, comprising detecting a level of cromolyn salt indicative of aspiration of gastrointestinal contents into the respiratory tract, and administering to the subject a pharmacological or surgical treatment, or other interventions to reduce or prevent such aspiration. The invention also provides a method treating a subject suffering from entry of gastrointestinal contents into the respiratory tract, comprising orally administering to a subject a diagnostic formulation comprising a cromolyn salt allowing the formulation to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract into the respiratory tract, accessing a body fluid from the subject, and analyzing the body fluid to determine the level of cromolyn salt in the body fluid, determining the fluid contains a level of cromolyn salt indicative of aspiration of gastrointestinal contents into the respiratory tract, and administering to the subject a pharmacological or surgical treatment to or other intervention to reduce or prevent such aspirations.
The invention also provides administering a control formulation comprising the agent used in the diagnostic formulation to the subject at an occasion different to that when the orally administered diagnostic formulation is administered, accessing a body fluid from the subject following the administration of the control formulation, and analyzing the body fluid to determine if the fluid contains the agent.
The control formulation can be administered orally or by inhalation. Preferably, the body fluid analyzed is collected following the administration of the control formulation and prior to analyzing the body fluid. In some aspects, the control formulation is administered during a period of time when the subject is not expected to experience aspiration of gastrointestinal contents into the respiratory tract. In other aspects, the control formulation is administered during a period of time when the subject is expected to experience aspiration of gastrointestinal contents into the respiratory tract. In yet other aspects, the control formulation is a positive control administered to determine the amount of agent expected to be detected in a bodily fluid should aspiration occur.
A particular aspect of the invention involves the use of dipstick technology in order to assay for the presence of an agent such as cromolyn in a body fluid such as urine or saliva. When the dipstick indicates the presence of the agent such as cromolyn the presence of such is a positive result indicating that the subject is aspirating contents of the gastrointestinal tract into the respiratory tract of the subject. Those skilled in the art will appreciate that a wide range of different embodiments of dipstick technologies can be used in connection with the invention. Examples of such dipstick assays are disclosed within U.S. Pat. No. 5,256,372 issued Oct. 26, 1993; U.S. Pat. No. 4,968,604 issued Nov. 9, 1990; and U.S. Pat. No. 7,972,837 issued Jul. 5, 2011, all of which are incorporated herein by reference as are the patents and publications cited within these patents.
The dipstick assay methodology generally requires the presence of a paper or cardboard substrate which is dipped into a solution to be tested. The substrate allows for the solution to migrate upward by capillary action. Although different embodiments are possible, the substrate generally includes a reagent that will interact with cromolyn so that an observable effect is generated to detect cromolyn at least qualitatively, and preferably quantitatively. One example is that the dipstick substrate contains a reagent that reacts with the agent such as cromolyn, where the reaction gives rise to a distinct color which can be readily detected by an unaided human eye under normal room lighting. The intensity of this color is the measure of the amount of the agent in solution. Some intermediate steps may also be required to cause and enhance the formation of the color reaction. Such chemistry was described for example by K Görlitzer, G Badia, P G Jones. Pharmazie. 2001 May; 56 (5):401-6.
Another method uses an antibody which binds to a particular agent such as cromolyn with respect to the present invention. The substrate may include an anti-antibody which binds to the antibody that binds the agents such as cromolyn. Further, the antibody or anti-antibody generally includes a visually detectable label wherein the label can be readily detected by an unaided human eye under normal room lighting. The system may show a negative response when a signal or line across the paper appears at a particular location and a positive response when a signal such as a line appears at a different location on a substrate paper.
Certain devices can be used in the methods of the invention. Multiple forms of dipstick devices may be used to carry out the present invention.
In a first aspect, the dipstick device for the detection of an agent indicative of aspiration of gastrointestinal contents into the respiratory tract of a subject, comprising a substrate comprised of paper a first antibody which binds to an agent that is not absorbed from the gastrointestinal tract of a subject but is absorbed from the respiratory tract of a subject, a second antibody which binds to the first antibody; and a visually detectable label.
In another aspect, the dipstick device for the detection of an agent indicative of aspiration of gastrointestinal contents into the respiratory tract of a subject comprises a substrate comprised of paper and a first reagent that reacts with the agent to form a second reagent optically distinguishable from the first reagent. In a specific aspect, the first agent is a colored dye and the second reagent is a color distinguishable from the color of the first agent.
In another aspect, the dipstick device for the detection of an agent indicative of aspiration of gastrointestinal contents into the respiratory tract of a subject comprises a substrate comprised of paper and a first reagent that reacts with the agent, and a second reagent that enables the reaction of the first reagent to form a dye with the agent that is of a different color than the color either the first or the second reagent.
In another aspect, the dipstick device for the detection of an agent indicative of aspiration of gastrointestinal contents into the respiratory tract of a subject comprises a substrate comprised of paper and a reagent that reacts with the agent to form a compound with a visually detectable color.
In another aspect, the dipstick device for the detection of an agent indicative of aspiration of gastrointestinal contents into the respiratory tract of a subject comprises a substrate comprised of paper and a first reagent that reacts with the agent and a second reagent that enables the reaction of the first reagent to form a compound with a visually detectable color.
The dipstick devices of the invention generally detect a specific agent, e.g., cromolyn salts, cromolynic acid, nedocromil, nedocromil salts and muscarinic acid receptor antagonists.
Those skilled in the art will know that other methods of detection can be used based on various properties of the specific agents. Portable electronic technology devices including cellphones, smartphones, tablets and so on can be used to detect unique optical properties of the diagnostic agents in the collected body fluids. The subject being diagnosed can read the result on the electronic device, or the signal can be transmitted to a specialized center for analysis, or to a healthcare professional.
Both the agent and the particle approaches can be also used purely for qualitative purposes to detect the entry of gastrointestinal contents into the respiratory tract. A label that is destroyed neither in the respiratory tract, nor in the gastrointestinal tract and which also has the properties of being absorbed from the respiratory tract but not from the gastrointestinal tract, can be used for qualitative detection of the entry of gastrointestinal contents into the respiratory tract. Such a label is swallowed and its presence is detected in the blood samples, or in urine if it is excreted via kidneys from blood to urine. Alternatively, a label that is not absorbed or destroyed in the gastrointestinal and respiratory tracts can be swallowed and subsequently detected in the respiratory fluid if the subject suffers from a condition that moves the contents of the gastrointestinal tract into the respiratory tract.
Although GERD is generally referred to here, those skilled in the art will understand that this invention is applicable to use in connection with any disorder that causes entry of gastrointestinal contents into the respiratory tract of the subject. Different subjects may be suffering from different disorders which result in involuntary aspiration of gastrointestinal contents. This may result in some of the gastrointestinal contents entering the respiratory tract of the subject causing damage. The present invention is intended to detect the presence of such gastrointestinal contents in the respiratory tract regardless of a particular disease or disorder which may have resulted in the presence of the gastrointestinal contents in the respiratory tract. The invention also describes medical interventions, e.g., surgical or pharmacological interventions, to prevent the entry of gastrointestinal tract contents into the respiratory tract.
A method of diagnosing respiratory fluid in a subject suffering from gastro esophageal reflux disease (GERD) is disclosed. The method comprises (1) orally administering to a subject suspected of suffering from aspiration of gastrointestinal fluid into the respiratory tract, e.g., subjects at high risk who have gastro esophageal reflux disease (GERD), or subjects with respiratory condition of unknown origin, a formulation comprised of a plurality of particles comprised of a biocompatible material (e.g. carnauba wax) and a detectable label (e.g. a fluorescent label), (2) allowing the formulation to remain in the subject over a period of time during which the subject would be expected to regurgitate formulation, (3) collecting respiratory fluid from the subject, and (4) analyzing the respiratory fluid to determine if the fluid contains the detectable label, and thereby determining if the subject aspirated gastrointestinal contents into the respiratory tract.
Those skilled in the art will know that there are numerous ways in which the label contained within the material of the particles that are digested neither in the gastrointestinal tract, nor in the respiratory tract, can be detected. External counters can detect the presence of radiolabel in such particles in the respiratory fluid. Alternatively, magnetic detectors can be used for magnetic labels, or the magnetic particles can be extracted with a magnet and their quantity determined, e.g., by weighing or counting them. The preferred embodiment is to use fluorescein in the label contained in carnauba wax particles. The respiratory fluid can be heated to melt the carnauba wax and the fluorescein released from the particles can then be detected using its fluorescent properties. Other extraction methods that incorporate the use of organic solvents to dissolve or extract the carnauba wax can be employed.
By carrying out the steps as described above it is possible to analyze the fluid collected from the respiratory tract and determine the concentration of the label in the respiratory fluid. The higher the concentration of the label in the respiratory fluid the greater the potential damage to the subject's respiratory tract due to involuntary aspiration of gastrointestinal contents. Higher concentrations of the label may suggest more aggressive treatment of the subject.
In another embodiment of the invention, the formulation is also orally administered to the subject. However, instead of comprising particles with a fluorescent label (or other label) coated with carnauba wax (or other material) the formulation comprises a substance (an agent) such as cromolyn sodium. Cromolyn sodium is water soluble and harmless. Further, cromolyn sodium is not absorbed in the gastrointestinal tract, but is absorbed from the respiratory tract into the blood stream. Those skilled in the art will recognize other compounds which have these characteristics. However, it is important to select compounds that are known not to affect in that particular subject, or in that group of subjects, the aspiration of gastrointestinal contentss into the respiratory tract. When the formulation of such an agent that is not causing or preventing aspirations is orally administered to the subject and there is aspiration of gastrointestinal contents into the respiratory tract, it is possible to test for the presence of the agent in the subject's blood or urine.
Thus, in accordance with this embodiment of the method the respiratory fluids of the subject does not need to be extracted. This method allows for theestimation of the total amount of gastrointestinal contents which has entered the respiratory tract.
An example of a substance that is safe to both the respiratory tract and the gastrointestinal tract is cromolyn sodium. Cromolyn is in fact a drug with very few adverse reactions. Cromolyn sodium is thought to act by inhibiting of the release of histamine and leukotrienes (SRS-A) from the mast cell. It is therefore possible that in some subjects the cause of aspiration of the gastrointestinal tract contents into the respiratory tract is inhibited by the action of cromolyn sodium and similar drugs. This desirable pharmacological effect can be detected for example by administering orally to the subject on one occasion carnauba wax particles coated with fluorescein alone and on another occasion these particles together with cromolyn sodium. If on the first occasion the carnauba wax particles are detected in the respiratory tract fluids such as the sputum from the subject but they are not detected when such particles are co-administered with cromolyn, then this suggests that cromolyn is minimizing or blocking the aspiration of gastrointestinal contents into the respiratory tract. Of course, those skilled in the art will know that other types of biocompatible, non-reactive substances can be used instead of carnauba wax, fluorescein or cromolyn sodium.
When a substance such as a cromolyn sodium is administered to the subject it may be advisable to first administer a control formulation of cromolyn sodium orally to the subject in the morning. The dose is orally administered at a time when the subject would not be expected to experience any reflux. After administering the formulation such as cromolyn sodium the subject is not allowed to sleep or even lie down. Further, any steps that may need to be taken in order to avoid the subject experiencing reflux into the respiratory tract are taken. Blood and urine samples are then taken during the day and analyzed as a control. It may be that no cromolyn appears in the blood or urine. However, if a small amount appears, then that level of cromolyn can be used as a baseline to compare to the level when the formulation is administered and the subject is allowed to lie down, sleep and normally experience reflux into the respiratory tract. When the second administration occurs the same amount of cromolyn sodium is orally administered as was administered in the control. Carrying out a comparison will avoid false positives in the diagnosis of the subject, particularly in subjects that have abnormally high oral absorption of cromolyn. It is also possible to maximize the probability of aspiration in a particular subject, for example with heavy meals or foods that provoke GERD. It is pointed out that in most “normal” subjects there will be substantially no absorption of cromolyn into the blood or urine unless the cromolyn is absorbed via the respiratory tract.
Yet another means to establish whether the subject is likely to be suffering from the aspiration of gastrointestinal contents into the respiratory tract is to establish the amounts and concentration of the diagnostic substances in trials in which a group of subjects with aspirations documented by other methods such as video monitoring via bronchoscopy or gamma scintigraphic detection in the respiratory tract of ingested radioactive substances, are compared with the quantities detected in healthy subjects who do not have such aspiration. Threshold levels of these diagnostic markers above which the aspiration is likely can thus be established.
In yet another embodiment of the invention the two embodiments described above (coated particles and cromolyn sodium) are combined. Thus, the composition which is orally administered to the subject is a liquid formulation which includes the labeled particles coated with the biocompatible material such as carnauba wax and a material such as cromolyn sodium dissolved in the surrounding aqueous carrier. In accordance with this method follow-up analysis involves testing the respiratory fluid for the presence of the labeled particles to determine the concentration of the label in the fluid, and testing the blood and/or urine of the subject in order to calculate the total amount of gastrointestinal contents which was aspirated into the respiratory tract.
The combination method described above can, of course, also be carried out using the control. The control is carried out as described above or the cromolyn sodium formulation is administered to the subject purely as a control and samples of the subject's blood and/or urine are taken during a period of time when the subject is not expected to experience reflux, such as during the day when the subject is not lying down or sleeping.
In still another embodiment of the invention the labeled material is coated with a composition which does not degrade inside the human body but which can be removed or degraded readily outside the human body by the application of heat or other chemicals. More specifically, the material coating the label does not melt at body temperature may be removed by the application of heat at a temperature above body temperature (>40° C.) or by the application of compound which readily dissolves the composition coating the label.
In yet another aspect of the invention positive controls can be used. For example, the subject can be administered a cromolyn formulation by inhalation. By knowing the amount of cromolyn administered into the subject's respiratory tract, and thereafter testing for cromolyn in the subject's blood and urine a comparison can be made to later tests when the cromolyn will be absorbed from reflux out of the subject's stomach into the respiratory tract. It is also, of course, possible to carry out both a negative and a positive control on the same subject.
The invention includes a method of diagnosing respiratory tract fluid in a subject by first orally administering to a subject a formulation comprised of a plurality of particles comprised of a biocompatible material and a detectable label. The formulation may include any number of particles, but for example 100, 500, 1,000 or more, 10,000 or more, 100,000 or more particles. The biocompatible material may be carnauba wax or a different non-reactive biocompatible polymer and the formulation may be an aqueous carrier which may be simply water. The label is preferably a non-toxic label such as a fluorescent label that is encapsulated within the biocompatible material. The label may also be a radioactive label, a magnetic label and/or a UV labeled material. After administering the formulation the subject is allowed to rest during a period of time where aspiration of the formulation from the gastrointestinal tract into the respiratory tract would be expected to occur. After this time respiratory fluid is extracted from the subject such as by the use of bronchoscophy. Alternatively, the subject may spontaneously produce sputum as a sample of respiratory fluid and the labeled particles are then detected in this body fluid. Yet another option is to induce sputum production by one of the methods known to be used for this purpose, such as inhalation of hypertonic saline. The respiratory fluid collected from the subject is then analyzed in order to determine if the fluid contains the detectable label present within the formulation which was orally administered. The presence of the formulation label indicates that the subject has experienced aspiration of the gastrointestinal contents into the respiratory tract.
If the diagnosis is thus made, then it may be advisable to start treating the subject to minimize or eliminate the aspiration of gastro-intestinal contents into the respiratory tract, or at least to minimize the adverse effects of such aspirations.
There are several types of interventions to prevent or reduce aspirations or minimize them and their effects that have been described. Medical treatments for use with the present invention include pharmacologic treatments and surgical treatments. The three main types of medicines to treat GERD are antacids, H2RAs (histamine type 2 receptor antagonists), and PPIs (proton pump inhibitors). Exemplary pharmacologic treatments that can be used with the invention include administration of H2Ras, e.g., Famotidine, Nizatidine, Ranitidine, or Cimetidine; or proton pump inhibitors, e.g., Omeprazole, Lansoprazole, Pantoprazole, Rabeprazole, Esomeprazole, or Dexlansoprazole. Surgical treatments include fundoduplication and endoscopic techniques. Other forms of intervention include assistance with the institution of lifestyle changes in the subject, including changes to a subject's sleeping circumstances or other behavior modification (e.g., dietary changes, changes in consumption of drugs or alcohol, and the like).
It is common for patients suspected of having recurrent GERD with aspiration simply to be treated with a proton-pump inhibitor to reduce the acidity of gastric contents. While this is effective for reflux esophagitis, it is ineffective for the consequences of aspiration of the other components of gastric contents, including food particles and digestive enzymes. Effective prevention of microaspiration secondary to GERD would require surgical intervention, such as gastric fundoplication. At present, the impact of surgical interventions in GERD with microaspiration is difficult to assess without a simple, direct diagnostic test. The present invention therefore combines diagnosis of aspirations with a medical intervention such as gastric fundoplication or pharmacological treatment. A milder intervention may be change in the timing, quality and quantity and food and drinks for the subject, sleeping position and so on. The impact of these interventions can be monitored using the methods described in this invention, with diagnostic substances such as a fluorescent marker encapsulated in small particles made from a non-digestable biocompatible matrix, or solutions of substances such as cromolyn sodium which is chemically stable in the body, safe and well tolerated, poorly absorbed from the gastrointestinal tract but well absorbed from the respiratory tract.
An aspect of the invention is that it is safe, and convenient for the subject.
Another aspect of the invention is that it is easily administered even in a primary healthcare setting, fast and cost-effective, with high specificity and selectivity. The use of simple “dipstick” methods is particularly attractive: the subject is given a dose of the substance such as cromolyn, then urine is collected from the subject. A dipstick is placed in contact with the urine sample, followed by minimum manipulation and observation of changes in the dipstick appearance indicative of the presence and quantity of the diagnostic substance, such as cromolyn sodium.
Another aspect of the invention is that it avoids the use of radiolabels, because they are not practicable in a routine setting and multiple exposures to radioactivity raises safety concerns.
Another aspect of the invention is that to be able to estimate the concentration of the gastrointestinal contents that entered the respiratory tract, it is necessary to to avoid the use of labels that enter the blood circulation.
Another aspect of the invention is that it uses labels that stay as a tracer of the GI fluids that enter into the respiratory tract and remain intact in the GI and respiratory tracts.
Another aspect of the invention is that it uses materials presented in forms that are safe in the respiratory and GI tracts.
Another aspect of the invention is that it retains the label while in the body, presents the label readily when outside the body to a detector providing high specificity and selectivity (i.e., only the label material that was initially swallowed or otherwise placed into the GI tract and then enter the respiratory tract will be detected).
Another aspect of the invention is that the label used can be detected even if only minute quantities of the gastrointestinal materials entered the respiratory tract.
Another aspect of the invention is that the diagnostic method to detect the presence of aspirations of gastro-intestinal contents into the respiratory tract is used in a subject and if the result is positive, treatment of the condition starts. The impact of the treatment can be then also evaluated with the diagnostic method.
Yet another aspect of the invention is to use two different diagnostic methods to eliminate the possibility that a substance used in the diagnostic test itself is having an effect on aspirations of gastro-intestinal contents into the respiratory tract.
Another aspect of the invention is that if one of the substances used as a diagnostic test is found to be reducing or eliminating the aspirations, then that substance can be used as the agent to minimize or prevent aspirations.
These and other objects, advantages, and features of the invention will become apparent to those persons skilled in the art upon reading the details of the methods and formulations as more fully described below.
DETAILED DESCRIPTION OF THE INVENTION
Before the present methods and formulations are described, it is to be understood that this invention is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present invention will be limited only by the appended claims.
Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, some potential and preferred methods and materials are now described. All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. It is understood that the present disclosure supersedes any disclosure of an incorporated publication to the extent there is a contradiction.
It must be noted that as used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a particle” includes a plurality of such particles and reference to “the label” includes reference to one or more labels and equivalents thereof known to those skilled in the art, and so forth.
The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided may be different from the actual publication dates which may need to be independently confirmed.
The invention includes different methods for diagnosing respiratory fluid in a subject wherein the respiratory fluid has been regurgitated from the gastrointestinal tract from the subject. The method includes orally administering to a subject a formulation comprised of a plurality of particles which particles are comprised of a biocompatible material such as a biocompatible polymer or a wax such as a caruba wax wherein the particles include some type of detectable lable which may be a fluorescent label, a radioactive label, a magnetic label or a UV detectable label. The formulation is allowed to remain in the subject over a period of time during which the subject would be expected to aspirate the formulation from the gastrointestinal tract. For example, the subject might be administered the formulation just prior to going to sleep. After allowing for sufficient time respiratory fluid is extracted from the patient. That respiratory fluid is analyzed in order to determine if it contains the detectable label.
Once the patient has been determined as aspirating fluid from the gastrointestinal tract into the respiratory tract the patient will require treatment. That treatment involves orally administering to the subject a formulation which comprises a pharmacological substance. That pharmacological substance or pharmaceutically active drug is administered in order to reduce or prevent aspiration of fluid from the gastrointestinal tract into the respiratory tract. The pharmaceutically active drug is preferably a drug which acts locally on the gastrointestinal tract and is not absorbed systemically. Examples of such drugs are drugs selected from the group consisting of cromolyn salts, cromolynic acid, nedocromil, nedocromil salts or muscarinic acid receptor antagonist.
Dosing of the drug to the patient will vary depending on a wide range of factors including the patient's age, size, weight, sex and condition. However, dosing of the drug to the patient is generally carried out by oral administration of the drug in the form of pills, capsules or solutions. Pills and capsules may contain the drug in combination with a pharmaceutically acceptable excipient. Solutions or suspensions may contain the drug in an aqueous solution or suspension with pharmaceutically acceptable carriers.
The oral formulation may be administered to the subject just prior to going to bed at night. Further, additional doses may be administered during the night depending on the subjects responsiveness to the medication. The dose may be administered before and/or after an activity such as going to sleep which is likely to result in aspirations. That activity can be going to sleep for the evening, taking an afternoon nap, or after eating a large meal or drinking heavily.
In one embodiment of the invention patients undergoing lung transplants are treated prophylactically in order to reduce or prevent intestinal fluid into the newly transplanted lung.
The dosing amount will also vary with the particular drug. When administering cromolyn and in particular cromolyn salts currently marketed safe dosages for children for other indications have been shown to be in the range of about 20 mg 4 times per day to 40 mg 4 times per day. Adults have been dosed in the amount of 200 mg 4 times per day to 400 mg 4 times per day.
The formulation may include both an immediate release component where a drug is immediately released and a controlled release component where the drug is not released immediately (e.g. over the first hour) but released gradually during hours 2 to about 8 hours after administration. Oral liquid formulations can be viscous formulations which provide a degree of coating to the gastrointestinal tract.
When administering cromolyn in order to carry out diagnostics the cromolyn should be delivered with significant amount of water, e,g. 6 oz or more, 12 oz or more, 16 oz or more of water. However, when the cromolyn is being administered in order to treat the subject it is preferably delivered in the absence of water or with a very small amount of water e.g. 4 oz or less, 2 oz or less, 1 oz or less.
EXAMPLES
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the present invention, and are not intended to limit the scope of what the inventors regard as their invention nor are they intended to represent that the experiments below are all or the only experiments performed. Efforts have been made to ensure accuracy with respect to numbers used (e.g. amounts, temperature, etc.) but some experimental errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, molecular weight is weight average molecular weight, temperature is in degrees Centigrade, and pressure is at or near atmospheric.
Example 1
Fluorescein-Spray Drying
Prepare nuclei of <1 micron fluorescein particles by spray drying aqueous solutions of fluorescein. Then condense vapors of respiratory-tract compatible waxes such as carnauba was upon the fluorescein particles completely encapsulating the fluorescein. Make a suspension of these particles in water using usual pharmaceutical methods to stabilize these, add flavor etc. Subject swallows a precise amount of the liquid suspension prior to activity that is causing GIT reflux (e.g., prior to going to sleep).
The health care provider takes a sample of airway fluid through induced coughing, bronchoscopy, spontaneous coughing etc. The sample may be diluted in additional water, or a solvent that dissolves the wax. The fluorescent label is then released either as a result of the addition of a suitable solvent, or by increasing the temperature to dissolve the wax, or both.
The concentration of material in the respiratory tract entering due to reflux is estimated from the intensity of fluorescence using one of many detectors for fluorescence. The important parameter is the concentration of the fluorescent label per volume of the airway fluid in which it was contained as that is likely to be related to the harmful effects of the gastrointestinal contents in the respiratory tract.
Example 2
Fluorescein-Flow Focusing
Prepare nuclei of <1 micron fluorescein particles by extruding a biocompatible wax (carnauba) in an outer tube and a fluorescein label in an inner tube in order to completely encapsulate the fluorescein. Details of the flow focusing method are described in U.S. Pat. No. 6,116,516 and related issued patents, all of which are incorporated herein by reference. Make a suspension of these particles in water using usual pharmaceutical methods to stabilize these, add flavor etc. Subject swallows a precise amount of the liquid suspension prior to activity that is causing GIT reflux (e.g., prior to going to sleep).
The health care provider takes a sample of airway fluid through induced coughing, bronchoscopy, spontaneous coughing etc. The sample may be diluted in additional water, or a solvent that dissolves the wax. The fluorescent label is then released either as a result of the addition of a suitable solvent, or by increasing the temperature to dissolve the wax, or both.
The concentration of material in the respiratory tract entering due to reflux is estimated from the intensity of fluorescence using one of many detectors for fluorescence. The important parameter is the concentration of the fluorescent label per volume of the airway fluid in which it was contained as that is likely to be related to the harmful effects of the gastrointestinal contents in the respiratory tract.
Example 3
Magnetic Particles-Flow Focusing
Magnetic particles may be suspended in a formulation and then swallowed for the diagnostic purposes described in this invention. However, it may be desirable to protect these particles from digestion in the gastrointestinal tract. Further, unencapsulated magnetic particles could be harmful to either the gastrointestinal tract, or the respiratory tract, or both. Using the flow focusing method it is possible to manufacture biocompatible encapsulated magnetic particles that are not digested in the gastrointestinal tract. Prepare nuclei of <1 micron magnetic particles by extruding a biocompatible wax (carnauba) in an outer tube and a magnetic particle label in an inner tube in order to completely encapsulate the magnetic particle. Make a suspension of these particles in water using usual pharmaceutical methods to stabilize these, add flavor etc. Subject swallows a precise amount of the liquid suspension prior to activity that is causing GIT reflux (e.g., prior to going to sleep).
The health care provider takes a sample of airway fluid through induced coughing, bronchoscopy, spontaneous coughing etc. The concentration of the gastrointestinal contents in the respiratory tract can be estimated by collecting with a magnet the magnetic particles and then counting them using one of the many methods available for such counting, or by measurement of the total magnetism. The sample may be also diluted in additional water, or a solvent that dissolves the wax. The magnetic particles can then be released either as a result of the addition of a suitable solvent, or by increasing the temperature to dissolve the wax, or both.
The important parameter is the concentration of the magnetic particle label per volume of the airway fluid in which it was contained as that is likely to be related to the harmful effects of the gastrointestinal contents aspirated into the respiratory tract.
Example 4
UV Labeled Particles-Flow Focusing
Prepare nuclei of <1 micron UV labeled particles by extruding a biocompatible wax (carnauba) in an outer tube and a UV label or UV labeled particle in an inner tube in order to completely encapsulate the UV labeled particle. Make a suspension of these particles in water using usual pharmaceutical methods to stabilize these, add flavor etc. Subject swallows a precise amount of the liquid suspension prior to activity that is causing GIT reflux (e.g., prior to going to sleep).
The health care provider takes a sample of airway fluid through induced coughing, bronchoscopy, spontaneous coughing etc. The sample may be diluted in additional water, or a solvent that dissolves the wax. The UV labeled particle is then released either as a result of the addition of a suitable solvent, or by increasing the temperature to dissolve the wax, or both.
The amount of material in the respiratory tract entering due to reflux is estimated from the UV labeled particles detected using standard detectors. The important parameter is the concentration of the UV labeled particles per volume of the respiratory fluid in which it was contained as that is likely to be related to the harmful effects of the gastrointestinal contents aspirated into the respiratory tract.
Example 5
Phosphorescent Particles-Flow Focusing
Prepare nuclei of <1 micron phosphorescent labeled particles by extruding a biocompatible wax (carnauba) in an outer tube and a phosphorescent labeled particle in an inner tube in order to completely encapsulate the phosphorescent labeled particle. Make a suspension of these particles in water using usual pharmaceutical methods to stabilize these, add flavor etc. Subject swallows a precise amount of the liquid suspension prior to activity that is causing GIT reflux (e.g., prior to going to sleep).
The health care provider takes a sample of airway fluid through induced coughing, bronchoscopy, spontaneous coughing etc. The sample may be diluted in additional water, or a solvent that dissolves the wax. The phosphorescent labeled particle is then released either as a result of the addition of a suitable solvent, or by increasing the temperature to dissolve the wax, or both.
The amount of material in the respiratory tract entering due to reflux is estimated from the phosphorescent labeled particles detected using standard detectors. The important parameter is the concentration of the phosphorescent labeled particles per volume of the airway fluid in which it was contained as that is likely to be related to the harmful effects of the gastrointestinal contents aspirated into the respiratory tract.
Example 6
Fluorescein-Flow Focusing with Cromolyn Sodium)
Prepare nuclei of <1 micron fluorescein particles by extruding a biocompatible wax (carnauba) in an outer tube and a fluorescein label in an inner tube in order to completely encapsulate the fluorescein. Make a suspension of these particles in water using usual pharmaceutical methods to stabilize these, dissolve cromolyn sodium and add flavor etc. Subject swallows a precise amount of the liquid suspension including the dissolved cromolyn sodium prior to activity that is causing GIT reflux (e.g., prior to going to sleep).
The health care provider takes a sample of airway fluid through induced coughing, bronchoscopy, spontaneous coughing etc. The sample may be diluted in additional water, or a solvent that dissolves the wax. Fluorescein is then released either as a result of the addition of a suitable solvent, or by increasing the temperature to dissolve the wax, or both.
If the carnauba wax particles were suspended in a solution of cromolyn, blood or urine samples are also taken and checked for cromolyn to estimate the total amount of gastrointestinal contents that entered the respiratory tract. The amount of cromolyn in the blood or urine shows how much of the formulation of cromolyn swallowed did enter the respiratory tract, because cromolyn will not enter the blood stream, or urine,via the GI tract.
The fluorescein particles encapsulated in carnauba wax enter the respiratory tract if the subject aspires the contents of her/his gastrointestinal tract. Fluorescein can be released from the carnauba wax particles present in the respiratory fluid by heating or dissolving the wax using organic solvents. The concentration of material in the respiratory tract entering due to such aspiration is estimated using one of many methods to detect and quantify fluorescein. The important parameter is the concentration of fluorescein per volume of the airway fluid in which it was contained as that is likely to be related to the harmful effects of the gastrointestinal contents aspirated into the respiratory tract. The presence of cromolyn in a body fluid such as plasma, serum or preferably urine can be quantified by a variety of methods used to measure cromolyn concentrations, such as HPLC with a suitable detector or radioimmunoassay. Measurement of samples of body fluid enables to estimate the total amount of cromolyn that entered the respiratory tract, and therefore provides an estimate of the total amount of gastrointestinal fluid that entered the patient's respiratory tract. Therefore, the combination of the two diagnostic agents provides estimates of both the concentration of the gastrointestinal fluid in the respiratory tract as well as the total amount of the contents of gastrointestinal fluid that entered the respiratory tract.
Example 7
Treatment of Aspirations of Gastrointestinal Contents into the Respiratory Tract
The subject swallows prior to going to bed an aqueous suspension of carnauba wax particles that contain encapsulated fluorescein. The subject then collects any sputum that has been spontaneously produced overnight. If insufficient sputum is obtained, the subject is administered a mist of hypertonic saline by inhalation to induce sputum production. The sputum sample is diluted with a high pH buffer and organic solvent immiscible with water is added to extract the wax. The aqueous phase is separated and a sample is analyzed for fluorescence using a fluorescence detector such as a fluorimeter. If the fluorescence intensity exceeds the limit previously established for healthy subjects, it is assumed that the subject who has just undergone the test suffers from aspirations of gastrointestinal contents into the respiratory tract. The test may need to be repeated several times in case the aspirations do not occur every night, especially if the subject already has a condition that is suspected to cause such aspirations, or the subject has respiratory symptoms of aspirations. When the diagnosis is confirmed, the subject takes (prior to going to bed) a dose of cromolyn sodium and collects urine samples overnight as well as the first thing in the morning. The subject then either sends the urine sample for analysis of cromolyn to a laboratory, or uses a dipstick test at home. The subject repeats the test for several days. If the amount of cromolyn detected in the urine does not exceed the amounts typically found in subjects without aspirations, or the cromolyn concentration in the urine continues to get smaller upon successive testing, it may be concluded that cromolyn (in this subject) is effective to minimize or prevent aspirations of gastric contents into the respiratory tract and it will be therefore used for this purpose for as long as the condition exists, or the treatment ceases to be effective.
Example 8
Treatment of Aspirations of Gastrointestinal Contents into the Respiratory Tract
The subject swallows prior to going to bed an aqueous suspension of carnauba wax particles that contain encapsulated fluorescein. The subject then collects any sputum that has been spontaneously produced overnight. If insufficient sputum is obtained, the subject is administered a mist of hypertonic saline by inhalation to induce sputum production. The sputum sample is diluted with a high pH buffer and organic solvent immiscible with water is added to extract the wax. The aqueous phase is separated and a sample is analyzed for fluorescence using a fluorescence detector such as a fluorimeter. If the fluorescence intensity exceeds the limit previously established for healthy subjects, it is assumed that the subject who has just undergone the test suffers from aspirations of gastrointestinal contents into the respiratory tract. When the diagnosis is confirmed, the subject takes (prior to going to bed) carnauba wax particles that contain encapsulated fluorescein, suspended in an aqueous solution of cromolyn sodium. The subject then collects a sputum sample in the morning, or goes to a healthcare professional who will collect a sample of the respiratory fluid which is then analyzed for the presence of the fluorescein. If the test is negative, the subject may need to repeat for several days to confirm that the cromolyn prevents or reduces the aspiration of gastrointestinal fluid into the respiratory tract.
The preceding merely illustrates the principles of the invention. It will be appreciated that those skilled in the art will be able to devise various arrangements which, although not explicitly described or shown herein, embody the principles of the invention and are included within its spirit and scope. Furthermore, all examples and conditional language recited herein are principally intended to aid the reader in understanding the principles of the invention and the concepts contributed by the inventors to furthering the art, and are to be construed as being without limitation to such specifically recited examples and conditions. Moreover, all statements herein reciting principles, aspects, and embodiments of the invention as well as specific examples thereof, are intended to encompass both structural and functional equivalents thereof. Additionally, it is intended that such equivalents include both currently known equivalents and equivalents developed in the future, i.e., any elements developed that perform the same function, regardless of structure. The scope of the present invention, therefore, is not intended to be limited to the exemplary embodiments shown and described herein. Rather, the scope and spirit of present invention is embodied by the appended claims.
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A method of diagnosing in a subject for the purpose of determining if the subject's gastrointestinal contents has entered the subject's respiratory tract. The qualitative analysis can be also expanded into quantitative analysis, enabling the estimation of either the concentration, or the amount, or both, of the gastrointestinal contents that entered the respiratory tract. The invention also provides methods of treatment based on the identification of aspiration using the methods of the invention.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This Patent Application is a continuation-in-part of patent application Ser. No.: 09/419,140 filed Oct. 15, 1999 and 09/467,599 filed Dec. 20, 1999, pending payment of Issue Fee.
BACKGROUND ART
[0002] Tesla Pat. No. 382,280 disclosed a ring built up of insulated annular iron plates and wound with poly-phase distributions forming an early rotating field stator for generator/motor use, Field utility was limited to the winding window of the toroidal stator. In the cited Logue patent applications the rotating hemispherical flux fringing from the plane of this toroidal stator (pot-core half) was utilized for inducing eddy currents in conducting workpieces e.g. aircraft splice joints The driving flux is directly coupled from the toroidal plane to the workpiece.
[0003] The preferred pick-up assembly to date is a pot-core half with a pick-up coil of many turns of small guage magnet wire e.g. 42 ga., wound around the central pole, filling the annular coil space. For more complete annular space filling of the pick-up core, flat small guage magnet wire may be spool-less wound, using H. P. Reid Co (trademark). adhesive pre-coated voice-coil wire.
[0004] Alternately multiple parallel smaller gauge magnet wires e.g. 46 gauge, may be used.
[0005] This high-density method of pick-up coil winding accentuates the z-axis permeability modulation of the pot-core half, increasing ramping signal build-up re: Logue Pat. No. 5,909,118. As taught in Logue application Ser. No. 09/467,599 a polar coordinates sensor may be reduced to a ferrite pot-core core (integral x-y-z axes of permeability) having a pick-up coil of many turns wound around the central pole 284 (FIG. 1), combined with a rotating driving field generated by sine-cosine currents flowing sine-cosine excitation windings wound through mounting hole (now a winding hole) 184 , in FIG. 1. The pot-core half must be segment-less (no lead slots).
[0006] Oscillatory Signal Build-up
[0007] The polar coordinates signal disclosed in the asending Logue patents is actually formed by succesive revolutions of the hemispherical driving field acceleration; the axis of which is displaced by an asymmetry (flaw) in the eddy current reflection.
[0008] This is a rotary type of parametric pumping.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] [0009]FIG. 1 is a sectional-perspective viewof eddy current probe PS 1 spatially illustrating the disclosed methods of increasing resolution.
[0010] [0010]FIG. 2, is a block-circular diagram of the preferred excitation/connection method for probe PS 1 in FIG. 1.
[0011] [0011]FIG. 3, is a perspective-quadrant view of an eddy current probe utilizing concentric integral driving-sensing pot-cores on increasing radii.
OBJECTS OF THE DISCLOSURE
[0012] A primary object of this disclosure is pursuant to the benefit of the filing date of pending Logue application Ser. No. 09/467,599 pertaining to a coil wound in the annular groove formed in a toroidal core i.e. a pot-core half (element 188 in FIG. 1). The referred benefit is found in Section 201.08 (MPEP). In the cited application Ser. No. 09/467,599 described the dual/alternate functions of a coil ( 190 , FIG. 1) wound in the annular groove ( 179 , FIG. 1) were: 1, poloid axis excitation, 2) as an auxiliary pick-up coil for detecting an asymmetry in the hemispherical probe driving field (flaw in a conducting workpiece,) A claim covering this alternate utility was inadvertently left out of application Ser. No., 09/467,599 by the Applicant.
DETAILED DESCRIPTION
[0013] A second object of the disclosure is an improved method of fitting a Lenz lens/caseing 177 , in FIG. 1, (a higher cross-section ratio than formerly utilized) around integral driving/sensing core 188 , for tighter focusing of the driving field. Previously, (cited Logue application Ser. No. 09/467,599) the copper Lenz lens left a concentric air gap between driving-sensing core and subject high cross-section Lenz lens 177 .
[0014] To prevent any cutting of magnet wire insulation Lenz lens is covered with a hard insulating coating.
[0015] Another object of the disclosure is to teach a method of assembling a simple/robust eddy current probe comprising: a pot-core of high permeability, a Lenz reflecting lens and encompassing x-y axes excitation winding distributions. This novel winding method as illustrated in FIG. 1, x-y axes excitation windings 162 a , (show in partial i.e. one quadrant represents all four quadrants) are wound through winding hole 193 , encompassing integral driving-sensing pot-core 188 , Lenz lens 177 , and pick-up coil 190 . Winding connections to all four quadrants are symbolized by leads Ea. 162 a are An alternate method of excitatation winding 162 b (drawn in partial by dashed lines), which is toroidal wound through mounting hole 193 having leads Eb. For signal nulling pick-up coil 190 (having leads SIG. a) is precision wound around cylindrical pole 184 filling annular space 179 . Pot-core half 188 has a base portion 185 and an open annular sensing face 166 .
[0016] An object of the disclosure is to teach a simple method of signal nulling e.g. under dynamic conditions, the all encompassing excitation winding turns 162 t , are individually adjusted (angularly shifted slightly) for a near flat-line null on an oscilliscope, and then glued in place. Further the described probe assembly may be encased in a cylindrical metal/plastic housing, and set in a potting compound (a thin layer covering the annular sensing face 166 .)
[0017] An object of the invention is an improved method of sine-cosine excitation connection configuration (including series resistors in each lead to a bipolar excitation source (FIG. 2)
[0018] Preferred Core Materials 1) Integral driving/sensing toroids: Square Permally 80 , Supermalloy (tape wound), from MAGNETICS* Butler, Pa.
[0019] 2) Pot-core half: Ferrite part no. 5578000721i, from Fair-Rite Products Corp. Wallkill, N.Y.
[0020] Method of Driving Excitation and Connections
[0021] [0021]FIG. 2, digrammatically illustrates a preferred method of: 1) sine-cosine excitation windings 162 a , FIG. 1, (connections in the probe case and to the excitation source EXx.) The preferred method of connecting configuration of poly-phase excitation windings 162 a , FIG. 1, is a mesh-connected (a single winding 62 a , FIG. 2, is continously wound the circumference of toroid 88 a ) being tapped at each quadrant (x-axis taps are LXa, LXb, and y-axis taps are LYa, LYb.) This method allows the currents flowing through windings 162 a , FIG. 1, to circularly equalize as in a gramme-ring GR, FIG. 2 increasing eddy current resolution and also allowing a greater probe tilt angle (signal has less tilt noise). Referring again to FIG. 2, Current Lo the quadrant taps LXa, LXb, LYa, LYb, are respectively fed through series resistors XRa, XRb, YRa, YRb, for enhanced differential x-y axes tilt-ability e.g. a probe tilt toward quadrant Qa, results in an increase of eddy current reflection in quadrant Qa. The gramme-ring, being a series circuit allows a differential (diametric) current-shift toward quadrant Qb. Quadrants Qc, Qd, respond to tilt in their directions in a likewise redistribution of exitation currents. Digital values of the predetermined poly-phase sinusoidal wave shapes are loaded into the HOST COMPUTER on bus 05 . The computer generated digital values are fed to plural digital-to-analog converters DAC (PLURAL) by bus 06 . The analog waveforms are carried by buses 01 - 04 to the x-y axes amplifiers Xa, Xb, Ya, Yb, and from there to the respective series resistors XRa, XRb, YRa, YRb.
[0022] Concentric Pot-core Halves
[0023] The light of cited Logue application Ser. No. 09/467,599 combined with the present teachings on integral driving-sensing pot-cores wound according to the discription, obviously pot-cores of increasing radii may be disposed concentrically as shown in FIG. 3 (a perspective-quadrant view of probe PS 2 ). Eddy current probe PS 2 , includes in the outer radius wound integral driving-sensing toroidal core 255 a , (a pot-core of enlarged diameter.) Core 255 a is fully circumferentially wound with poly-phase excitation windings 262 a , (leads not drawn) and is formed of a high permeability material with an annular pick-up coil groove 279 a . Core 255 a has outer and central poles 286 a , 284 a . Pick-up coil 290 a in concentrically disposed in groove 279 a (leads not shown) generating a first flaw signal. Integral driving-sensing pot-core 255 b , is formed of a high permeability material, having outer and central poles 286 b , 284 b , leaving an annular pick-up coil space 279 b . A pick-up coil 290 b is wound within groove 279 b for generating a second flaw signal. Polyphase windings 262 b are wound around core 255 b.
[0024] Contemplated Excitation Methods
[0025] Just as a toroidal deflection yoke around the neck of a TV picture tube magnetically moves the electron beam/s to any location on the screen according to a predetermined program, so also the subjec As part of this disclosure, an eddy current scan pattern similar to television raster may be generated in a planar workpiece by the polar coordinates probe utilizing a programable (software) method. Radar display type scans e.g. plan-position indicator (ppi) is also covered as a programable method of eddy current excitation for extending resolution (both cylinder and planar workpieces). It is contemplated the preceding methods would be useful for detecting aircraft flaws.
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An axial direction groove is formed in a high permeability toroidal core taking the form of a pot core half with a mounting hole, a high cross-section ratio copper casing being tightly fit around core circumference, having poly-phase excitation windings shuttled thriugh the mounting hole to encompass both the copper casing and the pot-core, forming an integral driving-sensing eddy current probe. A naked pot-core is wound as an integral driving-sensing probe. Poly-phase excitation of the probe is mesh-connected as a gramme-ring.
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FIELD OF THE INVENTION
[0001] The invention pertains to a round baler with a frame and a cover plate attached thereto in a vertically pivoted fashion, with a baling chamber being formed in said components that is partially encompassed by a tension means that is guided over several rolls.
BACKGROUND OF THE INVENTION
[0002] DE-A1-43 08 646 discloses a round baler with a baling chamber of variable size which is formed by a frame on the front side and a housing at the rear side that is hinged so that it can be opened. A substantially vertical plane of partition results between the frame and the housing. The hinged housing is pivoted away from this plane of partition in order to allow a round bale that has been formed in the baling chamber to be ejected from the baling chamber. An axle for supporting the round baler on the ground is situated behind the plane of partition.
[0003] The above-identified German patent typifies the prior art and exhibits the drawback of requiring the housing to be swung a significant angle about its hinge joint to, and hence in requiring an excessively long time for the housing to be swung open about the hinge joint to, a position at which the round bale, which may reach a height up to 1.8 meters, can be ejected from the baling chamber and for the round baler with the raised housing to be additionally advanced without causing a collision between the housing and the round bale.
SUMMARY OF THE INVENTION
[0004] According to the present invention, there is provided an improved large round baler baling chamber arrangement.
[0005] An object of the invention is to provide a large round baler having a baling chamber defined by components which cooperate to permit a bale formed in the baling chamber to be quickly discharged.
[0006] A more specific object of the invention is to provide a large round baler including a baling chamber defined in part by cooperating opposite side walls of the main frame and of a discharge gate that is mounted for pivoting between a lowered, closed position and a raised discharge position, the respective side walls of the main frame and discharge gate meeting at a line of separation which inclined to the rear from top to bottom to a location near the rear of the baler. immediately preceding object and further including a bottom conveyor which serves to support the bale during its formation and which is inclined downwardly from front to rear to a location near the rear of the baler.
[0007] Yet another object of the invention is to provide a baler, as defined in one or more of the foregoing objects, wherein a lower front roll for supporting a tensioning means, that forms a further portion of the baling chamber, is mounted to a lower end of a tension arm that is pivoted such that the tension means supported by it remains in contact with a lower rear location of a bale being formed and moves to the rear as the bale grows.
[0008] These and other objects of the invention will become apparent from a reading of the ensuing description together with the appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] [0009]FIG. 1 is schematic, left side elevational view of a large round baler constructed in accordance with a first embodiment, wherein a partially filled baling chamber is surrounded by a tension means and stationary rollers.
[0010] [0010]FIG. 2 is a view like that of FIG. 1 but showing a completely filled baling chamber.
[0011] [0011]FIG. 3 is a schematic, left side elevational view showing the details of a forward end of a large round baler constructed in accordance with a second embodiment, wherein a partially filled baling chamber is surrounded by a tension means and rollers that are mounted on a pivoted carrier.
[0012] [0012]FIG. 4 is a schematic, left side elevational view showing the details of a forward end of a large round baler constructed in accordance with a third embodiment, wherein the bottom conveyor is constructed of a plurality of support rolls.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0013] Referring now to FIG. 1, there is shown a large round baler 10 including a frame 12 and a rear discharge gate 14 .
[0014] The round baler 10 conventionally serves to receive a mowed crop and compress it into round bales of variable size.
[0015] The frame 12 includes an axle 16 , on which are mounted wheels 18 , a hitch 20 and side walls, with the frame carrying a pick-up 24 , a conveyor 26 , a cutting mechanism 28 , a bottom conveyor 30 and a carrier 32 with rollers 34 , rolls 36 , a tensioning device 38 and tension means 40 . The frame 12 is supported on the ground by the axle 16 and wheels 18 such that the round baler 10 can be towed over a field by a not-shown towing vehicle.
[0016] The hitch 20 is positively, non-positively or adjustably arranged on the frame 12 and serves to connect the round baler to the towing vehicle. The side walls 22 are rigidly mounted on the frame 12 and laterally limit a baling chamber 42 for a round bale 44 .
[0017] The pick-up 24 is conventionally constructed, and may have the same or a wider width than the width of the baling chamber 42 . The pick-up 24 collects the crop that lies on the ground with prongs 46 that convey in an overshot fashion, and moves the crop to a cutting mechanism 28 along a transport surface that is not illustrated in greater detail, with the crop being fed into the baling chamber from the cutting mechanism.
[0018] The conveyor 26 operates in an undershot fashion and is realized in the form of a rotor that assists in feeding the crop delivered by the pick-up 24 into the cutting mechanism 28 . The conveyor 26 may have a smooth surface or be equipped with dogs, prongs, teeth, ribs, worm screws or the like. The cutting mechanism 28 customarily has a bottom 48 , a cover 50 , a rotor 52 , knives 54 and strippers 56 . The cutting mechanism 28 is not important for the invention and only is cited as a supplement to this embodiment; it is in particular, possible to omit the knives 54 such that the rotor 52 simply acts as a conveyor. If the cutting mechanism 28 is provided, it serves to comminute the crop delivered by the pick-up 24 such that it can be better compacted in the baling chamber 42 .
[0019] The bottom 48 extends between the pick-up and the bottom conveyor 30 , and has a curvature that essentially follows the radius of the rotor 52 .
[0020] The cover 50 has the same curvature and extends between the conveyor 26 and the carrier or a roller 34 arranged on the lower end region of the carrier. The bottom 48 and the cover 50 form a receptacle opening upstream of the rotor 52 and an inlet 58 of the baling chamber 42 downstream of the rotor, with the inlet simultaneously being limited by the lower roller 34 and the bottom conveyor 30 . When viewing the round baler 10 from the left, the inlet 58 is situated in the first quadrant of the rotor 52 , and is consequently arranged essentially laterally to it.
[0021] The rotor 52 includes a central tube 60 and dogs 62 that are attached to the central tube 60 such that they are curved in a trailing fashion. The central tube 60 is driven in the clockwise direction, when viewing the round baler 10 from the left side, by means of a not-shown drive. The dogs 62 have an essentially triangular shape, the tip of which extends almost to the bottom 48 and the cover 50 . A total of five rows of dogs 62 are welded or screwed to the central tube 60 along helical lines, with the dogs 62 being spaced apart from one another in the axial direction of the rotor 52 . The diameter of the rotor 52 is of considerable size, and occupies approximately 0.6 m.
[0022] The knives 54 are realized conventionally and can preferably be locked in different positions, with the knives also bein able to yield in case of an overload. The knives 54 extend into all or only a few of the intermidiate spaces between the dogs 62 through slots in the bottom 48 that are not visible in the figures. The knives 54 are held by a common adjustable carrier, not illustrated in the figures, and may extend up to the central tube 60 in one end position and up to the inner edge of the bottom 48 in the other end position. As mentioned previously, the knives 54 can also be omitted such that the rotor 52 does not perform a cutting function, but rather acts only as a conveying rotor 52 . The knives 54 are situated below the rotor and upstream of the inlet 58 ; they may, however, also be arranged above the rotor 52 if the rotor conveys in an overshot fashion.
[0023] The strippers 56 are situated downstream of the knives 54 and are also arranged in the intermediate spaces between the dogs 62 . An edge of the dogs 62 that faces the baling chamber 42 extends nearly vertically and is slightly curved. The strippers 56 border the central tube 60 on the one side and the lower roller 34 on the other side, with the strippers very; closely following their contours. The position of the strippers 56 is chosen such that the round bale 44 is able always to support itself on the strippers against a forwardly directed movement, with the strippers consequently covering a certain part of the inlet 58 .
[0024] The bottom conveyor 30 in the embodiment according to FIGS. 1 - 3 is formed by two support rolls 64 that are stationarily, rotatably mounted in the frame 12 or in its side walls 22 , with a tension means 82 being looped around the support rolls. The rear support roll 64 is arranged lower than the front support roll 64 , but is still situated above the axle 16 . A descending transport surface is thus created on the two support rolls 64 and the tension means 82 . Instead of using the two support rolls 64 and the tension means 82 , it would also be conceivable to provide a larger or smaller number of support rolls, a chain conveyor, a conveyor belt or the like (see FIG. 4). The bottom conveyor 30 limits the baling chamber 42 in its lower region with part of the periphery, with said part of the periphery increasing as the size of the round bale 44 increases. The support rolls 64 are preferably driven.
[0025] The carrier 32 is realized in the form of a rail that is resistant to bending and is provided twice, namely on each side wall 22 . In this case, sufficiently known reinforcing elements that, however, are not illustrated in the figures, are provided between the two carriers. In the embodiment according to FIGS. 1 and 2, the carrier 32 is realized rigidly and is slightly inclined toward the front, with the carrier according to FIG. 3 being pivoted in a vertical plane about a horizontal pivot axis 66 that extends transverse to the driving direction of the round baler 10 . The pivoting axis 66 is situated between the ends of the carrier 32 and in this particular embodiment, approximately in its center such that it is able to move similarly to a rocker. In another embodiment that is not illustrated in the figures, the carrier 32 can be pivoted about a pivoting axis that coincides with the rotational axis of the lower roller 34 .
[0026] Assuming three rollers 34 are provided, which, however, is not absolutely imperative, the rollers 34 consist of a lower, a central and an upper roller 34 . The rollers 34 are rotatably accommodated between the two carriers 32 and extend across the entire width of the baling chamber 42 . The arrangement is chosen such that the surfaces or boundaries facing the round bale 44 lie on a curved surface, with this curved surface following the diameter of the round bale 44 once the round bale 44 has essentially reached its full size. The diameters of the lower roller and the central roller 34 are smaller than the diameter of the upper roller 34 . The lower roller 34 is always situated near the rear edge of the cover 50 . The rotational axis of the central roller 34 also forms the pivoting axis 66 . However, this is not absolutely imperative, and may be achieved differently in other embodiments. The pivoting axis 66 may, in particular, be offset toward the bottom, toward the top, toward the front or toward the rear. A gap through which the tension means 40 extends is formed between the central roller and the upper roller 34 . The lower roller and the central roller 34 directly form part of the wall of the baling chamber 42 , with the crop being baled therein directly acting upon said rollers. Instead of using the carrier 32 with its rollers 34 , it would also be possible to provide only one roller 34 or only one deflection roller 36 , around which the tension means 40 extends.
[0027] Several rolls 36 , of which at least one is driven, extend between the side walls 22 , and are, in part, rotatably supported in these parallel to the rollers 34 . According to FIG. 1, four rolls 36 are provided about which the tension means 40 revolves in an endless fashion. Two of the four rolls 36 are stationarily supported in the side walls 22 , with the other two rolls being movably supported on the tensioning device 38 such that they are able to move together with the tensioning device.
[0028] The tensioning device 38 conventionally includes an arm 68 , a bearing 70 and an energy storage device 72 . The arm 68 is formed by a massive steel rail or tube and provided twice, analogously to the carriers 32 , i.e., in the vicinity of both side walls 222 . The arm 68 extends almost over the entire length of the side wall 22 and is provided with two rolls 36 in the end region that is situated distant from the bearing 70 . These two rolls are spaced apart from one another in the radial direction. These rolls 36 are situated in interior spaces that are surrounded by the tension means 40 . The arm 68 extends beyond the bearing 70 in the end region that is situated near the bearing 70 , and is slightly angled so as to form a lever arm 74 . The bearing 70 accommodates the arm 68 in a vertically pivoting fashion at the end region situated opposite to the rolls 36 . For this purpose, a separate bearing 70 may be respectively provided on each side wall 22 , or one bearing may extend between the side walls 22 .
[0029] The energy storage device 72 is realized in the form of a helical tension spring in this embodiment; alternatively, it would be possible to utilize a hydraulic cylinder with a gas pressure accumulator or a throttle, a different type of spring, a combination thereof or the like. The energy storage device 72 is mounted at one end to the lever arm 74 and at the other end to the holder 76 , with the holder acting stationarily on the frame 12 or the side wall 22 . The energy storage device 72 normally is at least slightly pre-stressed. However, it would also be possible to realize an embodiment in which the resistance of the energy storage device 72 can be varied, e.g., by means of a controllable throttle, such that a different degree of compaction is realized across the diameter of the round baler 44 , so-called soft core is achieved. The effective direction of the energy storage device 72 is chosen such that the arm 68 with its rolls 36 is always pressed toward the inlet 58 , i.e., in the direction of the smallest possible baling chamber 42 .
[0030] The tension means 40 is conventionally formed of several narrow belts that extend parallel to one another in this embodiment. The tension mans 40 represents a closed tension means and extends through the frame 12 and the discharge gate 14 . It would also be conceivable to conventionally provide two separate tension means in the frame 12 and the discharge gate 14 . Beginning at the front roll 36 on the arm 68 , the tension means 40 runs through the gap between the upper and the central roller 34 on the carrier 32 , over a lower front roll 36 , an upper front roll 36 and on into the discharge gate 14 via an upper central roll, an upper rear roll, a lower rear roll, a movable roll, the rear roll on the arm 68 , an upper roll 36 , with the movable roll being identified by the reference symbol 90 and described in greater detail below. Due to the ability to pivot the arm 68 and the carrier 32 , the section of the tension means 40 which runs between the gap and the roll 36 on the arm 68 can be subjected to an excursion, and varied with respect to its size. This section represents part of the wall of the baling chamber 42 , and is directly acted upon by the crop situated in the baling chamber 42 .
[0031] The baling chamber 42 has a variable size and is surrounded by the inlet 58 , the rollers 34 on the carrier 32 , the section of the tension means 40 runs between the gap and the roll 36 on the arm 68 , a tension means section between the rear roll 36 on the arm 68 and the movable roll 90 , and the bottom conveyor 30 . On the end faces, the baling chamber 42 is partially closed by the side walls 22 .
[0032] The round bale 44 is formed of the crop that is would up in a helical fashion and ultimately reaches the size indicated in FIG. 2. In order to unload the round bale 44 from the baling chamber 42 , the discharge gate 14 is raised such that the round bale 44 is able to roll along the bottom conveyor 30 and onto the ground. The density of the round bale 44 is obtained by means of the tension means 40 , which is generated by the energy storage device 72 .
[0033] The discharge gate 14 is connected to the frame 12 in a vertically pivoting fashion in a bearing 78 , with the pivoting movement being caused by sufficiently known hydraulic cylinders that, however, are not illustrated in the figures. The discharge gate 14 has two side walls 80 , the aforementioned rolls 36 , a section of the endless tension means 40 , two arms 84 and the movable roll 90 . The side walls 80 extend in the same plane as the side walls 22 of the frame 12 and close the baling chamber 42 on its still-open end faces. Known reinforcing elements that, however, are not illustrated in the figures, extend between the side walls 80 . The four rolls 36 used in this embodiment are stationarily accommodated in a rotatable fashion in the side walls 80 and extend over the entire width of the baling chamber 42 , parallel to the rolls 36 in the frame 12 . Each arm 84 is connected in a vertically pivoting fashion in the vicinity of the upper edge of the cover plate 14 , and approximately centrally, in a bearing 92 , with the arms having a trough-like or Ushaped form when viewed from the side of the round baler 10 . The interior space of the arm 84 resulting from this particular shape is large enough that it can accommodate part of the circumference of the round bale 44 once it has reached is maximum size, i.e., the “trough” is open toward the front.
[0034] The arm 84 rotatably carries the roll 90 on its lower end, with the movable roll traveling along the surface of the bottom conveyor 30 as the diameter of the round bale 44 increases. The tension means 40 is guided over the movable roll 90 such that the movable roll 90 and the tension means section extending over it are always indirect or indirect contact with the round bale 44 . Another energy storage device 94 , which may be realized analogously to the energy storage device 72 , i.e., in the form of a helical tension spring, a hydraulic cylinder with a throttle or a pressure accumulator, etc., engages the arm 84 between the bearing 92 and the movable roll 90 . The energy storage device 94 is mounted, at the end that is situated distant from the arm 84 , to a holder 96 , with the holder being mounted on the side walls 80 . The energy storage device 94 is pre-stressed in such a way that it always presses the arm 84 toward the inlet 58 .
[0035] The side walls 22 and 80 abut one another in a plane of partition 98 that extends from the bearing 78 to the rear support roll 64 , from the upper front toward the lower rear, with an incline of approximately 600 with reference to the horizontal.
[0036] According to the previous description, the round baler 10 of the embodiment illustrated in FIGS. 1 and 2 functions as described below.
[0037] In a not-shown situation in which the tension arm 68 is situated in its lowest position due to the effect of the energy storage device 72 , the arm 84 and the movable roll 90 assume approximately the position shown in FIG. 1. The sections between the upper roller 34 on the carrier 32 and the rolls 36 on the arm 38 or the movable roll on the arm 84 extend essentially from the upper font toward the lower rear in a plane inclined by approximately 45°. In this case, the baling chamber 42 assumes a nearly triangular shape, the hypotenuse of which is formed by the two aforementioned sections, with the triangle almost standing on one of its tips. The baling chamber 42 has the smallest possible volume in this instance.
[0038] At the beginning of the baling process, the round baler 10 is moved over a field on which the crop is, for example, arranged in windrows, with the crop bein collected by means of the pick-up 24 and fed to the cutting mechanism 28 . The rotor 52 conveys the crop into the baling chamber 42 in an under shot fashion, if applicable, past the knives 54 . In the baling chamber 42 , the crop comes in contact with the strands of the tension means 40 that revolve in the same direction. Due to the cooperation between the rotatable support, and optionally the drive of the support rolls 64 and the rollers 34 , and the packing surface of the tension means 40 , 82 , the crop begins to rotate once it reaches a sufficient volume, namely in the clockwise direction in the figures. In another embodiment, the round bale 44 may also be would up in the counterclockwise direction.
[0039] As the baling process progresses, the round baler 10 reaches the operating state shown in FIG. 1, namely the operating state in which the arm 68 has been moved slightly upward against the -force of the energy storage device 72 and consequently subjects the strands to an upward excursion such that they are displaced out of the common plane and assume the shape of a blunt roof. In the embodiment according to FIG. 3, the carrier 32 is slightly pivoted about the pivoting axis 66 in the counterclockwise direction, such that its lower roller 34 moves into the baling chamber 42 . In this position, the round bale 44 is essentially supported on the front support roll 64 of the bottom conveyor 30 .
[0040] As the baling process progresses, the round bale 44 reaches the size shown in FIG. 2. In this operating state, the arm 68 is completely pivoted upward and the energy storage device is completely tensioned, such that the highest density possible is achieved on the circumferential surface of the round bale 44 . Since the bottom conveyor 30 is unable to yield and the carrier 32 with its rollers 34 is either realized stationarily or can, according to FIG. 3, pivot only to a limited degree, the round bale 44 is built up toward the top and the rear such that its circumferential region acts upon the section between the rear roll 36 on the arm 68 and the movable roll 90 or upon the movable roll 90 itself, although only indirectly. The arm 84 retreats in opposition to the force of the energy storage device 94 , and starting from a position near the inlet 58 , moves backward up to the plane of partition 98 and slightly into the discharge gate 14 , into a position situated distant from the inlet 58 . During this process, the round bale 44 is increasingly supported on the bottom conveyor 30 .
[0041] In order to eject the round bale 44 , the discharge gate 14 and consequently the arm 84 , are raised in the counterclockwise direction in the figure such athat the round bale 44 is able to roll, on the surface of the bottom conveyor 30 that is inclined toward the rear, out of the region of the baling chamber that is situated in the frame 12 . It is quite obvious that an opening through which the round bale 44 can be ejected is produced more rapidly, and with a shorter adjusting distance of the discharge gate 14 , due to the inclined plane of the partition 98 , as well as to the fact that the moveable roll 90 moves toward the rear. Both measures make it possible to attain the objective of the invention independently of one another, and can be carried out independently of one another. However, the described combination improves the respective effect. Due to the nearly triangular shape of the discharge gate 14 , an interfering front edge is reduced to a minimum, and the discharge gate 14 does not have to be raised as height in order to be moved over the round bales 44 lying on the ground when the round baler 10 is advanced in order to continue the baling process.
[0042] [0042]FIGS. 3 and 4 show embodiments of the invention which largely correspond to the embodiment according to FIGS. 1 and 2, and also fulfill the same function.
[0043] The difference between the embodiment according to FIGS. 1 and 2 and the embodiment according to FIG. 3 can be see in the fact that the carrier 32 is movable about a horizontal pivot axis 66 in FIG. 3.
[0044] The difference between the embodiment according to FIGS. 1 and 2 and the embodiment according to FIG. 4 can be seen in the fact that the bottom conveyor 30 in FIG. 4 does not consist of two support rolls 64 and an endless tension means 82 that extends over these two support rolls, but rather of a series of support rolls 64 that lie parallel to one another and exhibit the same surface that descends toward the rear. This is, among other things, achieved by means of diameters that decrease toward the rear.
[0045] In a not-shown embodiment, the bottom conveyor 30 can be pivoted downward about the rotational axis of the front support roll 64 on the rear side. This can be controlled by means of a hydraulic cylinder. Consequently a third measure is made available for rapidly realizing the required opening cross section.
[0046] Having described the preferred embodiment, it will become apparent that various modifications can be made without departing from the scope of the invention as defined in the accompanying claims.
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A baling chamber for a large round baler includes a discharge gate having opposite side walls which meet respective side walls of the main frame along a line of separation that inclines downwardly and to the rear from top to bottom. The bottom of the baling chamber is defined in part by a bottom conveyor which slopes downward to the rear from a front end which delimits a lower side of an inlet through which crop is fed into the baling chamber. The discharge gate carries a lower front roll that supports an endless tension element arrangement and that is itself supported on a tensioning arm arrangement that pivoted to the discharge gate for movement against the resistance of a yieldable spring arrangement so as to permit the lower front roll to move rearwardly from a first position adjacent the inlet, which it occupies at the beginning of bale formation, as the bale grows.
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FIELD OF THE INVENTION
This invention relates a wood reinforcing material for strengthening wood material and a reinforced wood material reinforced with the wood reinforcing material.
BACKGROUND OF THE INVENTION
Heretofore, single wood materials or so-called bonded wood materials formed by bonding sawn woods or small square lumbers cut longitudinally in the direction of fibers with the direction of the fibers being in parallel with each other have been used mainly as frame materials such as post and beams in buildings, as well as for wooden bridges or large scale domes.
Particularly, since the bonded wood materials are assembled from sawn woods and small square lumbers, they have excellent characteristics such as high degree of freedom for the size and dimension, less variation in the strength of products, cracks or errors cause by drying, as well as capable of easily manufacturing bent materials.
However, when such bonded wood materials are used for large buildings and structures, since the rigidity and strength of the bonded materials have to be increased, it is necessary to increase the thickness for the bonded materials and, as a result, this causes problems such as lowering of ceilings in the buildings and structures, or.unnecessary increase in the height of roofs.
Therefore, for providing the bonded wood materials and single wood materials with high rigidity and strength and also providing sufficient water proofness, corrosion resistance, fire resistance, heat resistance and adhesion required for the buildings or structures of woods, it has been proposed to bond carbon fibers by adhesives such as phenolic resins or resorcinolic resins to obtain reinforced wood materials such as carbon fiber-reinforced single wood materials or carbon fiber-reinforced bonded wood materials.
As one of methods for manufacturing such reinforced wood materials, Japanese Laid-Open No. 230904/1991, for instance, discloses a method of coating an adhesive on the surface of wood material, disposing carbon fibers thereon and impregnating an adhesive between the fibers and also bonding the same with the wood material (Prior Art 1).
As another method of manufacturing the carbon fiber-reinforced single wood material or carbon fiber-reinforced bonded wood material, Japanese Patent Laid-Open No. 108182/1978 proposes a method of using a so-called prepreg in which an adhesive is previously impregnated sufficiently to carbon fibers and bonding the same to a wood material (Prior Art 2). This method enables working in various places and is suitable also in view of the fabricability and, accordingly, has been used generally.
The present inventors have proposed a wood reinforcing material by bonding a wood reinforcing carbon fiber prepreg and a wooden sheet in Japanese Patent Laid-Open No. 254319/1997 (Prior Art 3). In this cited invention, release paper is not necessary, the resultant wood reinforcing material has high strength and high rigidity and can obtain high stable properties regarding adhesion performance between the wooden sheet and the wood material, or adhesion performance between the wooden sheet and carbon fibers.
In the Prior Arts 1 and 2, since the wood material is natural products having different natures depending on the growing environments, it involves a problem that adhesion fluctuates when the carbon fiber prepreg and the wood material are bonded. Further, for ensuring the bondability, it requires a frequent control for selecting and optimizing the state such as solid, semi-solid or liquid and amount thereof, which leaves various problems with view point of cost performance and quality.
In the Prior Art 2 described above, since carbon fiber prepregs are generally transported or stored being rolled or stacked into sheets, so that release paper is disposed on one surface or both surfaces of the prepreg. However, when bonding with the wood materials, troublesome and time consuming fabrication operations are necessary such as for removal of the release paper, as well as removed release paper yields wastes and the use of prepregs have resulted in environmental contamination.
In the Prior Art 3 described above, the wooden sheet itself causes shear failure in the bending failure test and sufficient reinforcing effect can not always be obtained.
The present inventors have intended to provide a wood reinforcing material which is applied to wood materials or bonded wood materials for reinforcement capable of overcoming the problems in the prior art, as well as a reinforced wood material in which the wood reinforcing material is applied to the surface of the wood material or to the inner layer of the bonded wood material.
Specifically, this invention intends to provide a wood reinforcing material excellent in bondability with the wood material and handlability, not causing environmental contamination such as forming wastes of release paper, and having a sufficient reinforcing effect for the wood material, as well as reinforced wood material.
More specifically, this invention intends to provide a wood reinforcing material of reducing fluctuation of adhesion performance, strength and rigidity caused by variation in wood materials as natural products and minimizing the complexity in view of the working and minimizing the wastes, as well as having high bondability, strength and rigidity, as well as a reinforced wood material applied with the wood reinforcing material.
SUMMARY OF THE INVENTION
It is an object of the present invention to solve the foregoing problems.
In accordance with a wood reinforcing material of this invention, a phenol resin-impregnated sheet with a degree of cure of 70% or more and 95% or less in which a porous sheet is impregnated with a phenol resin is disposed on the surface of a carbon fiber-reinforced thermosetting resin sheet.
Further, in accordance with a reinforced wood material of the invention, the wood reinforcing material is integrated and cured by way of a phenol resin-impregnated sheet on the surface of a wood material.
In the wood reinforcing material of the invention, since a phenolic resin-impregnated sheet with a degree of cure of 70% or more and 95% or less is disposed, it forms a molding product showing excellent adhesion to a wood material to be reinforced and also free from stickiness, so that it does not require release paper. Accordingly, the reinforced wood material according to this invention which is reinforced by applying the wood reinforcing material of the invention to the surface of the wood material has a feature of high strength, high rigidity and high shear strength.
Carbon Fiber-reinforced Thermosetting Resin Sheet
A carbon fiber-reinforced thermosetting resin sheet as a constituent factor of the wood reinforcing material of this invention is reinforced with carbon fiber in the thermosetting resin as reinforcing fibers.
There is no particular restriction on the carbon fibers and carbon fibers obtained from polyacrylonitrile fibers with a nitrogen content of 0.1 to 15% by weight, a tensile strength of 2,500 to 7,000 MPa and a modulus of elasticity of 150-700 GPa are preferred and, particularly, carbon fibers of 5 to 9 mm diameter containing 3 to 10% of a nitrogen content and having 3,500 MPa or more of tensile strength and 200 to 350 GPa of modulus of elasticity are preferred in view of the adhesion.
Further, those in which the oxygen/carbon ratio of 0.01/1 to 0.3/1, particularly, 0.01/1 to 0.25/1 at the surface of the carbon fibers of this invention by an ESCA surface analyzer (manufactured by Shimazu Seisakusho) are preferred since the adhesion strength can be improved.
It is desired that carbon fibers with the fiber diameter of from 5 to 9 mm and fiber strands comprising the fibers by the number of 1,000 to 300,000 are used by being bundled or spread in a sheet-like shape in an amount, with no particular restriction only thereto.
The form of the carbon fiber may be a multi-directional sheet such as woven or non-woven fabrics or linear materials such as uni-directionally oriented sheets or rovings.
Kinds of the thermosetting resins reinforced with carbon fibers have no particular restrictions and, in view of use for buildings, one or more member selected from isocyanate type resins or resorsinol resins, or resol type phenolic resins are preferred, formaldehydes are preferred as the curing agent for the thermosetting resin and inorganic acids or organic acids are preferred for curing catalysts.
Referring more specifically to the thermosetting resins, known resol type phenol resins (phenol formaldehyde initial polycondensation resins) and resorcinol resins obtained by methyloling phenols having a phenol hydroxy group such as phenol, cresol, xylenol, ethylphenol, chlorophenol and bromophenol or phenols having two or more phenolic hydroxy groups such as oligomer, and resorcin, hydroquinone, catechol and fluoroglycinol, and aldehydes such as formaldehyde, para-formaldehyde, acetoaldehyde, fulfural, benzaldehyde, trioxane and tetraoxane, at a molar ratio of phenols/aldehydes=2/1 to 1/3, preferably, 5/4 to 2/5, under the presence of an alkali catalyst such as potassium hydroxide or sodium hydroxide can be used.
More preferably, resins having an average molecular weight as polystyrene of 120 to 2000, and, particularly, 150 to 500 according to high speed liquid chromatography (HPLC) are preferred and those resins having viscosity adjusted to 3 to 150 poise at 25-C are preferred.
Among known curing agents used for resorcinol resins and resol type phenol resins curing agents which become paste or liquid when mixed with the resins such as formaldehyde, acetoaldehyde, furfural or trioxane are preferred.
Curing catalysts which are dissolved into liquid form when mixed with resins such as para-toluene sulfonic acid, benzene sulfonic acid, xylene sulfonic acid and phenol sulfonic acid are preferred.
In view of the production process of the carbon fiber-reinforced thermosetting resin sheets, curing agents or curing catalysts which form homogeneous liquid at 35-C or lower as a temperature for usual production of prepregs when prepared as mixed resins for uniformly curing the prepregs are preferred.
In the fiber reinforcing material of this invention, the carbon fiber-reinforced thermosetting resin sheet as a constituent factor may be a prepreg sheet or a completely cured sheet. It is preferred that the sheet is completely cured with an aim of increasing the strength of the carbon fiber-strengthened resin composite material per se.
Phenol Resin-impregnated Sheet
The phenol resin impregnated sheet as a constituent factor of the wood reinforcing material of this invention is a sheet formed by impregnating a porous sheet with a phenol resin, for improving the adhesion strength when the wood reinforcing material is bonded by an adhesive on the surface of wood material. Accordingly, it is important that the sheet has thin and uniform thickness.
The thickness of the phenol resin-impregnated sheet is preferably 0.01 mm or more and 1.0 mm or less. If the thickness is less than 0.01 mm, the sheet performance is deteriorated by unevenness caused to the form of the phenol resin-impregnated sheet and, depending on the case, curling in the lateral direction and, in addition, the strength of the sheet is lowered to allow easy tearing by an external force or result in difficulty in the handlability. On the other hand, if the thickness is more than 1.0 mm, the water proofness or shear strength is sometimes lowered.
The porous sheet can include, regarding the form, for example, non-woven fabric, paper and wooden fabric and can include, regarding material, for example, pulp, glass fiber and carbon fiber and synthetic fiber.
The resin impregnating in the phenol resin-impregnated sheet used in this invention is a highly viscous or solid resin such as a phenolic resin or phenol/melamine resin mixture, with no restriction for the presence or absence of the curing agent, and use of a less reactive resin capable of controlling the degree of cure is preferred for attaining the purpose of this invention.
The phenol resin is used because this is excellent in fire proof and heat resistant performance and, further, excellent in water proofness, corrosion resistance and bondability and, thus, this can be used suitably to building materials.
Actual examples of such phenol resins are phenols having one phenolic hydroxy group such as phenol, cresol, xylenol, ethylphenol, chlorophenol and bromophenol or phenols having two or more phenolic hydroxy groups such as oligomer and resorcine, hydroquinone, catechol and fluoroglycinol and, further, resins formed by mixing one or more of resins such as melamine, epoxy, and unsaturated esters with the resins mentioned above.
In the wood reinforcing material of this invention, it is preferred that the degree of cure of the phenol resin in the phenol resin-impregnated sheet as the constituent factor is controlled to 70% or more and 95% or less, preferably, 75% or more and 90% or less, in order to keep favorable adhesion and shear strength. That is, if the degree of the cure of the resin is less than 70%, peeling occurs in the phenol resin-impregnated sheet because of the low degree of the cure of the phenol resin and, on the other hand, if it exceeds 95%, curing proceeds excessively and reactivity with the adhesive is lowered to result in peeling at the boundary with the wood material.
Further, when the degree of cure of the resin in the phenol resin-impregnated sheet is controlled to 70% or more and 95% or less, the wood reinforcing material of this invention forms a molding product with no stickiness thus making it unnecessary for the use of release paper which is indispensable for usual prepregs during storage or transportation.
The degree of cure is measured as follows.
{circle around (1)} For identical phenol resin-impregnated sheets, an uncured phenol resin-impregnated sheet and an optionally cured phenol resin-impregnated sheet are dried each by 100 cm 2 in a desiccator containing a silica gel at a normal temperature for 30 min. under a reduced pressure and then further dried in a pressure reduced state for 15 hrs. The weight for the uncured phenol resin-impregnated sheet and the optionally cured phenol resin-impregnated sheet in this case is defined as WO, WO′, respectively.
{circle around (2)} Each of the uncured phenol resin-impregnated sheet and the optionally cured phenol resin-impregnated sheet in above {circle around (1)} is extracted for five hours with the solvent for the phenol resin-impregnated sheet such as acetone using a Soxhlet extractor, dried in a desiccator containing silica gel at a normal temperature for 2 hours under a reduced pressure and, further, dried for 15 hrs in a pressure reduced state. The weight for the uncured phenol resin-impregnated sheet and the optionally cured phenol resin-impregnated sheet in this case is defined as W1, W1′, respectively.
{circle around (3)} Degree of cure is calculated based on and described above {circle around (1)} and {circle around (2)} in accordance with the following equation 1.
Degree of cure (%)=( 1−( W 0 ′−S 1′)/( W 0 −W 1))×100 formula (1)
Composite Structure of Wood Reinforcing Material
The carbon fiber-reinforced thermosetting resin sheet and the phenol resin-impregnated sheet can take the following composite structures (1) and (2).
Composite Structure (1):
A composite structure in which the carbon fiber reinforced thermosetting resin sheet and the phenol resin-impregnated sheet are entirely bonded and integrated.
Composite Structure (2):
A composite structure in which the carbon fiber-reinforced thermosetting resin sheet and the phenol resin-impregnated sheet are point-bonded and integrated.
Such composite structures (1) and (2) can be obtained by the following manufacturing method.
Manufacturing Method:
A phenol resin-impregnated sheet is appended on one surface or both surfaces of a so-called prepreg sheet formed by impregnating carbon fibers with a thermosetting resin for wood reinforcement, and then integrating them by using a hot press or the like such that the degree of cure of the phenol resin-impregnated sheet is 70% or more and 95% or less. The thermosetting resin for the carbon fibers in this case may not always be cured completely.
Reinforced Wood Material
The reinforced wood material in this invention can include single wood materials or bonded wood materials and there are no particular restrictions so long as they are existent wood materials and, usually, wood materials used for building such as cedar, hinoki cypress, larch, Pseudotsuga taxifolia Britt and peel of Citrus aurantium and wood material used for plywoods such as Japanese oak, paulownia, zelkova, maple, horse chestnut, Magnolia obovata Thumb, cherry, teak, lauan and SPINAL can be used.
Reinforcement of Wood Material
Wood reinforcing material of this invention (carbon fiber reinforced resin composite material) is used for wood reinforcement as shown below.
The wood reinforcing material of this invention is appended on the surface of a single wood material or to the surface of the single board or any one of board, or between single boards or the surface of a bonded material comprising a plurality of boards or single board and integrated and cured into a reinforced wood material, optionally, with the interposition of adhesives or further necessary, under heating and under pressure.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an example of a wood reinforcing material of this invention which is shown being decomposed on every constituent factors. In FIG. 1, in the wood reinforcing material (carbon fiber-reinforced resin composite material) of this invention, a phenol resin-impregnated sheet 1 is disposed on both surfaces of a carbon fiber-reinforced thermosetting resin sheet 2 .
FIG. 2 illustrates an example of a wood reinforcing material of this invention which is shown being decomposed on every constituent factors. In the reinforced wood material in FIG. 2, a wood reinforcing material 4 of this invention is disposed for reinforcement on both surfaces of a single wood material 3 . Although not shown particularly in FIG. 2, an adhesive resin is usually present between the single wood material 3 and the wood reinforcing material 4 .
FIG. 3 is a cross sectional view for an example of a reinforced wood material in which bonded material is reinforced by using the wood reinforcing material of this invention. In the reinforced wood material in FIG. 3, a wood reinforcing material 4 comprising a plurality of layers is disposed on a bonded material 5 laminated in a plurality of layers and, further, a single wood material 3 is disposed on the wood reinforcing material 4 . Although not particularly illustrated in FIG. 3, an adhesive layer is usually interposed between the single wood material 3 and the wood reinforcing material 4 , between the wood reinforcing material 4 and the wood reinforcing material 4 , between the wood reinforcing material 4 and the bonded material 5 or between the bonded material 5 and the BONDED material 5 .
DETAILED DESCRIPTION OF THE INVENTION
The wood reinforcing material of this invention will described more specifically with reference to the accompanying drawings.
The wood reinforcing material of this invention can be manufactured, for example, as shown below.
It is manufactured by dipping strands of carbon fibers continuously in a liquid resin mixture formed by mixing one or more of thermosetting resins, a curing agent or a curing catalyst and, optionally, an inorganic filler such that the resin mixture is 30 to 80% by weight based on the carbon fibers, drying evaporative contents, if necessary, then winding the fibers so as to be in parallel with each other on a phenol resin-impregnated sheet previously wound around a drum, drying optionally and cutting the same in the lateral direction of the drum, or manufactured by a method of impregnating a resin into fibers while arranging carbon fiber strands on a phenol resin-impregnated sheet in which the resin is previously coated while pressing by a roll on the surface in parallel with each other.
It is preferred that the resin mixture is a homogeneous solution for uniformly impregnating the carbon fibers and conducting curing uniformly. If it is not uniform, the resultant carbon fiber-reinforced thermosetting resin sheet (prepreg) causes curing failure, or the adhesion is lowered, which is not preferred.
Further, when the amount of the resin mixture of the carbon fiber-reinforced thermosetting resin sheet impregnated with the resin mixture is 30% by weight or less, not only the strength property is not developed but also the bondability with the phenol resin-impregnated sheet is poor because of the insufficiency of the amount of the resin. On the other hand, when the amount of the resin mixture in the carbon fiber-reinforced thermosetting resin sheet is more than 80% by weight, the strength property is not developed which that the carbon fibers are disturbed being caused by the resin flow during molding, as well as difficulty is caused to the handlability such as drop of the resin from the carbon fiber-reinforced thermosetting resin sheet because of excessive amount, which is not preferred.
Particularly, it is preferred when the amount of the resin mixture in the carbon fiber-reinforced thermosetting resin sheet is from 40 to 60% by weight, since the strength property, bondability with the phenol resin-impregnated sheet or handlability of the carbon fiber-reinforced thermosetting resin sheet are favorable.
Further, the viscosity of the resin mixture at 25-C is preferably from 3 to 150 poise. If the viscosity is 3 poise or less, the resin tends to drop from the prepreg and, on the other hand, if it is 150 poise or more, impregnation of the resin into the carbon fibers is deteriorated, which is not preferred.
The viscosity can be controlled with addition of water or alcohol.
The wood reinforcing material of this invention can be manufactured by appending a phenol resin-impregnated sheet to a carbon fiber-reinforced thermosetting resin sheet, pressurizing them and, optionally, heating them into integration. The degree of cure of the phenol resin-impregnated sheet in this case is controlled 70% or more and 95% or less, which may be controlled by heating for once or heating for twice or more during preparation, or by culture at normal temperature.
The wood reinforcing material of this invention and a single wood material and a bonded wood material are bonded and integrated as shown below.
That is, an existent wood adhesive, if necessary, the resin formed by mixing the resin and an inorganic acid or an organic acid as a curing agent or curing catalyst used in this invention, a resin mixture used for the carbon fiber prepreg can be coated to the surface of the single wood material or the bonded wood material, and the surface of the thin board of the bonded wood. After coating the resin to the wood surface, the wood reinforcing material is appended such that the direction of the carbon fibers is parallel with the fiber direction of the wood and, in a case where the reinforced wood material is a thin board for bonded wood material, the wood reinforcing material and other several thin boards for bonded wood material are laminated by way of an adhesive by a known method and then heated under a pressure of 1 to 15 kg/cm 2 at a temperature of normal temperature to 120-C for 5 to 24 hours to obtain the reinforced wood of this invention.
This invention is to be explained concretely by way of examples but the invention is not restricted to the following examples unless it exceeds the scope thereof.
The viscosity of the resin for use in the carbon fiber resin composite material was measured and determined by using a rheology physical property tester (manufactured by Rheology Co.).
Further, bending test and bondability test (cole test, boiled test and block shearing test) for wood material, bonded wood material and carbon fiber reinforced wood material and bonded wood material thereof were conducted in accordance with Agricultural and Forest Standards of Japan for structural bonded wood material. The cold test and the boiled test were conducted in application circumstance 1.
EXAMPLE 1
Strands of carbon fibers “BESFITE (registered trade name) HTA12K” (manufactured by Toho Rayon Co.) having fiber characteristics of a single fiber diameter of 7 mm, total number of fibers of 12,000, a tensile strength of 3,890 MPa and a tensile modulus of elasticity of 236 GPa were passed through a resin bath containing a resin mixture obtained by uniformly mixing and dissolving 82 parts of resol type phenol resin “AH-343” (manufactured by Lignite Co.) having a viscosity at 20-C of 35 poise and 18 parts of an organic curing agent mainly comprising para-toluene sulfonic acid “D-5” (manufactured by Lignite Co.) by 5 mm/min, at a room temperature and for a dip time of 0.5 min., and wound around a drum of 127 cm diameter to a width of 100 cm such that the strands were in parallel while controlling by a squeeze roll such that the resin content was 55% by weight to form a carbon fiber-reinforced thermosetting resin sheet of 100 cm width and about 4.0 m length, with the total carbon fiber weight of 150 g/M 2 .
After cutting the carbon fiber-reinforced thermosetting resin sheet to a rectangular shape of 100 mm width and 250 mm length and laminating them by two layers, a phenol resin-impregnated sheet of 0.25 mm thickness (trade name of products: phenol resin-impregnated sheet PFP2, manufactured by Lignite Co.) was appended on both surfaces and heat cured to be integrated under a pressure of 5 kg/cm 2 at a temperature of 100-C for a retention time of 3 hrs to form a flat board of a wood reinforcing material of this Example 1 (a carbon fiber reinforced resin composite material). The carbon fiber content in the wood reinforcing material is 50% by volume and the degree of cure for the phenol resin-impregnated sheet is 80%.
A single cedar board of 60 mm width, 75 mm length and 10 mm thickness was bonded to both surfaces of the flat board of the wood reinforcing material of 60 mm width and 75 mm length cut out of the flat wood reinforcing material by using a resin formed by mixing 85 parts of resorcinol resin D300 (trade name) and 15 parts of para-formaldehyde H30M (trade name), the curing agent therefor manufactured by Ohkashinko Co., to prepare the reinforced wood material of this Example 1.
Cold test, boiled test and block shearing test were conducted for the thus obtained reinforced wood material as the specimen.
Further, in the same manner as in the method described above, rectangular flat boards of wood reinforcing material of 30 mm width, 500 mm length and 45 mm width and 2 m length were prepared in the same manner as described above. They were bonded to a cedar board of 30 mm width, 500 mm length and 25 mm thickness and a bonded wood material formed by laminating four cedar layers each of 45 mm width, 2 m length and 25 mm thickness respectively using the resin consists of the above-mentioned D300 and H30M and bending strength was measured.
The results are shown in the following Table 1. The reinforced wood material formed by integrating the wood reinforcing material of Example 1 and the wood material had excellent adhesion performance and strength characteristic capable of satisfying Agriculture and Forestry Standard of Japan.
COMPARATIVE EXAMPLE 1
A wood reinforcing material (FRP) was prepared in the same manner as in Example 1 by using the carbon fiber-reinforced thermosetting resin sheet manufactured in the same manner as in Example 1 except for laminating the sheet by two layers and not appending the phenol resin-impregnated sheet thereto. This was bonded and integrated with the wood material (cedar) in the same manner as in Example 1 to obtain a reinforced wood material of Comparative Example 1, to which adhesion test and bending test were conducted. The results are shown in the following Table 1. This did not satisfy the adhesion test according to Agriculture and Forestry Standards of Japan and the bending strength showed no satisfactory value although improved somewhat.
COMPARATIVE EXAMPLE 2
A wood reinforcing material was prepared by using the carbon fiber-reinforced thermosetting resin sheet prepared in the same manner as in Example 1 except for laminating the sheet by two layers and appending a wooden sheet (spruce) instead of the phenol resin-impregnated sheet. This was bonded and integrated with the wood material (cedar) in the same manner as in Example 1 to prepare a reinforced wood material, to which adhesion test and bending test were conducted. The results are shown in the following Table 1. Although this satisfied the adhesion test according to Agriculture and Forestry Standards of Japan but shear fracture was caused in the spruce in the bending test and no sufficient value was obtained for the improvement of the bending strength.
TABLE 1
Comparetive
Comparative
Item
Not-reinforced
Example 1
Example 1
Example 2
Molding material
Surface material
None
Phenol resin-
FRP sheet
Spruce sheet
impregnated
sheet
Thickness
—
0.25 mm
—
0.45 mm
Degree of cure
—
80%
—
—
Material in FRP
None
CF/phenol
CF/phenol
CF/phenol
Form of fiber
None
Umidirectional
Umidirectional
Umidirectional
CF amount 2 m bending test
None
300 g/m 2 × 4
300 g/m 2 × 4
300 g/m 2 × 4
layer
layer
layer
Other test
None
150 g/m 2 × 2
150 g/m 2 × 2
150 g/m 2 × 2
layer
layer
layer
Bonded material
Cedar
Cedar
Cedar
Cedar
Adhesive
Phenol resin
Phenol resin
Phenol resin
Phenol resin
Boiled test
Delamination (%)
1st
0
0
32
0
2nd
0
0
69
0
Main Delamination form
None
None
Between wood
None
sheet
Cold test
Delamination (%)
1st
0
0
15
0
2nd
0
0
26
0
Main Delamination form
None
None
Between wood
None
sheet
Block shearing test
Shear strength
98 kgf/cm 2
112 kgf/cm 2
92 kgf/cm 2
102 kfg/cm 2
Wood failure
100%
88%
46%
5%
rate
Failure form
Wood broken
Wood broken
Between wood
Spruce shear
sheet
50 cm bending test
Bending strength
742 kgf/cm 2
1430 kgf/cm 2
1270 kgf/cm 2
1230 kgf/cm 2
Failure form
Wood broken
Wood broken
Between wood
Spruce shear
sheet
2 m bend test
Bending strength
283 kgf/cm 2
763 kgf/cm 2
442 kgf/cm 2
397 kgf/cm 2
Failure form
Wood broken
Wood broken
Between wood
Spruce shear
sheet
EXAMPLE 2
A test specimen was prepared in the same manner as in Example 1 except for changing the fabrication temperature to 90-C upon manufacture of the wood reinforcing material in Example 1, and adhesion test was conducted. The results are shown in the following Table 2.
The degree of cure of the phenol resin-impregnated sheet of the wood reinforcing material in Example 2 was 75%, which showed adhesion performance satisfying the Agriculture and Forestry Standards of Japan.
EXAMPLE 3
A test specimen was prepared in the same manner as in Example 1 except for changing the fabrication temperature to 110-C upon manufacture of the wood reinforcing material in Example 1, and an adhesion test was conducted. The results are shown in the following Table 2.
The degree of cure of the phenol resin-impregnated sheet of the wood reinforcing material in Example 3 was 90%, which showed adhesion performance satisfying the Agriculture and Forestry Standards of Japan.
Comparative Example 3
A test specimen was prepared in the same manner as in Example 1 except for changing the fabrication temperature to 80-C upon manufacture of the carbon fiber-reinforced thermosetting resin sheet in Example 1, and adhesion test was conducted. The results are shown in the following Table 2.
The degree of cure of the phenol resin-impregnated sheet of the wood reinforcing material in Comparative Example 3 was 50%, which showed adhesion performance not satisfying the Agriculture and Forestry Standards of Japan.
COMPARATIVE EXAMPLE 4
A test specimen was prepared in the same manner as in Example 1 except for changing the fabrication temperature to 150-C upon manufacture of the carbon fiber-reinforced thermosetting resin sheet in Example 1, and an adhesion test was conducted. The results are shown in the following Table 2.
The degree of cure of the phenol resin-impregnated sheet of the wood reinforcing material in Comparative Example 4 was 99% or more, which showed adhesion performance not satisfying the Agriculture and Forestry Standards of Japan.
TABLE 2
Comparative
Comparative
Item
Example 2
Example 3
Example 3
Example 4
Molding material
Surface material
Material
Phenol resin-
Phenol resin-
Phenol resin-
Phenol resin-
impregnated
impregnated
impregnated
impregnated
sheet
sheet
sheet
sheet
Thickness
0.25 mm
0.25 mm
0.25 mm
0.25 mm
Degree of cure
75%
90%
50%
99%
FRP sheet
Material
CF/phenol
CF/phenol
CF/phenol
CF/phenol
CF form
Unidirectional
Unidirectional
Unidirectional
Unidirectional
Bonded material
Cedar
Cedar
Cedar
Cedar
Wood sheet adhesive
Phenol resin
Phenol resin
Phenol resin
Phenol resin
Boiled test
Delamination (%)
1 st
0
0
5
100
2 nd
0
0
7
100
Delamination form
None
None
In impregnated
Between wood
sheet
sheets
Cold test
Delamination (%)
1 st
0
0
0
15
2 nd
0
0
3
32
Delamination form
None
None
In impregnated
Between wood
sheet
material
Block shearing test
Shear strength
110 kgf/cm 2
109 kgf/cm 2
95 kgf/cm 2
64 kgf/cm 2
Failure form
Wood broken
Wood broken
In impregnated
Between wood
sheet
Industrial Applicability
Since the wood reinforcing material of this invention is formed by disposing a phenol resin-impregnated sheet with a degree of cure of 70% or more and 95% or less on the surface of the carbon fiber-reinforced thermosetting resin sheet, it can solve the problem of wastes caused by release paper resulted in existent carbon fiber prepregs and has excellent bondability to wood materials.
Since the reinforced wood manufactured by using the wood reinforcing material of this invention has high strength, particularly, high strength in a bending failure test and high adhesion and rigidity, and has sufficient water proofness, corrosion resistance, fire proofness, heat resistance and long time stability, wood materials and bonded materials reduced in the weight and increased in the size can be manufactured efficiently.
The reinforced wood material (reinforced single wood material and bonded wood material) of this invention are applicable to application uses in which they are used as usual wood materials and bonded wood materials and, in particular, they are suitable as aggregates for large buildings such as schools, gymnasiums, assembly houses, various kinds of indoor ball game stadia and domes, three or more storied residences and aggregates for wooden bridges. Further, even wood materials not usable so far because of low strength of low rigidity can be employed, which can lead to effective utilization of various resources and are useful in view of environmental preservation.
Furthermore, this can extend the application uses of wood materials to large scale buildings and structures not possible so far, as well as can reduce the amount of natural wood materials used.
The reinforced wood material of this invention can reduce the fluctuation of adhesion performance, strength and rigidity caused by scatterings present in wood materials as natural products.
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A phenol resin-impregnated sheet formed by impregnating a porous resin sheet with a phenol resin having a degree of cure of from 70% to 95% is arranged on and lamininated to the surface of a carbon fiber-reinforced thermosetting resin sheet. The thickness of the phenol resin impregnated sheet is between 0.01 mm and 1.0 mm. A very even, strong and water-proof wood reinforcing material is obtained. The wood reinforcing material is intergrated and cured on the surface of the wood material by the phenol resin-impregnated sheet to reinforce wood material (single board or bonded board) to form a reinforced wood material. The wood reinforcing material adheres suitably with the wood material and does not cause environmental contamination.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of and priority to U.S. Provisional Application Ser. No. 61/637,141, filed Apr. 23, 2012, entitled “Modular LED Lighting Apparatus,” the contents of which is incorporated by reference herein in its entirety.
BACKGROUND
[0002] 1. Field
[0003] The subject disclosure relates to LED lighting apparatus and more particularly to such apparatus providing a string of LED circuit board carrying capsules.
[0004] 2. Related Art
[0005] Various decorative and/or accent linear lighting apparatus such as rope light, luminous incandescent lighting, and festoon lighting have been in use for some time.
SUMMARY
[0006] An illustrative stringed LED capsule lighting apparatus comprises a plurality of adjacent capsules, each capsule comprising (a) a base component, (b) a body component carrying an LED circuit board thereon, and (c) a lens component, wherein, in one embodiment, the body and the base snap together and the lens snap-fits to the body. Electrical conductors for supplying power to the LEDs enter at one end of the body and exit at an opposite end of the body and attach to respective internal metal connector components, which pass through a surface of the body to supply power to one or more LEDs. The electrical connector components may attach to the body, for example, by snapping into the body in an interior portion thereof to thereby hook the capsules to the conductors, thereby forming a flexible string of LED light capsules. In one embodiment, a guide track and means on the capsule bodies for attaching the capsules to the guide track are provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a side view illustrating a plurality of LED light capsules and a guide track which may find use therewith;
[0008] FIG. 2 is a perspective view of a base component of a light capsule;
[0009] FIG. 3 is a top view of the base component of FIG. 2 ;
[0010] FIG. 4 is a perspective view of a body component of a light capsule;
[0011] FIG. 5 is a top view of the body component of FIG. 4 ;
[0012] FIG. 6 is a sectional view taken at VI-VI of FIG. 5 ;
[0013] FIG. 7 is a sectional view taken at VII-VII of FIG. 5 ;
[0014] FIG. 8 is a perspective view of a lens component;
[0015] FIG. 9 is a bottom view of the lens component of FIG. 8 ;
[0016] FIG. 10 is a sectional view of an illustrative guide track taken at X-X of FIG. 1 ;
[0017] FIG. 11 is a cutaway view of a portion of a light capsule unit illustrating internal electrical conducting componentry;
[0018] FIG. 12 is a perspective view of the underside of a light capsule unit with the base component removed;
[0019] FIG. 13 is a perspective view of an illustrative embodiment of an electrical connector;
[0020] FIG. 14 is an end view of the connector of FIG. 13 ;
[0021] FIG. 15 is an end view of an opposite end of the connector of FIG. 13 ;
[0022] FIG. 16 is a side view of the connector of FIG. 13 ; and
[0023] FIG. 17 is a side view of the connector of FIG. 13 .
DETAILED DESCRIPTION
[0024] FIG. 1 shows an illustrative embodiment of a string of LED light modules or “capsules” 11 and a flexible guide track 61 to which the capsules 11 may attach. According to an illustrative embodiment, each LED light capsule 11 comprises a base 13 , a body 25 , and a lens 51 , all three of which may snap together to form the unit 11 .
[0025] A base member 13 is shown in FIGS. 2-3 and includes a generally flat floor portion 14 from which extends a generally rectangular inner vertical support 15 and respective end supports 17 , 18 . Along each side of the floor 14 are respective vertical lips 16 , indentations 19 in the vertical lips 16 , and mounting tabs 21 . The indentations 19 allow passage of guide track mounting tabs 31 of the body 25 , while the tabs 21 snap into recesses 30 ( FIG. 7 ) in the inner sidewalls 33 , 35 of the body 25 to enable the base 13 to snap or press fit to the body 25 .
[0026] FIGS. 4-7 further show that the body 25 includes vertical side walls 32 , 34 and front and back walls, 36. 38. A wire guide 37 protrudes from the front wall 36 , while an oval opening 40 ( FIG. 12 ) is formed in the back wall 38 . The guide track mounting tabs 31 are formed along the bottom edges of the side walls 32 , 34 , while slots 39 are formed along the top edges. The slots 39 accommodate tabs 53 formed on respective sides of the lower rectangular edge 54 of the lens 51 ( FIG. 8 ) and facilitate snap fitting of the lens 51 onto the body 25 . Flexible fingers 44 extend from a top surface 48 of the body 25 and serve to attach an LED-carrying circuit board 115 ( FIG. 11 ) to the surface 48 .
[0027] A pair of holes 41 , 43 are provided through the top surface 48 of body 25 and facilitate passage of electrical pins 109 , 111 ( FIG. 11 ) to supply power to the LEDs, e.g., 112 and related circuitry on the LED carrying circuit board 115 . In one embodiment, one or more relatively low power LEDs are employed to achieve various decorative lighting effects. As shown in FIGS. 5 and 6 , wire guides are formed on the underside of surface 49 , which in the illustrative embodiment include a central vertical guide tab 45 and a horizontal tab 46 with wire guide slots 47 and 48 .
[0028] FIGS. 11 and 12 illustrate how the respective electrical conductors (wires) 101 , 102 are guided through the body and employed to interconnect one adjacent module or capsule 11 to the next. In particular, in one illustrative embodiment, metal connector components 105 , 107 are clamped onto the respective wires 101 , 102 so as to pierce and make electrical contact with the current carrying electrical conductors inside respective outer insulative layers of the wires 101 , 102 . Additionally, the wire guides 37 capture and hold the electrical cable to further assist in attaching the capsules 11 to the cable.
[0029] As noted above, the connector components 105 , 107 include the vertically extending pins 109 , 111 , which carry power to the circuit board 115 . As may be seen in FIG. 12 , respective cylindrical portions of the connector components 105 , 107 snap into or otherwise attach to the respective wire guide slots 47 , 48 and are separated by the central vertical guide tab 45 . The conductors 101 , 102 are guided out of the body 25 at one end by the wire guide 37 , which, in an illustrative embodiment, extends into the oval opening 40 of an adjacent capsule 11 and is shaped and sized to be pivotable or rotatable therein to guide and shield the conductors 101 , 102 , while at the same time allowing each module or capsule 11 in a string of modules or capsules to freely bend in any direction and to provide decorative “string lighting” effects. In one embodiment, strings of modules can be removably attached to a guide track 61 , which may be stapled to adjacent surfaces and optionally also glued, employing the teeth on the underside of the guide track ( FIG. 10 ) which serve to provide more surface area to promote adhesion. The flexibility of the guide track 61 may also vary in various embodiments.
[0030] An illustrative embodiment of a connector 105 is shown in more detail in FIGS. 13-17 . The connector 105 includes a horizontal channel 121 which unitarily forms or bends into a vertically disposed pin 109 . The channel 121 includes respective sides 125 , 127 , which extend on either side of an arcuate bottom portion 129 . First and second teeth 131 , 133 protrude upwardly from the bottom portion 129 . In one embodiment, the second connector 107 may be identical to connector 105 . Connectors so constructed may be readily attached to insulated electrical conductors or cable utilizing a machine which pushes the teeth 131 , 133 through the insulation and into the electrically conductive portion as the sides 125 , 127 are crimped around the cable.
[0031] Various embodiments may provide low-profile (¾″ H×⅝″ W), dimmable high-performance, LED articulated accent lighting and may employ Class I or Class II low voltage (12V) transformers. Illustrative embodiments may further comprise a series of low-voltage LED capsules directly attached to a flexible wire harness. Such embodiments can conform to a radius as small as six-inches, allowing attachment to inside and outside curves in a multitude of interior and exterior applications, and in one embodiment, employing lighting-class LEDs, of, for example, 40 to 80 milliamps with 3 LEDs per board 115 . Runs of 30 feet, and optionally 60 feet, are available according to various embodiments. In one embodiment, the length “L” of the lens 51 , may be 3.0 inches, but of course may vary in other embodiments.
[0032] Those skilled in the art will appreciate that various adaptations and modifications of the just described illustrative embodiments can be configured without departing from the scope and spirit of the invention. Therefore, it is to be understood that, within the scope of the appended claims, the invention may be practiced other than as specifically described herein.
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A plurality of adjacent capsules, each comprising a base component, a body component carrying an LED circuit board, and a lens component, wherein the body and the base snap together and the lens snap-fits to the body. Such capsules are attached to a flexible electrical power cable by electrical connector components internal to the body and which conduct power from the power cable through the body to the LED circuit board.
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The invention is directed to an apparatus for treating a textile material which apparatus includes a container in which the material to be treated is guided over a plurality of rollers and is exposed to the influence of a liquor, at least one applicator being arranged in the container adjacent to the web of the material and having an admission for the liquor to be applied onto the material, means for supplying thermal energy for the formation of an aerosol of the liquor and having a discharge means for the high-pressure application of the aerosol onto the textile material conducted past the applicator, and a steamer for steam treatment of the textile material charged with the liquor. The invention is also directed to a method for the treatment, particularly bleaching, washing, dyeing, boiling, desizing, mercerizing, etc., of a textile material wherein the material is treated with a chemical liquor in the apparatus.
In known apparatus for bleaching, washing, dyeing, boiling, desizing, mercerizing, etc., a textile material, this textile material is conducted through baths formed in the container wherein the textile material is saturated with the liquor. In order to enable an adequate reaction time of the liquor, a plurality of upper and lower rollers over which the textile material is conducted before it departs the container are arranged following the baths as seen in through put direction.
A shorter dwell time of the textile material in the container derives when, as is the case in the apparatus of the species (European patent No. 545,681) the textile material is charged with an aerosol of the liquor and is then subjected to a steam treatment of a known type that allows the applied liquor to act on the textile material. The treatment agent referred to as "liquor" (usually, aqueous solutions or dispersions of suitable chemicals) is thereby applied to the textile material to be treated as an aerosol under high pressure, whereby the formation of the aerosol that is applied onto the textile material under high (vapor) pressure is effected by the application of thermal energy.
In the apparatus of the species, the steamer is integrated in the container that accepts the applicators, whereby the volume of the container is necessarily relatively large. Since the boiling point of, for example, a hydrogen peroxide solution lies above the boiling point of pure water and heated cover plates or the like that are hotter than 100° C. lead to an evaporation of the water, and thus, to a concentrating of, for example, the peroxide in the container, there is an explosion risk in the known apparatus because the peroxide tends to spontaneously decompose above a defined limit concentration and limit temperature. This can particularly occur given the presence of metal ions acting as catalysts that are situated in the material web. Oxygen, water and heat arise in the decomposition of the hydrogen peroxide. The heat leads to the evaporation of the water. The increase in volume due to the decomposition thereby amounts to up to 4,000 times the original volume. The explosion risk is thus considerable.
SUMMARY OF THE INVENTION
The object of the invention is to create an apparatus of the species wherein such an explosion [or:deflagration] risk is not present.
In accord with the invention, this object is achieved with respect to the apparatus by the features of a sluice or lock wherein the steamer is arranged spatially separated from the application container that accepts the applicator or applicators; and in that the application container that accepts the applicator or applicators is provided with a means for steam rinsing. Particularly preferred embodiments of the apparatus of the invention are the subject matter of dependent apparatus claims. With respect to the method, the object underlying the invention is achieved by the features of applying the liquid, which may be either a single chemical or different chemicals, from either a single or both sides at either a single or multiple location, onto the material with a subsequent dwell in the steamer for reaction purposes ensues, whereby identical chemicals are preferably provided for opposite sides of the textile material. Particularly preferred embodiments of the method of the invention are that the steaming is followed by at least one further single-sided or both-sided chemical application, whereby the textile material is directly supplied to following handling processes following the last chemical application, preferably after only a short dwell time in the steamer and that the dwell times in the steamer between the individual chemical applications are variable.
The invention is based on the perception that one can successfully oppose the explosion risk present in the apparatus of the species due to concentrating of, for example, peroxides in that the container in which the applicators are arranged is spatially separated from the actual steamer, so that the volume of the space that accepts the applicators can be relatively small. In accord with the invention, further, the container accepting the applicators is always steam-rinsed, so that the chemicals, particularly the peroxide, that have/has not proceeded onto the weave and threatens to concentrate are/is constantly eliminated. An explosion is thus reliably prevented.
When the apparatus for supplying thermal energy that, first, effects the formation of the aerosol and, second, manages the adequate application pressure is fashioned for the introduction of water or, respectively, steam residing under excess pressure, as can be provided in the invention, then the high thermal energy of the water residing under excess pressure or, respectively, of the super-pressurized steam effects an evaporation of the liquor upon formation of an aerosol. When the applicator is formed by at least two unary nozzles directed onto the same point, as can likewise be inventively provided, the supply of thermal energy to the liquor (and, thus, the activation) occurs immediately on the textile material. Given such a fashioning, the liquor is applied onto the material through the one nozzle and the steam is applied onto the material through the other nozzle, whereby the thermal and the kinetic energy of the steam effect a penetration of the liquor into the material and the activation thereof.
A uniform charging of the textile material with the aerosol of the liquor can be particularly achieved when, as inventively proposed, a plurality of applicators arranged side-by-side essentially transversely relative to the conveying direction of the material are provided, whereby the aerosol jets emerging from the nozzles overlap on the material to be treated. When the individual applicators are provided with controllable valves, as can be likewise provided in the invention, then a controlled charging of the textile material to be treated can be achieved dependent on the position and width thereof. An adaptation to the respective objective can be achieved in that the distance between the applicator or, respectively, the applicators and the web of the material is adjustable.
The applicator or applicators is/are preferably arranged and directed such that the material is charged with the liquor when lying against one of the rollers. This roller can thereby be a sieve drum i.e., a roller whose circumference is formed by a sieve. This allows one to anticipate a better penetration of the liquor and/or of the steam into the material since the water can emerge from the material in the direction toward the sieve drum. This drum can also be fashioned heatable, this contributing to a further activation of the liquor applied onto the material.
Various references (German patent No. 47 553, German patent No. 885 534 EP No. 0 139 617 A2) in fact already disclose various types of applicators, even for wet-treatment of textile material; the separation of the steamer from a constantly steam-rinsed application container that is critical to the invention, however, is not addressed therein. These publications likewise contain no teaching of an especially preferred embodiment of the invention wherein an activation of the aerosol or, respectively, of the liquor is initially achieved on the textile web on the basis of polynary nozzles with external mixing or by employing two unary nozzles directed onto one point of the textile material.
A particular embodiment of the invention is concerned with the problem that the chemical liquor sprayed from the nozzle onto the material does not proceed entirely onto the textile material; on the contrary, a part remains in the free vapor space as chemical fog. Even when the applicators, as inventively provided, precede the steamer in a separate application container, whereby a constant steam rinsing of the application container ensues, the chemical fog can nonetheless stick to the walls and to the cover of the application container. After combining to form larger drops, these can drop down onto the material and cause spots there that can be seen on the finished goods. Insofar as they are lead in the steam space, the pipelines for the chemical liquor leading to the applicators--even given encapsulation in a housing--are colder than the surrounding steam atmosphere and lead to the formation of condensate, wherefrom drip spots can likewise result on the goods. Painting inside surfaces of the application container is not a feasible way of eliminating this problem because of the above-discussed risk of explosions in the application container.
In the described application method wherein the mixture of aqueous chemical liquor and steam is applied onto the moving material web with nozzles in the application container in a steam atmosphere at about 100° C. and about 1 bar pressure, whereby the application is undertaken at the discharge of a guide roller and preferably over the entire width of the material with nozzles arranged next to one another, namely preferably with similar geometry for both sides of the textile material in order to achieve an evensided effect of the process, the invention therefore preferably provides that the sluice situated between the application container and the steamer be fashioned in the form of a spill shaft closed from the surrounding atmosphere through which the material and the steam flowing over into the application container from the steamer under slight excess pressure are guided in co-current or counter-current flow.
This not only has the advantage that the excess steam of the steamer is not lost but is also co-employed for rinsing the application container; rather, it is also guaranteed that the textile material permanently dwells at 100° C. in steam atmosphere, i.e., also upon transfer from the application container into the steamer, and does not come into contact with colder air, even for a brief time, wherefrom a cooling of the material and a deterioration of the achieved treatment effect could result.
The formation of droplets is already considerably reduced by the above-described measure. A further improvement can be achieved in that the chemical droplets are removed from the mixture of air-steam, chemical droplets extracted at the output of the application container before the mixture is supplied to the ambient atmosphere. This ensues partially on the basis of the centrifugal force in radial ventilators employed as extraction fans. In addition, a commercially available demister can follow. This thereby involves a weave of stainless steel or plastic wire through which the mixture flows, preferably vertically. Whereas the gaseous constituents can freely move in the gaps of the weave, the droplets collect on the wires as a consequence of the forces of gravity, combined to form larger droplets, ultimately drip vertically down and are eliminated. The eliminated liquor is preferably recirculated.
For overcoming the "dripping problem", i.e., for farther-reaching avoidance of the dripping of liquor from the walls of the application container or--even if encapsulated--liquor conduits, the invention further teaches that all walls except the bottom walls in the application container be fashioned vertically or inclined at at least 30° relative to the horizontal through a maximum of 90° relative to the horizonal. What is thereby achieved is that attaching droplets that combine to form larger drops do not drip down but run along the inside wall of the application container and thus can be eliminated in a way that is not harmful for the material. A covering, for example a sheet metal ply, above the nozzles of the applicators prevents the liquor that runs down from proceeding into the nozzle jet and leading to disturbances there. The nozzles themselves only have their nozzle end situated in the steam space, whereas the rest such as nozzle body and connecting conduits are situated in the airspace at ambient temperature. Apart from the nozzle jet orifice, the nozzle is sealed from the steam space of the application container. The advantage of this design is comprised in the free accessibility of all conduits, screwed connections, valves, etc., without dismantling. Maintenance and repair are considerably simplified. A suitable shaping of the application container also makes it possible to attach the nozzle cross pieces in chamber-like indented portions of the application container wall such that the nozzle end is situated at an optimum distance from the textile material, whereby inside walls of the application container that adjoin the nozzle end and proceed at a slant simultaneously guarantee an elimination of condensing chemical liquor without the risk of dripping onto the textile material, as already set forth. It should be emphasized that a dripping of condensed fog onto the material or onto the rollers via which the textile material guided and which could transfer drops onto the material is completely prevented in an especially advantageous way when the liquor conduits lie outside of the interior of the application container, i.e. the nozzles of the applicators have their nozzle ends sealed from the interior of the application container, and, further, when no material web proceeds under the liquor conduits, (or the encapsulation thereof).
In a preferred embodiment of the invention, the entire nozzle cross piece is replaceable as an integrated structural unit. The fastening and sealing ensue via rapid-action closures so that a nozzle cross piece can be replaced with only a short production outrage in case of a malfunction at the nozzles. From matching to specific, liquor-conditioned application conditions, for example given changing viscosity of the chemical liquor employed, the nozzles can also be replaced by replacing the nozzle crosspiece with one having a different jet characteristic. Different distances between the nozzle end and the textile web can also be achieved with the replacement of the nozzle crosspiece.
Moreover, it can also be provided in the invention that the steamer is followed by a further application container, whereby the textile material is initially returned from this further application container into the steamer and, in any case, is only conducted to different treatment steps or, respectively, to the ambient atmosphere proceeding from the steamer. A meaningful arrangement and design of the application containers thereby makes it possible, for example, to treat only one side of the textile material with a specific chemical liquor before entry of the textile material into the steamer, to subsequently steam it, to then treat the opposite side--but potentially the same side as well--with a further, different chemical liquor following the steaming process, to subsequently carry out another steaming and, finally, to discharge the textile material into the atmosphere. Deriving therefrom are broad possibilities of variation in applications wherein different acting of different liquors on the two, opposite sides of the textile material or, on the other hand, a chronologically offset application of different chemical liquors separated by a steaming process or, potentially, the repeated treatment with a single chemical liquor are desirable for achieving specific effects. This embodiment of the invention is considered an especially important feature. Various variations in the arrangement of steamer and preceding or, respectively, following application container are possible within the idea of the invention. For example, one application container comprising two (or a multiple of two) nozzle crossbeams lying opposite one another can be provided with following steamer. In addition thereto, for example, a further application housing comprising nozzle crossbeam of the type and arrangement set forth above can follow the steamer. In both instances, it is also possible to provide only a single nozzle crossbeam for every application container instead of an application container comprising a plurality of crossbeams whereby, however, at least one application container must be present per side of the material web; in this case, too, multiples of two application containers (or, respectively, nozzle crosspieces) can be provided for each side of the material web, i.e., at each side of the steamer.
On the basis of different combinations of application containers, potentially having different structures, as well as steamer or steamers, the following methods, for example, can be implemented in the invention: single or multiple, two-sided chemical application of the same or different chemicals (whereby the same chemicals are provided or, respectively, can be provided for the sides of the textile material lying opposite one another), with following dwell for reaction (steaming); in addition to the afore-mentioned procedure, following the steaming, likewise a chemical application of the described type and direct supply of the textile material to following processes with only a short dwell time following the last chemical application; further, a procedure as recited above but with arbitrary combination of a plurality of chemical applications (with identical or different chemicals, whereby, however, the two sides of the textile material are respectively charged with the same chemical) and arbitrary dwell times between the various chemical applications (i.e., steaming times).
Further features and advantages of the invention derive from the claims and from the following description wherein exemplary embodiments are set forth in detail with reference to the schematic drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross sectional view of a first exemplary embodiment of an applicator of an apparatus of the invention taken in a plane extending perpendicular to the plane of the textile material to be treated;
FIG. 2 is a cross sectional view similar to FIG. 1 of a second exemplary embodiment of an applicator of the invention;
FIG. 3 is a schematic cross sectional view of an application container in a further exemplary embodiment of the invention, comprising applicators and a means for steam rinsing, said view being in a plane extending perpendicular to the plane of the textile material to be treated;
FIG. 4 is a cross sectional view of a further exemplary embodiment of the invention in an illustration corresponding to FIG. 3;
FIG. 5 is a cross sectional view of a further, modified exemplary embodiment of an apparatus of the invention in an illustration corresponding to that in FIGS. 3 and 4;
FIG. 6 is a cross sectional view of a further modified exemplary embodiment of an apparatus of the invention in an illustration corresponding to that in FIGS. 3-5;
FIG. 7 is a diagrammatic view taken on line VII--VII of FIG. 3;
FIG. 8 is a cross sectional view of an embodiment of a roller of the invention; and
FIG. 9 is a cross sectional view of a modification of the embodiment of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the exemplary embodiment shown in FIG. 1, the applicator comprises a first pipe 2 that is directed onto the textile material 16 and comprises a second pipe 4 whose front end discharges in the discharge region of the first pipe 2. Super-pressurized steam emerges from the first pipe 2; liquor that is not preheated or is only slightly preheated is applied through the pipe 4. A mixture of the steam emerging from the pipe 2 and of the liquor emerging from the pipe 4 is thus formed so that an aerosol is formed. This aerosol impacts the material 16 with high pressure and penetrates thereinto.
The fact that the liquor is not heated until immediately before impact on the textile material effects that the chemical reactions will occur only in the material itself. Here, however, the chemical conversion, for example that of the peroxide utilized in bleaching, occurs suddenly because of the high temperature of the steam.
In the exemplary embodiment shown in FIG. 2, the applicator--referenced 10 herein--is cylindrically fashioned; a first pipe 26 is terminated with a disc at both sides upon formation of a chamber 24. The one disc thereby forms the admission or inlet 12 and the other disc forms the discharge 14. The liquor is introduced into the chamber 24 through the admission 12. The first pipe 26 is embraced by a helical heating element 20; the heating element 20 is in turn accepted by a further pipe 22 that is screwed into a mount 28.
The liquor injected into the chamber 24 through the admission 12 is suddenly evaporated therein and emerges from the discharge 14 under high pressure while charging the material 16.
Instead of the heating element 20, an applicator 10a (FIG. 9) has a first pipe 26a with an arrangement for burning alcohol which includes a jet 200 for spraying alcohol into the chamber 24 and an ignitor 201. Thus, liquor injected into the chamber 24 will be evaporated by the heat created by the arrangement for burning alcohol.
Differing from the first exemplary embodiment, the aerosol in the second exemplary embodiment is thus formed in a closed chamber and this aerosol is then applied onto the material web 16.
FIG. 3 schematically shows an exemplary embodiment of the application container 40 that accepts the applicators. The material web to be treated is introduced into the container 40 via a first roller 46. After passing deflection rollers 48, 50, the material web is supplied via an upper deflection roller 52. Applicators 10 fashioned in accord with the invention are arranged at both sides of this upper deflection roller 52, the material web being charged with the liquor particularly, thus, a solution containing peroxide, through these applicators 10. The material web is then conducted by further rollers 54, 56 around a lower deflection roller 58 in whose region the material web is again charged with the liquor via further applicators 10. After guidance over rollers 60, 62, the material web is then conducted out of the container 40 through a sluice 64 and is supplied to a traditional steamer for further treatment.
As illustrated in FIG. 7, the applicators 10 are arranged side-by-side in two facing rows 100 and 101 that extend parallel to the roller 58 and transverse to the conveying direction of the web. The jets emerging from the applicators 10 will overlap on the web or goods being treated. The applicators 10 of the row 100 are offset half the distance between two applicators relative to the applicators of row 101. Each applicator 10 has a separate controllable valve 103. Each row 100 and 101 can be moved in the direction of arrow 105 to change the spacing between the web and the applicators. Each applicator can be rotated in the direction of arrow 106 (FIG. 7) or arrow 107 (FIG. 2) to change the angle of attack.
As illustrated in FIG. 7, the roller 58 is a sieve roller with openings 110. However, the roller 58 could also be constructed as a heatable roller 158 (FIG. 8) which has a heating element 159.
For permanent rinsing of the interior of the container 40, this is fashioned with a plurality of steam entry pipes 66 that are preferably arranged above the applicators 10. A blower 68 is arranged in the lower region of the container 40, this blower in turn eliminating the steam introduced into the container 40 via the steam entry pipes 66 therefrom. Overall, of course, care is thereby exercised that the steam rinsing event in fact occurs under constant supply of steam into the container while preventing a "blow-back" of container atmosphere into the steam entry pipes.
It can thereby be seen in the apparatus of the invention that the application container 40 in which the liquor containing the peroxide or, respectively, a similar substance is applied onto the material web via the applicators 10 is separated from the actual steamer. What this spacial separation achieves is that the volume of the space that accepts the applicators can be relatively small. During operation, the container 40 accepting the applicators 10 is therefore constantly steam-rinsed, so that the peroxide that does not proceed onto the weave and which threatens to concentrate is constantly eliminated. An explosion is thus reliably prevented.
The liquor that has not been used on the textile material and that is eliminated from the container 40 in the steam rinsing is preferably recirculated, whereby these chemicals are not only prevented from proceeding into the atmosphere in an environmentally safe fashion but the economic feasibility can also be considerably increased.
In the exemplary embodiment shown in FIG. 4, the textile material 16 becomes the content of the application container 40 obliquely from the lower right as seen in the drawing, as in the exemplary embodiment of FIG. 3, is conducted obliquely toward the upper right through the application container 40 that it then departs in the direction of the arrow 70 to the steamer (not shown in FIG. 4). All inside walls of the application container 40 are either vertical or, on the other hand, are arranged at an angle of at least 30° relative to the horizontal, so that attaching droplets that unite to form larger drops cannot drip down but run along the wall and can thus be eliminated in a way that is non-injurious for the textile material 16. The nozzles or, respectively, applicators 10 are arranged in a nozzle crosspiece 72 that, as an integrated structural unit, is inserted into a corresponding opening in the wall of the application container 40, being inserted replaceably therein with rapid-action closures 74, 76. Only a nozzle end 78 from which a nozzle jet emerges is thereby situated in the interior of the application container 40, whereas the remaining component parts such as conduits, screwed connections, valves, etc., are freely accessible from the outside, i.e., proceeding from the ambient atmosphere, in the way to be seen from the drawing. The nozzle jet emerging from the nozzle end 78 is stopped down such by covering 79--fashioned, for example, as a sheet metal ply--that chemical liquor can in fact proceed essentially only onto the textile material 16 and can satisfy its intended purpose there.
Windows 80 with lamps 82 in order to be able to illuminate the nozzle jets are attached at the bearing sides of the rollers 56, 58, 62, i.e., in the corresponding end walls of the application container 40, parallel to the plane of the drawing of FIG. 4. Slanting viewing windows 84 are present over the entire width of the apparatus above the nozzle crosspiece 72. Together with the illumination, thus, a continuous optical monitoring of the nozzle jets is possible during operation. Of course, it would also be possible to undertake an automatic monitoring, for example, with appropriate sensors and control devices, instead of a purely optical monitoring by an operator.
As may be seen in FIG. 4, a partition plate 86 is provided opposite the nozzle crosspiece 72, this partition plate 86 preventing droplets that rebound off the roller 58 from proceeding directly onto the textile material 16. The nozzle jet, moreover, emerges such from the nozzle end 78--the nozzles are rotatably attached around their center fastening point, as a result whereof an improved flexibility in view of the adjustment for various articles of material derives--that the nozzle jet impacts approximately in the seating or, respectively, contact region of the textile material 16 with the roller 58. As a result of this type of impact, preferably immediately behind the corresponding contact line in conveying direction of the textile material 16, a "suction effect" is exploited that is based on a slight expansion of the textile material 16 after it passes the roller 58, as a result whereof an especially intense penetration of the material with the chemical liquor is guaranteed.
As illustrated, a drain 170 is connected by a pipe 171 to means 172 for recirculating the liquor constituents. From the means 172 for recirculating, the liquor is taken by a line 175 back to the supply for the applicator 10.
It may be seen in the exemplary embodiment shown in FIG. 5 that the application container 40 is followed by a steamer 90 whose atmosphere is in communication with the application container 40 via a spill shaft 92 that is closed off from the ambient atmosphere. Steam from the steamer 90 that resides under slight over-pressure in comparison to the application container 40 constantly flows into the application container 40 through the spill shaft 92 that the material traverses from left to right in FIG. 5 and is employed for steam rinsing in said application container 40 in the way already set forth in conjunction with FIG. 3. The steam flows through the spill shaft in counter-current flow to the textile material 16 in this exemplary embodiment. The application container comprises a total of four nozzle crosspieces 72 of the type already described, whereby the extraction of the mixture of vapor, chemicals and air from the interior of the application container 40 ensues with the blower 68. The nozzle crosspieces 72 are, so to speak, allocated to the application container 40 in the form of individual chambers, whereby it is guaranteed that the two sides of the textile material 16 lying opposite one another are uniformly charged and no drops from the walls or pipelines of the application container 40 proceed onto the weave of the textile material 16. As may be seen from the drawing, respectively two crosspiece housings of the nozzle crosspieces 72 lying opposite one another belong together, i.e., the seen chemical liquor is applied onto the textile material 16 in them. An application container of the type shown in FIG. 5 and described above can be expanded in stages, i.e., both two as well as four, six and more nozzle crosspieces 72 in a single application container 40 are conceivable when the successive application of different chemicals is necessary for the process.
Such an application container comprising two of a plurality of nozzle crosspieces 72 can be attached both at the input of the steamer 90 as well as at its output when it is advantageous for the process. In the exemplary embodiment of FIG. 6, what is involved is an embodiment of the apparatus of the invention wherein the steamer 90 has a first application container 40 and a further application container 94 allocated to it, each of these comprising a single nozzle crosspiece 72. Every application container has an extraction fan 68 of the type already set forth allocated to it. With the apparatus shown in FIG. 6, the textile material 16 can dwell in the steamer 90 for reaction both before as well as after a specific chemical application. Here, too, a serial joining of 2, 4, 6 or a multiple of crosspieces 72 or, respectively, "application chambers" is possible in the respective application container 40 or, respectively, 94.
A continuous steam flow from the steamer 90 to the application container 40 or, respectively, to the further application containers 94 can be assured in that the steamer 90 is supplied with steam with a constantly controlled inflow. Since the textile material 16 and the liquor are already heated, only the losses over the surface that are independent of the textile material occur in the steamer 90 apart from the flow-off of steam through the spill shaft 92 as steam consumption. A supervision to see whether a droplet fog penetrates from the application container 40 or, respectively, 94 into the steamer 90 can ensue optically by the operator when the system is started up. Of course, a sensor-controlled control is also possible. The extraction with the extractor fan 68 ensues with a constant volume stream. The steam offering to the extractor that differs dependent on the articles of material is compensated by a more or less pronounced intake of ambient air.
The features of the invention disclosed in the above specification, in the drawing as well as in the claims can be critical for realization of the various embodiments of the invention both individually as well as inarbitrary combinations.
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Apparatus for the treatment, particularly bleaching, washing, dyeing, boiling, desizing, mercerizing, etc., of a textile material, comprising a container in which the material to be treated is guided over a plurality of rollers and is exposed to the action of a liquor, comprising at least one applicator arranged in the container neighboring the web of the material, said applicator having an admission for the liquor to be applied onto the material, having a means for supplying thermal energy for the formation of an aerosol of the liquor and having a discharge means for high-pressure application of the aerosol onto the textile material conducted past the applicator, and comprising a steamer for steam treatment of the textile material charged with the liquor, characterized in that, following a sluice (64), the steamer (90) is arranged spatially separated from the container (40) that accepts the applicator or applicators (10); and in that the container (40) that accepts the applicator or applicators (10) is provided with a means for steam rinsing; further, a method implementable with this apparatus (FIG. 5).
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FIELD OF THE INVENTION
The present invention relates to apparatus for and a method of degassing molten metal, in particular molten steel.
BACKGROUND OF THE INVENTION
Purification of molten metal, especially molten steel, by subjecting the molten metal to a vacuum has been known for some time. In such a process, the molten metal is poured into an open receptacle, or “ladle”, and covered with a layer of fused (liquid) mineral slag, which both insulates and isolates the molten metal, and is chemically formulated to aid the purification process. The ladle is positioned within a degassing chamber connected to a vacuum pumping arrangement for evacuating the chamber. The pumping arrangement typically comprises one or more primary pumps for exhausting gas drawn from the chamber to atmosphere, and one or more secondary mechanical vacuum booster pumps connected between the primary vacuum pumps and the degassing chamber. The pumping arrangement is operated to subject the chamber to a steadily decreasing pressure (increasing vacuum), which causes gaseous and metallic impurities to leave the liquid phase and be evacuated from the atmosphere above the melt.
However, as the pressure reduces a point may be reached at which vigorous chemical reactions occur at the interface between the molten metal and the molten slag, causing a rapid generation of gas that quickly inflates the slag layer by foaming. If uncontrolled, the foaming slag can rise up and overflow from the lip of the ladle, resulting in major loss of slag and potential disruption to the purification process.
SUMMARY OF THE INVENTION
In a first aspect, the present invention provides apparatus for degassing a molten metal, the apparatus comprising a chamber for receiving a receptacle containing molten metal and a layer of slag over the molten metal, a vacuum pumping arrangement for evacuating the chamber, a gauge for outputting a signal indicative of the level of a surface of the slag, and control means for using the signal to control the rate of evacuation of the chamber to inhibit overflowing of slag from the receptacle.
The apparatus can thus enable any sudden increase in the level of the slag surface to be detected and combated by a corresponding automatic prompt reduction in the rate of evacuation of the chamber, reducing the rate at which gas is generated at the interface between the molten metal and the slag and hence the degree of foaming. Once the level of the slag surface has receded, the evacuation rate of the chamber can be increased again. Therefore, in a second aspect the present invention provides apparatus for degassing a molten metal, the apparatus comprising a chamber for receiving a receptacle containing molten metal and a layer of slag over the molten metal, a vacuum pumping arrangement for evacuating the chamber, a gauge for outputting a signal indicative of the level of a surface of the slag, and control means for switching off at least one pump of the vacuum pumping arrangement in dependence on the signal to inhibit overflowing of slag from the receptacle.
In a third aspect, the present invention provides a method of degassing a molten metal, the method comprising the steps of positioning a receptacle containing the molten metal and a layer of slag over the molten metal within a chamber, evacuating the chamber, receiving from a gauge a signal indicative of the level of a surface of the slag, and using the signal to control the rate of evacuation of the chamber to inhibit overflowing of slag from the receptacle.
In a fourth aspect, the present invention provides a method of degassing a molten metal, the method comprising the steps of positioning a receptacle containing the molten metal and a layer of slag over the molten metal within a chamber, evacuating the chamber, receiving from a gauge a signal indicative of the level of a surface of the slag, and switching off at least one pump used to evacuate the chamber in dependence on the signal to inhibit overflowing of slag from the receptacle.
Features described above in relation to first aspect of the invention are equally applicable to the second to fourth aspects, and vice versa.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred features of the present invention will now be described with reference to the accompanying drawing, in which
FIG. 1 illustrates a first embodiment of a steel degassing apparatus;
FIG. 2 illustrates an example of a vacuum pumping arrangement for evacuating the degassing chamber of the degassing apparatus of FIG. 1 ;
FIG. 3 illustrates a pump controller for driving a motor of a booster pump of the pumping arrangement of FIG. 2 ;
FIG. 4 illustrates the connection of the pump controllers of the booster pumps of FIG. 2 to the system controller; and
FIG. 5 illustrates a second embodiment of a steel degassing apparatus.
DETAILED DESCRIPTION OF THE INVENTION
With reference to FIG. 1 , an apparatus for degassing a molten metal, for example, molten steel, comprises a degassing chamber 10 for receiving a receptacle, or “ladle” 12 , containing molten metal 14 and a layer of slag 16 overlying the molten metal 14 . The chamber 10 is closed by a lid 18 , on which is mounted a gauge 20 for monitoring the level of the upper surface 22 of the slag 16 within the ladle 12 . In the illustrated example, the gauge 20 is in the form of a radar transceiver. The gauge 20 is connected to a controller 24 for controlling a vacuum pumping arrangement 26 connected to an outlet 28 of the chamber 10 .
With reference now to FIG. 2 , an example of the vacuum pumping arrangement 26 comprises a plurality of similar booster pumps 30 connected in parallel, and a backing pump 32 . Each booster pump 30 has an inlet connected to a respective outlet 34 from an inlet manifold 36 , and an outlet connected to a respective inlet 38 of an exhaust manifold 40 . The inlet 42 of the inlet manifold 36 is connected to the outlet 28 from the chamber 10 , and the outlet 44 of the exhaust manifold 40 is connected to an inlet of the backing pump 32 . Whilst in the illustrated pumping system there are three booster pumps connected in parallel, any number of booster pumps may be provided depending on the pumping requirements of the enclosure. Similarly, where a relatively high number of booster pumps are provided, two or more backing pumps may be provided in parallel. An additional row or rows of booster pumps similarly connected in parallel may be provided as required between the first row of booster pumps and the backing pumps.
With reference to FIG. 3 , each booster pump 30 comprises a pumping mechanism 46 driven by a variable speed motor 48 . Booster pumps typically include an essentially dry (or oil free) pumping mechanism 46 , but generally also include some components, such as bearings and transmission gears, for driving the pumping mechanism 46 that require lubrication in order to be effective. Examples of dry pumps include Roots, Northey (or “claw”) and screw pumps. Dry pumps incorporating Roots and/or Northey mechanisms are commonly multi-stage positive displacement pumps employing intermeshing rotors in each pumping chamber. The rotors are located on contra-rotating shafts, and may have the same type of profile in each chamber or the profile may change from chamber to chamber. The backing pump 32 may have either a similar pumping mechanism to the booster pumps 30 , or a different pumping mechanism. For example, the backing pump 32 may be a rotary vane pump, a rotary piston pump, a Northey, or “claw”, pump, or a screw pump.
The motor 48 of the booster pump 30 may be any suitable motor for driving the pumping mechanism 46 . In the preferred embodiment, the motor 48 comprises a three phase AC motor, although another technology could be used (for example, a single phase AC motor, a DC motor, permanent magnet brushless motor, or a switched reluctance motor).
A pump controller 50 drives the motor 48 . In this embodiment, the pump controller 50 comprises an inverter 52 for varying the frequency of the power supplied to the AC motor 48 . The frequency is varied by the inverter 52 in response to commands received from an inverter controller 54 . By varying the frequency of the power supplied to the motor, the rotational speed of the pumping mechanism 46 , hereafter referred to as the speed of the pump, or pump speed, can be varied. A power supply unit 56 supplies power to the inverter 52 and inverter controller 54 . An interface 58 is also provided to enable the pump controller 50 to receive signals from an external source for use in controlling the pump 30 , and to output signals relating to the current state of the pump 30 , for example, the current pump speed, the power consumption of the pump, and the temperature of the pump.
In the embodiment shown in FIG. 4 , the pump controllers 50 of each of the booster pumps 30 are connected to the controller 24 . As illustrated, cables 60 may be provided for connecting the interfaces 58 of the pump controllers 50 to an interface of the controller 24 . Alternatively, the pump controllers 50 may be connected to the controller 24 over a local area network.
In use, the vacuum pumping arrangement 26 is operated to evacuate the degassing chamber 10 to degas the molten metal 14 contained within the ladle 12 . Gas is drawn from the chamber 10 into the inlet manifold 36 , from which the gas passes through the booster pumps 30 into the exhaust conduit 40 . The gas is drawn from the exhaust conduit 40 by the backing pump 32 , which exhausts the gas drawn from the chamber 10 at or around atmospheric pressure. During evacuation of the chamber 10 , the level of the surface 22 of the slag 16 is monitored using the gauge 20 . The gauge outputs a radar beam towards the slag 16 . The beam is first reflected from the surface 22 of the slag 16 , and then from the interface 62 between the molten metal 14 and the slag 16 . As a result, the gauge 20 receives a first, relatively weak echo of the radar signal after a first time period, due to the reflection of the radar beam by the surface 22 of the slag 16 , and a second, relatively strong echo after a second time period, due to the reflection of the radar beam from the interface 62 between the molten metal 14 and the slag 16 . The distance d 1 between the gauge 20 and the surface 22 of the slag 16 is proportional to the duration of the first time period. As the distance d 2 between the gauge 20 and the top of the ladle 12 is a constant, the distance d 3 between the top of the ladle 12 and the surface 22 of the slag 16 is thus also proportional to the duration of the first time period.
The gauge 20 outputs to the controller 24 a signal including, inter alia, the length, or an indication of the length, of the first time period. The controller 24 uses the data contained within the signals to monitor both the current level of the surface 22 of the slag 16 and the rate of change of the level of the surface 22 , for example, due to foaming of the slag 16 during degassing. These parameters are used by the controller 24 to control the rate of evacuation of the chamber 10 , which in turn controls the rate of degassing of the molten metal 14 , and thus the degree of foaming of the slag 16 . In this embodiment, the controller 24 varies the speeds of the booster pumps 30 to control the evacuation rate of the chamber 10 by issuing a command to the pump controllers 50 to vary the speeds of the booster pumps 30 . For example, a target speed for the booster pumps 30 can be provided to the pump controllers 50 in the form of a target frequency for the inverters 52 . In response to the command received from the controller 24 , each pump controller 50 controls the frequency of the power supplied to its motor 32 according to the target frequency provided by the controller 24 . This target frequency may be zero, so that the booster pumps 30 are effectively switched off. Alternatively, the target frequency may be progressively decreased towards zero depending on the data contained within the signals received from the gauge 20 .
As a result, a rapid increase in the level of the surface 22 of the slag 16 due to foaming can be rapidly detected and combated by a corresponding automatic prompt reduction in the rate of evacuation of the chamber 10 , thereby reducing the rate at which gas is generated at the interface 62 between the molten metal 14 and the slag 16 and hence preventing the slag 16 from overflowing from the ladle 12 . Once the level of the slag surface 22 has receded, the evacuation rate of the chamber 10 can be increased again by issuing an appropriate command to the pump controllers 50 to increase the speeds of the booster pumps 30 .
In the embodiment shown in FIGS. 1 to 4 , a system controller 24 determines a target speed for the booster pumps 30 , and advises the booster pumps 30 of the target speed. In the embodiment shown in FIG. 5 , the gauge 20 is connected directly to the pumping arrangement 26 . In this embodiment, the signals output from the gauge 20 are received directly by the pump controllers 50 , each of which has stored therein the functionality of the controller 24 of the first embodiment for controlling the speed of its respective pumping mechanism.
Any one of a number of different techniques may be used to provide an indication of the level of the slag surface within the receptacle. Examples include lowering a probe into the receptacle, and using a variation in an electrical property of the probe, such as inductance or resistance, to determine the level of the slag surface. A gas sensor may be used instead of a probe. Another alternative is to use a video camera to produce an image of the inside of the receptacle, and to use variations in the image as an indication of the level of the slag surface within the receptacle. In the preferred embodiment, the gauge comprises a radar transceiver for outputting a radar beam towards the slag and receiving an echo of the radar beam from the slag surface. The gauge is preferably positioned a fixed distance above the receptacle such that the period between output of the radar beam and the reception of the echo is indicative of the distance between the gauge and the slag surface, and thus the distance of the slag surface from the top of the receptacle. The signal output from the gauge may be indicative of the length of that period, with the control means being configured to control the rate of evacuation of the chamber in response thereto.
Whilst the evacuation rate of the chamber may be controlled in response to the current level of the slag surface, both the current level of the slag surface and the current rate of change of the level of the slag surface may be used to control the evacuation rate. The control means may be configured to determine the rate of change of the level of the slag surface from data contained within a plurality of signals received from the gauge over a predetermined period of time.
The control means is preferably configured to adjust the speed of rotation of at least one pump of the vacuum pumping arrangement to control the rate of evacuation of the chamber. The control means preferably comprises a pump controller for controlling the power supplied to a variable speed motor of the pump, and thus the speed of rotation of the pump. The pump controller is preferably configured to change the frequency of the power supply to the motor to adiust pump speed, for example by transmitting an instruction to an inverter to change the frequency of the power supplied thereby to the motor. However, the controller may be configured to adjust another parameter of the power supply, such as the size (or amplitude) of the voltage or current of the power supply to the motor.
In the event that a reduction in the frequency of the power supplied to the motor, or a reduction in another parameter of the power supply, does not cause the level of the slag surface to recede, the frequency of the power supplied to the motor, or said another parameter, may be reduced to zero so that the pump is effectively switched off, thereby significantly reducing the rate of evacuation of the chamber. Therefore, the control means may be configured to turn off at least one pump of the vacuum pumping arrangement in dependence on said signal.
In one arrangement, the pump controller receives directly the signals output from the gauge, and uses the signals to control the power supplied to the motor. In another arrangement, a system controller receives the signals output from the gauge, uses the signals to determine a target speed for the pump, and advises the pump controller of the target speed, for example, by advising the pump controller of the frequency of the power to be supplied to the motor. The functionality for determining the target speed can thus be provided by software stored on a single system controller, with the pump controller being responsive to the target speed received from the system controller to set its pump's speed.
While the foregoing description and drawings represent the preferred embodiments of the present invention, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the true spirit and scope of the present invention.
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To degas a molten metal, a receptacle containing the molten metal and a layer of slag over the molten metal is positioned in a chamber, and the chamber is evacuated. As the pressure in the chamber reduces, gas is generated at the interface between the molten metal and the slag, which causes the slag to foam. To inhibit overflowing of slag from the receptacle, a gauge outputs a signal indicative of the level of the surface of the slag, and the rate of evacuation of the chamber is reduced to reduce the rate of gas generation.
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BACKGROUND OF INVENTION
[0001] The present invention relates generally to closures used on automotive vehicles and more particularly to bumpers that are used on vehicle closures such as hoods and liftgates.
[0002] While operating a vehicle, the vehicle's liftgates may tend to move in their body openings, thus potentially creating undesirable noise and possibly damage to the vehicle. For example, liftgate chucking, which is a rattle condition that occurs during vehicle operation causing hard contact between a latch and striker, may sometimes occur. This situation is typically avoided by using wedge systems with the liftgate. Liftgate wedges are devices that provide additional constraint of the liftgate to improve the stability of the liftgate within the opening. The additional constraint tends to reduce unwanted noise, squeaks and rattles. However, these wedge systems are difficult to align and typically only provide marginal control over the movement of the liftgates in their openings.
[0003] In addition, for some vehicles, the corners of the hood may have a tendency to lift at high vehicle speeds due to aerodynamic loads. This condition is sometimes addressed by employing wedges, bumpers or additional latches. However, wedges and bumpers tend to only constrain the hood in one or two directions and are difficult to adjust, where too much contact causes high closing efforts and too little contact substantially reduces their effectiveness.
SUMMARY OF INVENTION
[0004] An embodiment contemplates a method for releasably securing a closure on a vehicle to a vehicle body, the method comprising the steps of: moving the closure from an open position to a closed position against the vehicle body; actuating a latch to retain the closure against the vehicle body upon the closure reaching the closed position; inserting a bumper, which is mounted on one of the closure and the vehicle body, into a pocket of a base, which is mounted on the other of the closure and the vehicle body, as the closure approaches the closed position; detecting if the latch is actuated to retain the closure against the vehicle body; detecting if the bumper is fully inserted into the pocket; and actuating an electronic locking mechanism to secure the bumper to the base after detecting that the latch is actuated to retain the closure against the vehicle body and after detecting that the bumper is fully inserted into the pocket.
[0005] An embodiment contemplates a method for releasably securing a closure on a vehicle to a vehicle body, the method comprising the steps of: receiving a signal to open the closure when closed; controlling an electronic locking mechanism to release a bumper, which is mounted on one of the closure and the vehicle body, from a pocket of a base, which is mounted on the other of the closure and the vehicle body, wherein the bumper, when in engagement with the base, restrains movement of the closure relative to the vehicle body in three axial directions; releasing a latch, which secures the closure in a closed position, to release the closure from the vehicle body, the latch being released after the electronic locking mechanism releases the bumper; and moving the closure from the closed position to an open position.
[0006] An embodiment contemplates a closure assembly that is releasably securable to a vehicle body of a vehicle having a controller. The closure assembly comprises a latch and a lockable bumper. The latch is secured to the closure and releasably engages the vehicle body, with the latch communicating with the controller to indicate a state of the latch being latched or unlatched. The lockable bumper assembly includes a bumper mounted to one of the closure and the vehicle body and a base mounted to the other of the closure and the vehicle body. The base includes a pocket complimentary in shape to the bumper for receiving a portion of the bumper therein, a bumper closed sensor assembly that detects when the bumper is seated in the pocket and communicate this status to the controller, and at least one electronic locking mechanism including a movable retaining flange, with the actuation of the electronic locking mechanism controllable by the controller. The bumper includes a retaining surface that is engageable with the movable retaining flange to selectively secure the bumper in the pocket.
[0007] An advantage of an embodiment is that the lockable bumper assembly provides an anti-chucking device for liftgates and a device for resisting hood liftoff at high speeds, while avoiding the difficulties with the alignment of wedges and avoiding the need for additional latches. The lockable bumper assembly provides for three-way constraint, thus significantly reducing movement of the closure relative to the vehicle body while the vehicle is operating. This is accomplished without the need to increase closing efforts for the vehicle closures.
[0008] In addition, an advantage of an embodiment is that the lockable bumper assembly provides an additional theft deterrent by preventing the hood or liftgate from being opened when an electronic locking mechanism in the lockable bumper assembly is engaged.
BRIEF DESCRIPTION OF DRAWINGS
[0009] FIG. 1 is a schematic plan view of a vehicle.
[0010] FIG. 2 is a schematic section view of a lockable bumper mounted to vehicle structure in an open position according to a first embodiment.
[0011] FIG. 3 is a schematic section view similar to FIG. 2 , but showing the lockable bumper in a closed position.
[0012] FIG. 4 is a schematic section view of a lockable bumper in an open position according to a second embodiment.
[0013] FIG. 5 is a schematic section view similar to FIG. 4 , but showing the lockable bumper in a closed position.
[0014] FIG. 6 is a schematic section view of a lockable bumper in an open position according to a third embodiment.
[0015] FIG. 7 is a schematic section view similar to FIG. 6 , but showing the lockable bumper in a closed position.
[0016] FIG. 8 is a schematic section view of a lockable bumper in an open position according to a fourth embodiment.
[0017] FIG. 9 is a schematic section view similar to FIG. 8 , but showing the lockable bumper in a closed position.
[0018] FIG. 10 is a schematic section view of a lockable bumper in an open position according to a fifth embodiment.
[0019] FIG. 11 is a schematic section view similar to FIG. 10 , but showing the lockable bumper in a closed position.
[0020] FIG. 12 is a schematic section view of a lockable bumper in an open position according to a sixth embodiment.
[0021] FIG. 13 is a schematic section view similar to FIG. 12 , but showing the lockable bumper in a partially closed position.
[0022] FIG. 14 is a schematic section view similar to FIG. 12 , but showing the lockable bumper in a closed position.
DETAILED DESCRIPTION
[0023] FIG. 1 illustrates a vehicle 20 having closures, such as a hood 22 and a liftgate 24 , each interacting with a pair of lockable bumper assemblies 26 . While a hood 22 and a liftgate 24 are discussed herein, the lockable bumper assemblies 26 may be applied to other vehicle closures as well. Also, there may be only one lockable bumper assembly 26 associated with a particular closure rather than multiple ones, if so desired.
[0024] The hood 22 is secured to a front portion of the vehicle body 28 via a hood latch 30 , and the liftgate 24 is secured to rear portion of the vehicle body 28 via a liftgate latch 32 . A first pair of lockable bumper assemblies 26 mount between the body 28 and the hood 22 , while a second pair of lockable bumper assemblies 26 mount between the body 28 and the liftgate 24 . The lockable bumper assemblies 26 are not meant to take the place of the latches 30 , 32 , but are in addition to the latches 30 , 32 .
[0025] A controller 34 , which may be a body control module, is located in the vehicle 20 and is in communication with the lockable bumper assemblies 26 , the hood latch 30 and the liftgate latch 32 . The controller 34 may also be in communication with a liftgate release or liftgate open button 36 , a liftgate handle 38 , a hood release lever 40 and/or a key fob 42 having buttons relating to release or closure of the liftgate 24 or possibly the hood 22 . The controller 34 may be made up of different combinations of electronics hardware and software as is known to those skilled in the art and may be a single controller or multiple separate controllers in communication with one another.
[0026] FIGS. 2 and 3 illustrate a first embodiment of the lockable bumper assembly 26 that may be employed with the vehicle of FIG. 1 . The bumper assembly 26 includes a bumper 46 , which includes a retaining surface 48 (in this embodiment, a slot) and a mounting member 50 , such as, for example, a threaded stud. The mounting member 50 may be mounted to the closure structure 52 , which may be part of a hood, liftgate or other vehicle closure structure. The bumper 46 may be a truncated cone shape.
[0027] The bumper assembly 26 also includes a base 54 that is mounted to the vehicle body 28 . Alternatively, the base 54 may be mounted to the closure structure 52 , with the bumper 46 mounted to the vehicle body 28 . The base includes a pocket 56 that is complimentary in shape to the bumper 46 and allows the bumper 46 to be received and nest therein.
[0028] The base 54 also includes a bumper-closed sensor assembly 58 that is configured to detect when the bumper 46 is seated in the pocket 56 . This sensor assembly 58 may include a channel 60 through which a plunger 62 can telescopically slide. A plunger spring 64 may be mounted in the channel 60 and bias the plunger 62 into the pocket 56 . The plunger 62 , channel 60 and plunger spring 64 cooperate to retain the plunger 62 in the channel 60 . A bumper engagement switch 66 may be mounted in the channel 60 , opposite the pocket 56 , and positioned to be actuated when the plunger 62 is pushed into the channel 60 by the bumper 46 .
[0029] The base 54 also includes at least one electronic locking mechanism 68 that includes an electronically actuatable, moving mechanism 70 that controls the movement of a movable retaining flange 72 . The moving mechanism 70 can move the retaining flange 72 into and out of contact with the retaining surface 48 on the bumper 46 when the bumper 46 is received in the pocket 56 . The moving mechanism 70 is preferably configured so that the retaining flange 72 extends into the pocket 56 when no electric current is applied to the electronic locking mechanism 68 and is retracted from the pocket when an electric current is applied to the electronic locking mechanism 68 . The bumper engagement switch 66 and the electronic locking mechanism 68 may be in communication with the controller 34 (shown in FIG. 1 ).
[0030] The moving mechanism 70 may be made of, for example, a shape memory alloy that changes shape as heat is applied, resulting in motion, and that returns to the original shape after the heat is removed. The heat applied may be from an electric current that is activated and deactivated by the controller 34 . Alternatively, other types of electronically actuatable, moving mechanisms may be employed instead, if so desired.
[0031] The operation of the lockable bumper assembly 26 will be described with reference to FIGS. 1-3 . When the closure (such as a hood 22 or liftgate 24 ) is partially or fully open, the bumper 46 is located outside of the pocket 56 (see position in FIG. 2 ). Thus, the bumper 46 does not push down on the plunger 62 , resulting in the bumper engagement switch 66 indicating an open position. While the bumper engagement switch 66 indicates an open position, the controller 34 assures that power is provided to the electronic locking mechanisms 68 , thus keeping the movable retaining flanges 72 in retracted positions.
[0032] As the closure structure (such as a hood 22 or liftgate 24 ) is moved to the closed position, the bumper 46 moves into the pocket 56 . The movement of the closure may be manual or may be an automated closing process that is activated by the key fob 42 or a button on the vehicle 20 . The truncated conical shape of the bumper 46 allows for a small amount of misalignment of the bumper 46 relative to the pocket 56 , with the sides of the pocket 56 guiding the bumper 46 . As the closure structure reaches the fully closed position (see position in FIG. 3 ), the bumper 46 pushes the plunger 62 against the bias of the plunger spring 64 and into contact with the bumper engagement switch 66 , which signals the controller 34 that the bumper 46 is seated in the base 54 . At this point, with the closure in a fully closed position, the latch (a hood latch 30 or a liftgate latch 32 , as the case may be) will be engaged, with the controller 34 receiving a signal that the latch is engaged.
[0033] With the latch engaged, a signal is sent from the controller 34 to the electronic locking mechanism 68 , causing the power to the locking mechanism 68 to be shut off. This causes the moving mechanism 70 to push the movable retaining flanges 72 into engagement with the retaining surface 48 of the bumper 46 . The bumper 46 is now secured to the base 54 in the fore-aft, cross-vehicle and vertical directions. The bumpers 46 , then, act as anti-chucking devices and a theft deterrent.
[0034] Alternatively, when the controller 34 receives a signal that the latch is engaged, the controller may wait until the vehicle speed reaches about five kilometers per hour, for example, and then send a signal that causes the moving mechanism 70 to push the movable retaining flanges 72 into engagement with the retaining surface 48 of the bumper 46 .
[0035] For opening of a closed hood 22 or liftgate 24 , upon a vehicle operator actuating the liftgate handle 38 , using a key fob 42 to signal the vehicle 20 to open the liftgate, actuating a liftgate release button 36 or actuating a hood release lever 40 , the controller 34 will cause the electronic locking mechanisms 68 to retract the movable retaining flanges 72 . This allows the hood 22 or liftgate 24 , as the case may be, to open once the particular latch 30 or 32 has been released.
[0036] FIGS. 4 and 5 illustrate a second embodiment of the lockable bumper assembly 126 that may be employed with the vehicle of FIG. 1 . The arrangement in FIGS. 4 and 5 have many items in common with that of FIGS. 2 and 3 and to avoid unnecessary repetition of the description, the same reference numbers have been used but falling within the 100-series. The significant difference between this embodiment and the first embodiment is the way that the electronic locking mechanisms 168 engage the bumper 146 . The electronically actuatable, moving mechanisms 170 engage movable retaining flanges 172 that are wedge-shaped and engage with a retaining surface 148 on the back side of the bumper 146 .
[0037] The lockable bumper assembly 126 essentially works the same as in the first embodiment. The bumper 146 pushes the plunger 162 against the bias of the plunger spring 164 into contact with the bumper engagement switch 166 as the bumper 146 becomes fully seated in the pocket 156 of the base 154 . When appropriate, the controller causes the moving mechanism 170 of the electronic locking mechanism 168 to push the retaining flanges 172 into engagement with the retaining surface 148 , locking the bumper 146 in place.
[0038] FIGS. 6 and 7 illustrate a third embodiment of the lockable bumper assembly 226 that may be employed with the vehicle of FIG. 1 . The arrangement in FIGS. 6 and 7 have many items in common with that of FIGS. 2 and 3 and to avoid unnecessary repetition of the description, the same reference numbers have been used but falling within the 200-series. The significant difference between this embodiment and the first embodiment is the way that the electronic locking mechanisms 268 engage the bumper 246 , and the shape of the bumper 246 . The electronically actuatable, moving mechanisms 270 engage pivotable retaining flanges 272 via small plungers 282 . The retaining flanges 272 are wedge-shaped at one end and engage with a retaining surface 248 on a cross member 280 of an I-shaped bumper 246 when pivoted into the pocket 256 . The I-shaped bumper 246 is shaped to slide into the pocket 256 of the base 254 without contacting the retaining flanges 272 while they are recessed into cavities 281 in the base 254 .
[0039] The lockable bumper assembly 226 essentially works the same as in the first embodiment. The bumper 246 pushes the plunger 262 against the bias of the plunger spring 264 into contact with the bumper engagement switch 266 as the bumper 246 becomes fully seated in the pocket 256 of the base 254 . When appropriate, the controller causes the moving mechanism 270 of the electronic locking mechanism 268 to push on the retaining flanges 272 , thus pivoting them into engagement with the retaining surface 248 and locking the bumper 246 in place.
[0040] FIGS. 8 and 9 illustrate a fourth embodiment of the lockable bumper assembly 326 that may be employed with the vehicle of FIG. 1 . The arrangement in FIGS. 8 and 9 have many items in common with that of FIGS. 2 and 3 and to avoid unnecessary repetition of the description, the same reference numbers have been used but falling within the 300-series. The significant difference between this embodiment and the first embodiment is the way that the electronic locking mechanisms 368 engage the bumper 346 , and the shape of the bumper 346 . The electronically actuatable, moving mechanisms 370 engage movable retaining flanges 372 , which are telescopically slidable along the path of guides 384 . The retaining flanges 372 have mushroom-shaped cross sections and engage with a retaining surface 348 on a concave curved portion 385 of a bumper 346 , having a somewhat I-shaped cross section, when slid into the pocket 356 . The bumper 346 is shaped to slide into the pocket 356 of the base 354 without contacting the retaining flanges 372 , which are recessed into cavities 386 in the base 354 .
[0041] The lockable bumper assembly 326 essentially works the same as in the first embodiment. The bumper 346 pushes the plunger 362 against the bias of the plunger spring 364 into contact with the bumper engagement switch 366 as the bumper 346 becomes fully seated in the pocket 356 of the base 354 . When appropriate, the controller causes the moving mechanism 370 of the electronic locking mechanism 368 to push on the retaining flanges 372 , thus sliding them into engagement with the retaining surface 348 and locking the bumper 346 in place.
[0042] FIGS. 10 and 11 illustrate a fifth embodiment of the lockable bumper assembly 426 that may be employed with the vehicle of FIG. 1 . The arrangement in FIGS. 10 and 11 have many items in common with that of FIGS. 2 and 3 and to avoid unnecessary repetition of the description, the same reference numbers have been used but falling within the 400-series. The significant difference between this embodiment and the first embodiment is the way that the electronic locking mechanisms 468 engage the bumper 446 , and the shape of the bumper 446 . The electronically actuatable, moving mechanisms 470 engage movable retaining flanges 472 , which are telescopically slidable in cavities 488 . The retaining flanges 472 have a truncated triangle-shaped cross section and engage with a retaining surface 448 on a complimentary concave portion 489 of a bumper 446 , having a somewhat I-shaped cross section, when slid into the pocket 456 . The bumper 446 is shaped to slide into the pocket 456 of the base 454 without contacting the retaining flanges 472 , which are recessed into cavities 488 in the base 454 .
[0043] The lockable bumper assembly 426 essentially works the same as in the first embodiment. The bumper 446 pushes the plunger 462 against the bias of the plunger spring 464 into contact with the bumper engagement switch 466 as the bumper 446 becomes fully seated in the pocket 456 of the base 454 . When appropriate, the controller causes the moving mechanism 470 of the electronic locking mechanism 468 to push on the retaining flanges 472 , thus sliding them into engagement with the retaining surface 448 and locking the bumper 446 in place.
[0044] FIGS. 12-14 illustrate a sixth embodiment of the lockable bumper assembly 526 that may be employed with the vehicle of FIG. 1 . The arrangement in FIGS. 12-14 have many items in common with that of FIGS. 8 and 9 and to avoid unnecessary repetition of the description, the same reference numbers have been used but falling within the 500-series. Similar to FIGS. 8 and 9 , the movable retaining flanges 572 have mushroom-shaped cross sections and include guides 592 for allowing telescopic movement of the flanges 572 . Also, the retaining surfaces 548 of the bumper 546 are concave curved portions. In this embodiment, however, the flanges 572 are biased partially into the pocket 556 by support springs 593 . In addition, the electronically actuatable, moving mechanisms 570 are oriented ninety degrees to the direction of orientation in FIGS. 8 and 9 . When actuated, the moving mechanisms 570 slide locks 594 behind the retaining flanges 572 , preventing them from disengaging with the bumper 546 . The other difference with the previous embodiments is that the bumpers 546 must push the retaining flanges 572 out of the way against the bias of the support springs 593 as they slide into and out of the pockets 556 .
[0045] While certain embodiments of the present invention have been described in detail, those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the invention as defined by the following claims.
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A closure assembly and method of operation for a vehicle closure includes a latch for selectively securing the closure to the vehicle, and a lockable bumper assembly that includes an electronic locking mechanism that can selectively secure the bumper in a pocket of the base to add an additional mechanism for securing the closure to the vehicle. The locking mechanism may be controlled to secure the bumper to the base after a controller detects that the latch is latched and the bumper is seated in the pocket of the base.
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BACKGROUND OF THE INVENTION
The present invention relates to a developing device for an electrophotographic image forming apparatus, and a toner cartridge for replenishing a fresh toner to the developing device.
A copier, facsimile apparatus, laser printer or similar electrophotographic image forming apparatus has a developing device for developing a latent image electrostatically formed on a photoconductive element, or image carrier, by using a toner. It has been customary with this kind of apparatus to replenish a fresh toner into the developing device from a toner cartridge removably mounted to the developing device. The developing device includes a toner storing section or hopper for receiving the fresh toner from the cartridge. During the course of development, the toner is sequentially fed from the hopper to the photoconductive element. The toner consists of toner particles and an additive. The problem with the conventional developing device is that as the developing device is operated a number of times, the additive concentration of the toner increases. As a result, the toner density, i.e., the density of an image developed by the toner is lowered. Specifically, although the additive should ideally be transferred to the latent image of the photoconductive element together with the toner particles, the additive is, in practice, left in the hopper without being consumed. Moreover, assume that the developing device or the entire image forming apparatus is held in an inclined position by accident. Then, because the toner is fed over the entire length of the photoconductive element, the additive concentrates on one end portion lower in level than the other end portion. This further increases the additive concentration of the toner and thereby aggravates the decrease in toner density or image density.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a developing device for an image forming apparatus and capable of preventing the toner density from decreasing, and a toner cartridge therefor.
In accordance with the present invention, a developing device for an image forming apparatus has a toner storing section for storing a single-ingredient type toner to be deposited on a latent image electrostatically formed on an image carrier. A toner cartridge is removably mounted to the body of the developing device, and stores a fresh toner to be replenished into the toner storing section. A circulating arrangement is provided for circulating the toner between the toner cartridge and the toner storing section.
Also, in accordance with the present invention, a developing device for an image forming apparatus has a toner storing section for storing a single-ingredient type toner to be deposited on a latent image electrostatically formed on an image carrier. An agitator agitates the toner existing in the toner storing section. A toner cartridge is removably mounted to the body of the developing device, and stores a fresh toner to be replenished into the toner storing section. The toner cartridge has toner outlets for replenishing the fresh toner, a conveying member for conveying the fresh toner to the toner outlets, collection openings for receiving the toner forced out by the agitator, and a collecting arrangement for conveying the toner received via the collection openings into the toner cartridge.
Further, in accordance with the present invention, a toner cartridge storing a fresh toner and removably mounted to the body of a developing device for replenishing the fresh toner into a toner storing section included in the developing device has toner outlets for replenishing the fresh toner. Collection openings receive a part of a toner existing in the toner storing section. A magnetic roller extends in the longitudinal direction of the body of the toner cartridge, and faces the toner outlets and collection openings. A blade contacts a portion of the magnetic roller facing the collection openings, and scrapes off the fresh toner and toner collected via the collection openings from the magnetic roller.
Furthermore, in accordance with the present invention, a developing device for an image forming apparatus has a toner storing section for storing a single-ingredient type toner. A conveying member causes the toner in the toner storing section to deposit on the surface thereof, and causes it to be transferred to a latent image electrostatically formed on an image carrier. A supply roller is rotatably disposed in the toner storing section for driving the toner in the toner storing section toward the conveying member. A coil member is fitted on the supply roller for shifting the toner in the axial direction of the supply roller. A movable member has a stationary end affixed to a predetermined position of the body of the developing device and free ends received between the nearby turns of the coil member. The free ends are movable up and down in association with the rotary motion of the supply roller.
Moreover, in accordance with the present invention, a developing device for an image forming apparatus has a toner storing section for storing a single-ingredient type toner. A conveying member causes the toner in the toner storing section to deposit thereon, and causes it to be transferred to a latent image electrostatically formed on an image carrier. A supply roller is rotatably disposed in the toner storing section for driving the toner in the toner storing section toward the conveying member while agitating it. A toner cartridge is removably mounted to the body of the developing device, and stores a fresh toner to be replenished into the toner storing section. The toner cartridge has toner outlets for replenishing the fresh toner, a conveying member for conveying the fresh toner to the toner outlets, collection openings for receiving the toner forced out by the supply roller, and a collecting arrangement for conveying the toner received via the collection openings into the toner cartridge. A coil member is fitted on the supply roller for shifting the toner in the axial direction of the supply roller. A movable member has a stationary end affixed to a predetermined position of the body of the developing device and free ends received between the nearby turns of the coil member. The free ends are movable up and down in association with the rotary motion of the supply roller.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description taken with the accompanying drawings in which:
FIG. 1 is a section of a conventional developing device operable with a toner cartridge;
FIG. 2 is an external perspective view of the toner cartridge shown in FIG. 1;
FIG. 3 is a section showing an arrangement around a magnetic roller disposed in the toner cartridge shown in FIG. 2;
FIG. 4 is a graph showing a relation between the number of runs of the developing device and the amount of an additive existing in a hopper included in the device;
FIG. 5 is a graph showing a relation between the number of runs of the developing device and the image density;
FIG. 6 is a fragmentary section of a developing device embodying the present invention and operable with a toner cartridge;
FIG. 7 is an external perspective view of the toner cartridge shown in FIG. 6;
FIG. 8 is a section along line Y--Y of FIG. 6;
FIG. 9 is a fragmentary side elevation of an agitator representative of an alternative embodiment of the present invention;
FIG. 10 is a perspective view of the agitator shown in FIG. 9;
FIG. 11 is a side elevation showing how a toner adheres to a supply roller;
FIG. 12 is a side elevation showing an agitator representative of another alternative embodiment of the present invention, together with an arrangement around the agitator;
FIG. 13 is a perspective view of the agitator shown in FIG. 12 and an arrangement adjoining it;
FIG. 14 is a side elevation of another specific configuration of the agitator; and
FIGS. 15 and 16 are perspective views each showing a particular configuration of an anti-deformation sheet metal attached to an agitator film.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
To better understand the present invention, a brief reference will be made to a conventional developing device using a toner cartridge, shown in FIG. 1. As shown, a toner cartridge 1 stores a fresh single-ingredient type toner therein. The cartridge 1 has a casing 2 accommodating an agitator 3 and a magnetic roller 4. The agitator 3 is rotated to agitate the toner existing in the casing 2. The casing 2 is formed with a plurality of toner outlets 5. As shown in FIG. 2, the toner outlets 5 are arranged in an array in the lengthwise direction of the casing 2.
A developing device 6 has a casing 7 including a toner storing section, or hopper as referred to hereinafter, 8. An agitator 9 is rotatable in the hopper 8 for agitating the toner existing in the hopper 8. A toner inlet 10 is formed in a portion of the casing 7 which faces the toner outlets 5 of the cartridge casing 2. A developing roller 11 causes the toner to deposit thereon. A doctor blade 12 causes the toner to form a thin layer on the surface of the developing roller 11. An intermediate roller 13 is held in contact with the developing roller 11, so that the toner is transferred from the roller 11 to the roller 13. A photoconductive element in the from of a drum 14 is held in contact with the intermediate roller 13. The toner is transferred from the roller 13 to the drum 14 in order to develop a latent image electrostatically formed on the drum 14. The resulting toner image is transferred from the drum 14 to a paper or similar recording medium by an image transfer unit 15. A cleaning unit 16 cleans the surface of the drum 14 after the image transfer. A charger 17 uniformly charges the surface of the drum 14. An exposing device 18 exposes the charged surface of the drum 14 imagewise so as to form the latent image.
The toner in the hopper 8 is conveyed toward the developing roller 11 while being agitated by the agitator 9. The toner deposited on the roller 11 is regulated by the doctor blade 12 to form a thin layer, while being frictionally charged thereby. As a result, the toner is electrically transferred from the roller 11 to the intermediate roller 13. On the other hand, the drum 14 is uniformly charged by the charger 17. The exposing device 18 electrostatically forms a latent image on the charged surface of the drum 14. When the latent image is conveyed by the drum 14 to a position where the drum 14 contacts the roller 13, the toner is transferred from the roller 13 to the latent image. The resulting toner image is transferred to the paper by the image transfer unit 15.
The magnetic roller 4 disposed in the cartridge 1 serves to replenish the fresh toner into the developing device 6. Hence, to insure stable replenishment into the hopper 8, it is preferable to use means for scraping off the toner from the surface of the roller 4, as will be described with reference to FIG. 3.
FIG. 3 shows an arrangement around the magnetic roller 4. As shown, an upright rib 19 extends in the lengthwise direction of the toner outlets 5 from the downstream edges of the outlets 5 with respect to the direction of toner conveyance. The edge of the rib 19 and the roller 4 are spaced from each other by a gap d. The agitator 3 rotating in the cartridge 1 conveys the toner, labeled T, to the roller 4. The toner deposited on the roller 4 is conveyed toward the toner outlets 5 by the roller 4 which is rotated in a direction A. Specifically, the toner T is deposited on the roller 4 over a clearance a between the roller 4 and the inner periphery of the cartridge casing 2. Because the gap d is selected to be smaller than the clearance a, the toner T deposited on the roller 4 is scraped off by the rib 19 and introduced into the hopper 8.
In the above configuration, the toner T is stably replenished from the cartridge 1 into the hopper 8 at all times. However, in the hopper 8, the concentration of an additive included in the toner sequentially increases with an increase in the number of runs of the developing device 6. As a result, the image density is lowered. Particularly, as shown in FIG. 4, the additive concentration of the toner noticeably increases at the end portions of the developing device 6, compared to the intermediate portion of the same. FIG. 5 shows the resulting decrease in image density.
Preferred embodiments of the present invention will be described hereinafter which are free from the problem discussed above. In the embodiments, the same or similar constituents as or to the constituents shown in FIGS. 1-3 are designated by the same reference numerals, and a detailed description thereof will not be made in order to avoid redundancy.
FIG. 6 shows a developing device embodying the present invention. As shown, a toner cartridge 20 has a casing 21. A blade 22 contacts the surface of a magnetic roller 4 and is made of polyethylene terephthalate (PET). Upright ribs 23 respectively extend from the casing 21 at both sides of the blade 22, and each faces the surface of the roller 4. The ribs 23 are equivalent in function to the rib 19 shown in FIG. 3. The edge of the blade 22 is oriented counter to the direction of rotation of the roller 4 and located downstream of the ribs 23 with respect to the direction of rotation of the roller 4. Collection openings 24 are formed in the casing 21, and each is flared from the inside to the outside of the casing 21.
A developing device 25 has a casing 26 formed with toner outlets 27 respectively facing the collection openings 24 of the casing 26. The toner outlets 27 are flared from the outside to the inside of the casing 26. A sponge 28 is affixed to the outer periphery of the casing 26 in such a manner as to surround the toner outlets 27 and toner inlets which will be described.
FIG. 7 shows the toner cartridge 20 in an external perspective view. As shown, the casing 21 is formed with toner outlets 29 for replenishing a fresh toner into the developing device 25. Specifically, the toner outlets 29 are located at opposite ends of the surface of the casing 21 that faces the developing device 25 (see FIG. 6) in the lengthwise direction. The previously mentioned collection openings 24 (three in the embodiment) are formed in the intermediate portion of the above surface of the casing 21. Hence, five openings in total are formed in an array in the casing 21.
FIG. 8 is a section along line Y--Y of FIG. 6. As shown, toner inlets 30 are formed in the casing 26 of the developing device 25 and respectively face the toner outlets 29 of the cartridge casing 21. The toner inlets 30 are each flared from the inside to the outside of the casing 26. Specifically, two toner inlets 30 are formed in opposite end portions of the casing 26 and respectively face the toner outlets 29 of the casing 21. Three toner outlets 27 are formed in the intermediate portion of the casing 26 and respectively face the collection openings 24 of the casing 21. Hence, five openings in total are also formed in an array in the casing 26.
When the cartridge 20 is mounted to the developing device 25, the sponge 28 contacts the edge portions the toner outlets 29 and collection openings 24 and thereby fills the gaps between the edge portions of the toner outlets 29 and the toner inlets 30 and the gaps between the edge portions of the collection openings 24 and the toner outlets 27. The walls of the toner outlets 29 and those of the toner inlets 30 smoothly merge into each other without any step. Likewise, the walls of the collection openings 24 and those of the toner outlets 27 smoothly merge into each other without any step.
The ribs 23 extend from the casing 21 at the downstream side of the toner outlets 29 with respect to the direction of rotation of the roller 4 and such that their edges adjoin the opposite ends of the roller 4. Hence, a space is formed by the ribs 23, roller 4 and casing 21 at the intermediate portion of the roller 4 at the downstream side of the three collection openings 24 with respect to the direction of rotation of the roller 4.
In operation, the agitator 3 in rotation conveys the toner T to the magnetic roller 4. Because the intermediate portion of the roller 4 is covered with the blade 22, the toner T deposits on the opposite end portions of the roller 4. While the roller 4 in rotation conveys the toner T deposited on its opposite end portions, the ribs 23 scrape it off. As a result, the toner T is introduced into the hopper 8 via the aligned toner outlets 29 and toner inlets 30. The toner T is sequentially transferred to a photoconductive element, not shown, by way of an agitator 9, a developing roller 11, and an intermediate roller 13.
The agitator 9 in rotation conveys the toner upward within the hopper 8. As a result, this toner is partly collected in the cartridge 20 via the aligned toner outlets 27 and collection openings 24. Then, the toner is deposited on the roller 4, conveyed by the roller 4, and then scraped off by the blade 22 into the cartridge 20. Although the toner tends to penetrate into the collection opening side 24, such a toner is caught and conveyed by the roller 4 together with the toner collected from the hopper 8, and then scraped off by the blade 22. In this manner, the toner is circulated between the hopper 8 and the cartridge 20.
Referring to FIGS. 9 and 10, an agitator representative of an alternative embodiment of the present invention is shown. As shown, the agitator, generally 9, has a supply roller 9a implemented by a sheet metal having bent portions at opposite edges thereof. An auger 9b is implemented as two coil members respectively wound round opposite ends of the roller 9a. The agitator 9 is rotatable about the longitudinal axis thereof. The bent portions of the roller 9a are oriented counter to the direction of rotation of the roller 9a. The coil members of the auger 9b are spirally wound round the roller 9a from the ends of the roller 9a toward the center in the same direction as the direction of rotation of the roller 9a. This embodiment differs from the previous embodiment in that the coil members constituting the auger 9b are wound round the opposite ends of the agitator 9.
When the agitator 9 shown in FIGS. 9 and 10 is rotated, it sequentially shifts the toner from the opposite ends toward the center. Hence, the toner density is prevented from decreasing at the end portions of the developing device 25. In addition, the amount of toner increases at the intermediate portion of the hopper 8 and can enter the toner outlets 27 in a great amount.
Generally, a toner is apt to cohere and form blocks when temperature around a developing device rises. This is also true when humidity around the developing device rises. When the developing device is operated under such conditions, the toner adheres to a supply roller in a hopper such that the roller turns out a rod. If the developing device is further operated with the toner sequentially adhering thereto, the toner further solidifies due to the temperature or the humidity, aggravating the configuration of the supply roller. When the supply roller rotating at a high speed turns out a rod, it cannot seize the toner existing therearound. As a result, a space is formed between the supply roller and the neighborhood thereof. In this condition, the supply roller looses its function, and so does an auger. Consequently, the supply roller fails to shift the toner toward the center thereof.
FIG. 11 is a section showing the supply roller turned out a rod due to the adhesion of the toner. As shown, a space is formed between the supply roller 9a and its neighborhood and causes the roller 9a to loose its expected function. Particularly, the portions of the roller 9a where the auger 9b is provided turn out a rod earlier than the other portion because the toner easily adheres to the auger 9b.
Referring to FIGS. 12 and 13, an arrangement around an agitator and representative of another alternative embodiment of the present invention will be described. As shown, an agitator film 31 is affixed to the casing 26 at its portion 31a in the vicinity of the toner outlets 27. A plurality of flexible teeth 31b extend out from the portion 31a like the teeth of a comb. The tips of the teeth 31b are each positioned between the nearby turns of the auger 9b and adjoins the supply roller 9a. The auger 9b is provided with a constant pitch l. The flexible teeth 31b of the film 31 are provided with a pitch L equal to the pitch l of the auger 9b. As shown in FIG. 12, when the roller 9a is rotated, the teeth 31b are raised by the roller 9a or the auger 9b and then lowered due to their flexibility.
With the above configuration, it is possible to agitate the toner existing between the turns of the auger 9b and to thereby prevent it from adhering to the roller 9a and auger 9b.
While the agitator film 31 has been shown and described as being affixed to the vicinity of the toner outlets 27, they may be affixed to the inner periphery of the hopper 8, as shown in FIG. 14. The crux is that the tips of the flexible teeth 31b be received in the auger 9b.
The agitator film 31 shown in FIG. 12 or 14 is likely to loose its flexibility due to aging and fail to return to the original position, i.e., to deform permanently. FIGS. 15 and 16 respectively show sheet metals 32 which may be used to prevent the films 31 shown in FIGS. 12 and 14 from bending. As shown, the sheet metals 32 of FIGS. 15 and 16 are respectively affixed to the films 31 of FIGS. 12 and 14. The sheet metals 32 each has a comb-like configuration for covering the affixing portion 31a of the film 31 and a part of the root portions of the teeth 31b.
In any of the embodiments shown and described, the toner is circulated between the cartridge 20 and the hopper 8, so that the additive of the toner existing in the developing device 25 is scattered. This prevents the additive from staying at limited portions and thereby insures stable images. Particularly, the coil members 9b attached to the opposite ends of the agitator 9, as shown in FIG. 10, promote the circulation of the toner and allow the toner to be rapidly fed from the end portions of the developing device 25.
Because the edges of the toner outlets 29 and toner inlets 30 and the edges of the collection openings 24 and toner outlets 27 are flared, the toner is allowed to move smoothly between the cartridge 20 and the hopper 8. The sponge 28 has both a sealing function and a guiding function. This, coupled with the fact that the walls of the openings 24 and 27 smoothly merge into each other without any step, prevents the toner from flowing reversely or from flying about, thereby further enhancing the smooth circulation of the toner.
The teeth 31b of the agitator film 31 positioned between the turns of the auger 9b, as shown in FIGS. 12 or 14, agitate the toner existing there and thereby prevent it from adhering to the supply roller 9a and auger 9b. Hence, when the supply roller 9a is rotated, the auger 9b forcibly and stably shifts the toner from the end portions of the developing device 25 toward the center. As a result, the amount of toner increases at the intermediate portion of the hopper 8 and enters the toner outlets 27 in a great amount. This promotes the circulation of the toner and allows the toner to be rapidly fed from the end portions of the hopper 8.
In summary, it will be seen that the present invention provides a developing device for an image forming apparatus and a toner cartridge having various unprecedented advantages, as enumerated below.
(1) A toner is circulated between a toner cartridge and a hopper so that the additive of the toner existing in a developing device is scattered. This prevents the additive from staying at limited portions and thereby insures stable images.
(2) Toner outlets and collection openings formed in the cartridge may be provided with a suitable arrangement, so that a path for the circulation of the toner may also be suitably arranged.
(3) The toner can be collected in the cartridge by simple means.
(4) Because the toner is replenished and collected by a magnetic roller, it is not necessary to provide the cartridge with an extra space for toner collecting means. Hence, the toner circulation is achievable with a minimum of cost.
(5) The toner is fed from opposite end portions of the hopper and then collected at the center. Hence, the toner whose additive concentration is apt to increase at the end portions of the hopper is efficiently scattered. This promotes the smooth circulation of the toner and thereby insures stable development.
(6) The movement of the hopper to the cartridge is smooth.
(7) During the circulation of the toner, the toner is prevented from dropping via gaps between the cartridge and the developing device.
(8) The cartridge has a toner replenishing function and a toner collecting function. This allows the toner to be circulated between the cartridge and the hopper. As a result, the additive included in the toner is prevented from staying in limited portions; otherwise the toner density would be lowered in the limited portions.
(9) Because a movable member is received between the turns of a coil member, the toner is prevented from cohering around the coil member. Hence, the toner is replenished and agitated in a stable manner.
(10) Because the toner is circulated between the cartridge and the hopper, the additive of the toner is prevented from staying in limited portions; otherwise the toner density would be lowered in the limited portions. The coil member surrounding a supply roller and the movable member received between the turns of the coil member achieve the above advantage (9), and further enhances the circulation of the toner.
(11) Because the coil member and the movable member have the same pitch, the toner can be efficiently agitated.
(12) A film member used as the movable member is inexpensive and can be freely designed.
(13) An anti-deformation member is associated with the film member and insures stable toner agitation and replenishment despite aging. Hence, a stable image is attainable at all times.
Various modifications will become possible for those skilled in the art after receiving the present disclosure without departing from the scope thereof. For example, the number of toner outlets and that of the collection openings of the cartridge shown and described are only illustrative. However, because the toner is replenished by being dropped and is collected by being raised, it is preferable that the number of the collection openings be equal to or greater than the number of the toner outlets.
Further, the arrangement of the toner outlets and collection openings of the cartridge and the arrangement of the blade and ribs shown and described are also only illustrative. However, because the additive concentration of the toner tends to increase at the end portions of the hopper 8 so long as the developing device is horizontal, it is preferable to feed the toner from the end portions of the hopper 8 toward the center and then collect it, as in the embodiments.
The agitator film may be replaced with a sheet metal, if desired. The crux is that portions corresponding to the flexible teeth be movable. Of course, the triangular teeth shown in FIG. 13 may be modified in various ways, e.g., they may be provided with holes or curved portions.
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A developing device for an electrophotographic image forming apparatus and a toner cartridge for replenishing a fresh toner to the developing device are disclosed. A toner is circulated between a toner cartridge and a hopper so that an additive included in the toner existing in the developing device is adequately distributed throughout the developing device. This prevents the concentration of additive in the toner from differing at the ends of the hopper with respect to the center of the hopper. This ensures that images are produced with constant toner density.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of copending International Application No. PCT/EP00/01080, filed Feb. 10, 2000, which designated the United States.
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to a cooling device for installation in a furniture niche of a kitchen unit or the like. The device includes at least one thermally insulating cooling space, which can be sealed by a door, and a base disposed therebeneath. The base serves to accept assemblies such as compressors, ventilators, and so on, and is force ventilated by the ventilator by way of at least one air inlet in the front region at the door side. To achieve an optimal volume of cooling space in built-in cooling devices, the prior art equips them with what is referred to as a base, within which the condenser/liquifier and the ventilator are disposed. As a result, these assemblies reduce the volume of the cooling space only marginally, if at all.
U.S. Pat. No. 3,142,162 to Herndon et al. describes such a cooling device. In the Herndon cooling device, a base is provided under the cooling space, the back of which accepts a compressor, a condenser, and a ventilator that force ventilates these assemblies. The ventilator supplies cool air to the assemblies that must be cooled by way of an air supply vent in the front region at the door side and an adjoining air inlet channel. The ventilator removes the hot air through an exhaust channel at its mouth and an exhaust vent in the front region at the door side. To prevent a short, which substantially degrades the cooling of the assemblies, a separating wall is provided in the base, which extends from the openings in the door-side front region into the rear region serving for receiving the assemblies. Thus, the wiring of the base is subdivided into two sections. However, the subdivision of the base interior substantially limits the possibility for configuring the assemblies suitably for cooling. In such regard, the condenser must be positioned on the air supply side to be able to cool it sufficiently to achieve an acceptable level of effectiveness for the cooling device. A consequence of such a function-specific configuration is that the condenser occupies a width of the air supply section to limit the area of the heat exchange surface of the condenser, particularly when the height of the base is fixed to a maximum value for optimizing the cooling space volume. Another consequence of the electrical subdivision is that the amount of cool air, which is necessary for cooling the assemblies, is only available when the air is moved along the channels at a relatively high velocity. Consequently, floating particles, which are commonly present in the standing area of a cooling device, are drawn into the base region and settle on the surface of the condenser (which is wound into several layers), causing the heat exchange characteristics to deteriorate substantially over the service life of the cooling device. Such deterioration results in a notable reduction of the effectiveness of the device. An additional reduction of the effectiveness derives from configuring the supply and exhaust openings immediately adjacent one another, because, with such a configuration, hot air that exits at the exhaust opening cannot be prevented from being drawn in again through the supply opening, at least to some extent, so that the preheated air is used to cool the condenser.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide a cooling device for installation in a furniture niche that overcomes the hereinafore-mentioned disadvantages of the heretofore-known devices of this general type and that provides at least one exhaust aperture in the back region of one of the walls of the base that is averted from the door.
With the foregoing and other objects in view, there is provided, in accordance with the invention, a cooling device for installation in a furniture niche, including at least one thermally insulating container defining a cooling space and having a door for sealing the cooling space, and a cooling apparatus including a compressor, a condenser, and a ventilator. The base has at least two sidewalls, a front region disposed in a vicinity of the door, a rear region, at least one air supply aperture disposed at the front region, and an exhaust aperture disposed at the rear region. The base houses the compressor, the condenser, and the ventilator. The base is disposed below the cooling space. The base is force ventilated by the ventilator through the at least one air supply aperture and the exhaust aperture. The exhaust aperture is disposed in at least one of the sidewalls. Preferably, the cooling device is installed in a furniture niche of a kitchen unit.
On one hand, the spatial separation of the air supply aperture from the exhaust aperture prevents the cool air that is drawn in by way of the supply aperture from mixing with the exhaust air that has already been heated in the process of cooling of the assemblies, and thereby noticeably improves the cooling of the assemblies and also the effectiveness of the device. Furthermore, because the supply and exhaust apertures are spatially separated, it is possible to forgo a channel formation within the interior of the base. Thus, the device assemblies are configurable in the base for optimum effectiveness. Moreover, because the electrical subdividing in the interior of the base is forgone, a larger air supply cross-section is possible, and the cool air that is required for sufficient cooling of the device assemblies can be transported at a low velocity. The low velocity produces a substantially reduced drag of particles into the interior of the base, which results in a substantially lower degree of contamination of the interior of the base and, thus, of the condenser. Accordingly, the heat exchange characteristics of the condenser are maintained nearly over the entire service life of the cooling device. It is particularly expedient when the exhaust aperture is disposed sitting in the rear region at one of the walls of the base, as provided in a preferred exemplifying embodiment of the invention.
According to a separate preferred embodiment of the invention, the exhaust aperture is disposed at least at one of the side walls of the base. With such a configuration of the exhaust aperture, it is already sufficiently spatially separated from the supply aperture so that a heating of the cool air streaming in through the supply aperture by the hot exhaust air that is removed from the exhaust aperture is at least substantially prevented to the benefit of a substantial improvement of the effectiveness of the cooling system. Additionally, an air throughput through the exhaust aperture, which is sufficient for cooling the assemblies, is easily achievable.
In accordance with another feature of the invention, there are at least two exhaust apertures, the sidewalls each have a sidewall rear region in a vicinity of the rear region of the base, and at least one of the exhaust apertures is disposed in the sidewall rear region of one of the sidewalls.
At least one respective exhaust aperture is provided at the sidewalls in the back region of the base. As such, a particularly minimal particle drag into the base space is achieved. Furthermore, the exhaust removal is substantially faster given constant ventilator power. The exhaust apertures are disposed particularly expediently with respect to a spatial separation of the supply and exhaust apertures when, in accordance with a further feature of the invention, the exhaust apertures are disposed at the sidewalls of the base immediately adjacent to its back wall.
In accordance with an added feature of the invention, at least one exhaust aperture is disposed at the back side of the base. By virtue of the configuration of the exhaust aperture, the hot air is reliably prevented from mixing into the cool air serving for the cooling of the assemblies, thereby increasing the effectiveness of the cooling system even further.
In accordance with an additional feature of the invention, the front region of the base has a front wall defining the at least one supply aperture, the front wall has a width, and the supply aperture extends at least substantially across the width of the front wall.
With such a base construction, a particularly large exhaust feed is possible given a low airspeed. Furthermore, it becomes possible to tune the width of the condenser, for example, to the width of the air supply aperture, whereby the condenser is cooled particularly intensively. Thus, the effectiveness of the cooling system is enhanced particularly expediently.
The condenser experiences a particularly intensive cooling when, in accordance with yet another feature of the invention, the condenser is positioned at least substantially in a vicinity of the at least one supply aperture and behind the at least one supply aperture in an air flow direction.
In accordance with a concomitant feature of the invention, the ventilator is disposed between the condenser and the compressor.
Other features that are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in a cooling device for installation in a furniture niche, it is, nevertheless, not intended to be limited to the details shown because various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary, front, perspective view of a kitchen unit integrated refrigerator with a base for receiving device assemblies;
FIG. 2 is a top, perspective view of a first embodiment of the base of FIG. 1 according to the invention;
FIG. 3 is a top, perspective view of a second embodiment of the base of FIG. 2 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In all the figures of the drawing, sub-features and integral parts that correspond to one another bear the same reference symbol in each case.
Referring now to the figures of the drawings in detail and first, particularly to FIG. 1 thereof, there is shown a kitchen unit 10 having three adjacent cabinets 11 a, 11 b and 11 c, whose front is formed by doors 12 that are constructed at different heights, and whose body rests on height-adjustable feet 13 that stand on the non-illustrated floor of the kitchen. For clarity, only the feet of the center cabinet element 11 b are shown. The cabinet elements 11 a and 11 c that adjoin the center element 11 b are constructed as conventional tall cupboards including sidewalls 14 , whose sides that face the kitchen floor are provided with a cutout 15 that recedes from the front of the kitchen unit 10 . The cutout 15 includes a limiting surface that serves as a stop for a base facing 16 and that, in the installed condition, covers the feet 13 and gives the kitchen unit 10 a base-type or pedestal-type return. The base facing 16 includes a recess 17 that is open at the margin and oriented in its installed position approximately centrally relative to the width of the center cabinet element 11 b, and that is covered by a ventilation blind 18 having an angular cross-section. A first leg 19 of the ventilation blind 18 extends parallel to the base facing 16 in the installed position and has ventilation slots 20 , while its second leg 21 , which is disposed perpendicular to the first leg 19 and points towards the kitchen unit 10 with its free end, serves for holding the ventilation blind 18 at the center cabinet element 11 b. In contrast to its neighboring cabinet elements 11 a and 11 c, the center cabinet element 11 b is constructed as a niche 22 that is formed substantially from a ceiling (not described in further detail) and a non-illustrated rear panel, as well as two side panels 23 that are disposed at least approximately at a parallel distance from each other. The inner surfaces of the side panels 23 that face each other are provided with protruding bearing strips 24 having flat profiles. The bearing strips 24 are disposed at the same height. The adjustment elements 13 are supported at the bearing strips 24 . At the same time, the bearing strips 24 serve for supporting a built-in cooling device 25 including a door 26 (shown in a closed position) and whose front side is provided with a front furniture panel 27 that is adapted to the adjacent pieces of furniture. To support the built-in cooling device 25 at its housing, a rigid, self-bearing base 28 is provided, of which a first variant is shown in FIG. 2 .
FIG. 2 illustrates the base 28 having two cantilevers 29 , whose free ends are averted from each other and whose bearing surface 30 , which is situated on top (when the base 28 is in the installed position), serves to support the device housing, while their bottom bearing face 31 , which is situated parallel to the top bearing surface, is supported at the bearing strips 24 . Besides the cantilevers 29 , the base 28 includes a trough 32 that has a solid floor 33 and a solid back wall 34 . Opposite the back wall 34 , the base trough 32 is furnished with a front wall 35 that has an opening 36 that is disposed at least approximately across its height and width and whose longitudinal side opposite the floor 33 is constructed open at the margin. The front wall 35 and the back wall 34 are connected to each other by sidewalls 37 , each of which is provided with vertically extending reinforcing ribs 38 on an interior surface that is averted from the free ends of the cantilevers 29 , and each of which includes a breakthrough 39 or gap in the back region of the base 28 . In the embodiment, the breakthrough 39 extends between the reinforcing ribs, which are disposed immediately adjacent the back wall 34 and the reinforcing ribs 38 , which are disposed approximately midway along the length of the sidewalls. The sidewalls 37 , together with the floor 33 , the back wall 34 , and the front wall 35 , define a trough space 40 , which serves to accommodate various device assemblies, namely a coiled condenser 41 , a ventilator 42 , and a compressor 43 . The condenser 41 is disposed in the vicinity of the front wall 35 and extends at least approximately with the dimensions of the aperture 36 . The ventilator 42 is disposed behind the condenser 41 in the direction of the back wall 34 . The compressor 43 is disposed behind the ventilator 42 in the direction of the back wall 34 and fixed to the floor 33 of the trough 32 , like the ventilator 42 , and the condenser 41 .
The ventilator 42 serves to force ventilate the condenser 41 , which must be cooled by cold air, and, to such an end, the ventilator 42 draws cold air through the aperture 36 provided in the front wall 35 as indicated by arrow A and transports the drawn-in air forward to the downstream compressor 43 , which must also be cooled. Together with the back wall 34 , the compressor 43 splits the forced cold air into sub-streams and deflects the air to the breakthroughs 39 that are provided in the sidewalls 37 . The breakthroughs 39 are disposed behind the configuration including the condenser 41 and the ventilator 42 in the direction of the back wall 34 . The cold air that is deflected to the breakthroughs 39 (see arrows B) escapes through these and flows along the channel formed between the exterior surfaces of the sidewalls 37 and the interior surfaces of the side panels 23 , before escaping from the niche 22 on the door side.
FIG. 3 illustrates a second exemplifying embodiment of a base 50 , which, like the base 28 , is equipped with two cantilevers 51 . The cantilevers each have a bearing surface 52 , the top surface of which in the installed position serves for supporting the housing of the built-in cooling device 25 , while their bottom bearing surface 53 , which is parallel to the top surface, is provided for supporting the rigid and self-bearing base 50 at the bearing strips 24 . The base 50 is also equipped with a trough 54 , which includes a solid floor 55 and two solid sidewalls 56 . The sidewalls 56 each have vertical reinforcing ribs 57 on their interior surface, which is averted from the side panels 23 . The sidewalls 56 are connected to each other at their door-side end portions by a front wall 58 having an aperture 59 that is open at the margin in the direction of bearing surfaces 52 and that serves as a ventilation opening. Opposite the front wall 58 , the trough 54 includes a back wall 60 that connects the two sidewalls 56 to each other at their ends averted from the door 26 . The back wall 60 , like the front wall 58 , has an aperture 61 having at least substantially the same area as the aperture 59 and extending in like manner at least substantially to the floor 55 . The back wall 60 , together with the front wall 58 , the two sidewalls 56 , and the floor 55 , define a trough space 62 for accommodating various device assemblies, namely a coiled condenser 63 , a ventilator 64 , and a compressor 65 . The condenser 63 is disposed in the immediate vicinity of the front wall 58 and at least substantially occupies the area of the aperture 59 . The ventilator 64 is disposed behind the condenser 63 in the direction of the back wall 60 . The compressor 65 is disposed behind the ventilator 64 . The compressor 65 is fixed to the floor 55 of the trough 54 , like the ventilator 64 and the condenser 63 .
As in the first embodiment, the ventilator 64 , which is disposed between the condenser 63 and the compressor 65 , serves to force cool the condenser 63 by drawing cold air across the surface of the condenser 63 by way of the aperture 59 in the front wall 58 (as indicated by arrows C), from where it is subsequently fed through the ventilator 64 to the compressor 65 in order to the compressor 65 . The cold air that is fed to the compressor 65 is split thereby into non-illustrated air sub-streams that sweep past the side of the compressor 65 , one of which is led along the solid sidewalls 56 , and one of which is led along the bottom of the cooling device housing at the base side. The two sub-streams are thereby conducted to the aperture 61 in the back wall 60 . The air sub-streams that are fed to the aperture 61 in the back wall escape from the trough by way of the aperture 61 and flow into the air channel formed by the back wall of the built-in cooling device 25 and the back wall of the niche 22 , through which the exhaust air that has been enriched with heat upon passing the device assemblies escapes into the standing area of the unit 10 . In the second exemplifying embodiment, as in the first embodiment, the structural unit formed by the condenser 63 and the ventilator 64 is positioned in front of the aperture 61 in the back wall 60 in the flow direction of the cold air that is force driven by the ventilator.
In the embodiments, the supply apertures 36 and 59 for the cold air are spatially separated from the escape apertures 39 and 61 , respectively, in the trough space 40 and 62 , respectively, to at least substantially prevent a mixing of the cold air that flows into the trough space 40 and 62 with the hot exhaust air that flows therefrom.
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A cooling device for installation in a furniture niche includes at least one thermally insulating container defining a cooling space and having a door for sealing the space, and a cooler having a compressor, a condenser, and a ventilator. The base has at least two sidewalls, a front region disposed near the door, a rear region, at least one air supply aperture at the front region, and an exhaust aperture at the rear region. The base houses the compressor, condenser, and ventilator. The base is disposed below the cooling space and is force ventilated by the ventilator through the air supply aperture and the exhaust aperture. The exhaust aperture is in at least one of the sidewalls, preferably, in the rear region of the base averted from the door. Preferably, the cooling device is installed in a furniture niche of a kitchen unit.
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BACKGROUND OF THE INVENTION
(The invention described herein was made under Grant GM 13980 from National Institutes of Health, Department of Health, Education and Welfare.)
It has been found desirable in the field of chemistry dealing with the morphine alkaloids to carry out molecular modifications which will alter the basic characteristics of morphine to obtain compounds which are either substantially non-addicting analgesics or narcotic antagonists or have other desirable properties. One of the major problems in this area has been the removal of the alkyl group, usually the methyl group, from the ring nitrogen and, under certain circumstances, its replacement with alkyl moieties other than the methyl group.
A substantial advance in this art was achieved by one of the co-inventors herein in the work patented by him and other co-workers in U.S. Pat. No. 3,905,981. In this work, it was discovered that vinyl chloroformate and certain derivatives thereof would replace the methyl group on the ring nitrogen, and be removable therefrom under mild conditions which did not adversely affect most of the other labile groups to be found on most of the starting materials in this field which are generally available.
In order that the present application not be too voluminous, the disclosure of the aforementioned U.S. Pat. No. 3,905,981, is incorporated herein by reference. Unfortunately, it was found that where a hydroxy group is present in the 14-position of the morphinan skeleton, the yields in the N-dealkylation step are not satisfactory for commercial purposes (see Example VI of the patent).
It was therefore believed desirable to seek a route by which the vinyl haloformate dealkylation could be applied to 14-hydroxylated compounds in a manner which would give rise to commercially satisfactory yields as well as clean products.
SUMMARY OF THE INVENTION
It has been found that when a N-alkylated, suitably N-methylated, 14-hydroxymorphinan, suitably a 3,14-dihydroxymorphinan, protected at the 3-position, is acylated at the 14 position, it may be readily N-dealkylated using vinyl haloformate. It has been found that other haloformates such as 2,2,2-trichloroethyl chloroformate are also operative. The process of the present invention is operative, as will be shown in more detail hereinbelow, regardless of whether or not a substituent is present at the 3, 4, 5, or 6 positions. Where, for example, a hydroxy group is originally present at the 3 position, this may, if desired, be regenerated together with the hydroxy group at the 14 position after the N-dealkylation step has taken place. The process of the present invention provides, inter alia, more commercially efficient routes to naloxone and naltrexone as well as providing the initial step for a more efficient synthesis of nalbuphine and for another competitive synthesis of naltrexone disclosed and claimed in Applicants' co-pending application filed concurrently herewith.
The process of the present invention may be summarized in the flow sheet set forth hereinbelow.
The flow diagram of structural formulae is of general applicability, the Examples shown however are illustrative and not limiting.
__________________________________________________________________________ (a) (b) (c) (d) (e) (f) Z=R.sub.1 O Z=R.sub.1 O Z=R.sub.1 O Z=R.sub.1 O Z=R.sub.1 O Z=R.sub.1 O R.sub.2 +R.sub.3 =O R.sub.2 +R.sub.3 =O R.sub.2 +R.sub.3 =O R.sub.2 +R.sub.3 =O R.sub.2 =R.sub.3 R.sub.2 =R.sub.3 =H Q = O Q = O Q = O Q = O Q = H,H Q__________________________________________________________________________ = O ##STR1## 1) R.sub.1 = H R.sub.5 = CH.sub.3 R.sub.1 = CH.sub.3 R.sub.5 = CH.sub.3 R.sub.1 = CH.sub.3 R.sub.5 R.sub.1 = CH.sub.3 R.sub.5 = CH.sub.3 R.sub.1 = H R.sub.5 = CH.sub.3 R.sub.1 = H R.sub.5 = CH.sub.3 ##STR2## ##STR3## 2) R.sub.1 = Ac R.sub.5 = CH.sub.3 R.sub.4 R.sub.1 = CH.sub.3 R.sub.5 = CH.sub.3 R.sub.4 = Ac R.sub.1 = CH.sub.3 R.sub.5 = CH.sub.3 R.sub.4 = Cb R.sub.1 = CH.sub.3 R.sub.5 = CH.sub.3 R.sub.4 R.sub.1 = Ac R.sub.5 = CH.sub.3 R.sub.4 = R.sub.1 = Ac R.sub.5 = CH.sub.3 R.sub.4 = Ac ##STR4## 3) R.sub.1 = Ac R.sub.4 = Ac R.sub.5 = VOC R.sub.1 = CH.sub.3 R.sub.4 = Ac R.sub.5 = R.sub.1 = CH.sub.3 R.sub.4 = Cb R.sub.5 = VOC R.sub.1 = CH.sub.3 R.sub.4 = Ac R.sub.5 = TOC R.sub.1 = Ac R.sub.4 = Ac R.sub.5 R.sub.1 = Ac R.sub.4 = Ac R.sub.5 = VOC ##STR5## ##STR6## ##STR7## ##STR8## ##STR9## ##STR10## ##STR11## ##STR12## 4) R.sub.1 = CH.sub.3 R.sub.4 = Ac R.sub.1 = CH.sub.3 R.sub.4 = Ac R.sub.1 = CH.sub.3 R.sub.4 R.sub.1 = CH.sub.3 R.sub.4 = R.sub.1 = Ac R.sub.4 = Ac R.sub.1 = Ac R.sub.4 = Ac ##STR13## 5) R.sub.1 = H R.sub.1 = CH.sub.3 R.sub.1 = CH.sub.3 R.sub.1 R.sub.1 = H (a) (b) (g) (e) (f) Z=R.sub.1 O Z=R.sub.1 O Z=R.sub.1 O Z=R.sub.1 O Z=R.sub.1 O R.sub.2 +R.sub.3 =O R.sub.2 +R.sub.3 =O R.sub.2 +R.sub.3 =O R.sub.2 =R.sub.3 R.sub.2 =R.sub.3 =H Q = O Q = O Q = O Q = H,H Q__________________________________________________________________________ = O ##STR14## 6) R.sub.1 = CH.sub.3 R.sub.5 ' = Cp R.sub.1 = CH.sub.3 R.sub.5 ' = Ay ##STR15## 7) R.sub.1 = H R.sub.5 ' = Ay R.sub.1 = H.sub.3 R.sub.5 ' = Cp R.sub.1 = H.sub.3 R.sub.5 ' = Ay R.sub.1 = H R.sub.5 ' = Ay R.sub.1 = H R.sub.5 ' =__________________________________________________________________________ Cp
In the foregoing reaction sequence only the common reagents or reagent factors are shown.
[A] is the anion of any proton acid capable of forming an acid addition salt with a secondary amine, included are the anions of mineral acids such as halide, suitably chloride or bromide, bisulfate, sulfate, nitrate, phosphate and the like, the anions of organic acids such as carboxylic or lower alkanoic acids such as formates, acetate, propionate and the like, and anions of sulfonic acids, suitably arylsulfonic acids such as benzene or toluene sulfonates and of alkylsulfonic acids such as methanesulfonate.
The foregoing list is not intended to be exhaustive or limiting but merely exemplary.
Z is hydrogen or R 1 O, R 1 is hydrogen, alkanoyl, phenylalkanoyl, substituted phenylalkanoyl, suitably alkyl or polyalkyl phenylalkanoyl, cycloalkylcarbonyl; alkyl; cycloalkyl; cycloalkyl alkyl, phenylalkyl and substituted phenyl loweralkyl;
R 2 and R 3 may each be hydrogen or when taken together are oxa;
Q is 2 hydrogen atoms or oxo;
R 4 is alkanoyl, phenylalkanoyl, substituted phenylalkanoyl, suitably alkyl or polyalkyl phenylalkanoyl, or cycloalkylcarbonyl;
R 5 is alkyl, usually methyl;
R 5 ' is alkyl, usually other than methyl, cycloalkyl, cycloalkyl alkyl, phenylalkyl, allyl, or alkyl substituted allyl.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the process of the present invention, there may be used any N-alkylated 14-hydroxymorphinans. While the process of the present invention would be operative for any members of this group, the natural and synthetic compounds to which the process would usually be applied carry a hydroxy or substituted hydroxy group at the 3 position; thus, R 1 may be hydrogen, alkanoyl, suitably lower alkanoyl -- for example, having 1 to 5 carbon atoms in the alkyl moiety thereof -- for example, acetyl, propionyl, butyryl, valeryl, and the like, phenylalkanoyl and substituted phenylalkanoyl suitably phenyl lower alkanoyl such as benzoyl, phenylacetyl, phenylpropionyl, phenylbutyryl, and the like, and as substituted pheyl lower alkanoyls may be included moieties having -- for example, alkyl substituents in phenyl nucleus, also included is cycloalkylcarbonyl such as cycloloweralkylcarbonyl of 3 through 6 carbon atoms in the cycloalkyl moiety, including in particular cyclopropyl and cyclobutyl, R 1 may also be alkyl, suitably lower alkyl of 1 to 5 carbon atoms such as methyl, ethyl, propyl, butyl, and the like, cycloalkyl of 3-6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, cycloalkyl lower alkyl wherein the cycloalkyl and alkyl, suitably lower alkyl moieties are then set for the immediately hereinabove, or phenylalkyl such as benzyl, phenethyl, phenylbutyl, and the like.
Where R 1 is hydrogen the hydroxy group at the 3-position is protected at least in steps 1-4 as shown in the flow sheet by any protecting group known in the art to be stable under the reaction conditions set forth, acylation suitably alkanoylation being most preferred.
R 2 and R 3 are each hydrogen or when taken together are oxa, Q is either 2 hydrogen atoms or oxo. Thus, in the synthetic morphinan series, R 1 , R 2 and Q are all hydrogen though Q may also be oxo and in the natural series R 1 is usually hydrogen or methyl, R 2 with R 3 is oxa, and Q is oxo. Among the most important starting materials may be mentioned oxymorphone which is utilized in the naloxone and naltrexone syntheses, and oxycodone which is utilized in the naltrexone synthesis, as well as in the nalbuphine synthesis.
R 5 is lower alkyl of 1-6 carbon atoms, phenyl lower alkyl having 1-6 carbon atoms in the lower alkyl moiety, cycloalkyl or cycloalkyl lower alkyl of 3-6 carbon atoms in the cyclic moiety and 1-5 carbon atoms in the lower alkyl moiety.
Any readily available acylating agent may be employed in the 14-acylation to give rise to the R 4 group. It is preferred to utilize an alkanoylating agent, suitably an acid halide suitably an acid chloride or an acid anhydride giving rise to a lower alkanoyl moiety having 1 to 5 carbon atoms in the alkyl moiety. There may also be included phenyl lower alkanoyl moieties suitably benzoyl, also included are cycloalkylcarbonyl moieties having from 1 to 6 carbon atoms in the cycloalkyl moiety. Especially favored are the acetylating agents such as acetyl chloride or acetic anhydride where it is desired to utilize the acetyl moiety purely as a protecting group. Where it is desired to proceed further to the synthesis of naltrexone or nalbuphine in the manner disclosed in the co-pending application, there is employed an alkanoylating agent generating initially 14-O-cyclobutylcarbonyl and 14-O-cyclopropylcarbonyl moieties such as cyclobutanecarboxylic acid anhydride and cyclopropanecarboxylic acid anhydride.
The acylation at the 14-hydroxy position is carried out by methods well known in the art. Among the suitable methods may be mentioned Lewenstein, British Pat. No. 955,493. In this procedure, the starting material containing the 14-hydroxy group is heated under reflux and agitation in an inert atmosphere, suitably a nitrogen atmosphere, with the alkanoylating agent, suitably with the acid anhydride, if that is the alkanoylating agent of choice. The heating is carried on for from about one to about three hours, suitably for about two hours, at between 80° C. and 120° C., suitably 100° C., and the volatiles removed under reduced pressure.
It is generally not necessary to purify the acylated compound (2). Indeed such a step can reduce the ultimate yields due to hydrolysis loss in the recrystalization step.
The 14-acyloxy-N-alkylated compound (2) wherein the alkyl moiety is usually methyl, is then treated with the appropriate haloformate. Haloformates having the formula
Y-O-CO.X
wherein Y is vinyl or substituted vinyl, 2-mono-, di-, or tri haloethyl, suitably 2,2,2-trichloroethyl, and phenyl or substituted phenyl may be employed. The vinyl haloformates which may be employed are more specifically disclosed in U.S. Pat. No. 3,905,981, column 3, lines 4 through 45, which are incorporated herein by reference. Of the haloformates which may be employed in this reaction, the best results have been obtained using vinyl chloroformate itself, although the results obtained using the trichloroethyl chloroformate are almost as good, excluding recoverable starting material.
The reaction between the tertiary amine group and the vinyl chloroformate is generally carried out in a suitable inert solvent such as 1,2-dichloroethane, benzene, ether, methylene chloride, toluene, chloroform, tetrahydrofuran, sulfolane, and the like. Although the reactants may be mixed together at or near room temperature or at elevated temperatures, and the vinyl chloroformate may be added to the tertiary amine, the preferred procedure for mixing the reactants, particularly in those reactions where HCl is lost on removal of the alkyl group (such as in the splitting off of some tertiary and secondary alkyl groups), is to add the tertiary amine slowly to a stoichiometric excess of the vinyl chloroformate in the cooled reaction solvent. The generally preferred addition temperature is in the range of -40° C. to 0° C., after which the mixture is allowed to warm to room temperature and then either left at room temperature for several hours or else heated for a shorter period. A short reflux period (for example, 30 minutes to an hour in 1,2-dichloroethane, often longer in benzene or ether) is often advantageous to eliminate a volatile alkyl halide if such is produced on dealkylation or to guarantee completion of the reaction when the dealkylation has not previously been attempted and its rate is unknown.
In the demethylation of complex and expensive tertiary amines, it is often commercially advantageous to perform the vinyl chloroformate addition at or above room temperature and to heat the reaction mixture at 60°-80° C. for several hours before work-up.
When HCl or other acid is liberated during the N-dealkylation, a suitable proton scavenger may advantageously be included in the reaction mixture to remove the acid. The proton scavenger may itself be a tertiary amine provided such is more basic but less reactive toward vinyl chloroformate than the amine to be dealkylated. Proton scavengers of this type which have been discovered to be particularly useful include 1,8-bis-(dimethylamino)-naphthalene, N-alkyldicyclohexylamines (such as N-methyl- or N-ethyldicyclohexylamines) and N-alkyl-2,2,6,6-tetramethylpiperidines. The former and the final series of proton scavengers above can be recovered in essentially quantitative yield after treatment with vinyl chloroformate in 1,2-dichloroethane at reflux for four hours. In N-dealkylation of tertiary amines with vinyl chloroformate, the inclusion of small amounts of proton scavengers like 1,8-bis-(dimethylamino)-naphthalene in the reaction mixture to tie up traces of acid impurities (generated for example from trace moisture) is often advantageous. If a stoichiometric amount of 1,8-bis-(dimethylamino)-naphthalene or a similar proton scavenger is included in the reaction medium for tertiary amino N-dealkylation with vinyl chloroformate, the tertiary amino hydrohalide or other acid salt may be used as the reactant without prior conversion to the free tertiary amine. This procedure is especially convenient when the tertiary amine to be N-dealkylated is most easily obtained or handled as some acid salt.
Reaction of vinyl chloroformate with a candidate tertiary amine having at least one alkyl group attached to the amino N atom results in the removal of the N-alkyl group or one of the N-alkyl groups from the amino N atom of the tertiary amine, and replacement thereof by the vinyloxycarbonyl or, as designated hereinbelow, the VOC group. The resulting VOC-amide of a secondary amine is thereafter cleaved to remove therefrom the VOC group and obtain the corresponding secondary amine as its hydrohalide or other acid salt.
Several techniques are available for removal of the VOC group from the amino N atom. For example, the VOC group may be split off by titration of the VOC-amide with bromine in an inert solvent followed by the addition of a volatile alcohol such as methanol or ethanol (ROH) and removal of the solvent, excess alcohol, and the BrCH 2 CH(OR) 2 at reduced pressure to produce the secondary amine hydrobromide.
In another procedure the alcohol is present in solution with the VOC-amide as the bromine is added. Alternatively, the VOC group may be split off by treatment with 1.1 to 5 or more stoichiometric equivalents of an acid such as HCl or HBr in the presence of a hydroxylic reagent, such as water, a carboxylic acid or preferably an alcohol, which also often functions as the solvent. When other groups in a particular VOC-amide are sensitive to alcoholic acid, this cleavage may preferably be carried out as two separate steps. First, the VOC-amide is treated with HX (for example, HCl or HBr) in an inert solvent such as an ether or chlorinated hydrocarbon. Then the intermediate ##STR16## is freed from most excess acid and finally warmed with a volatile alcohol such as methanol or ethanol (ROH) yielding the secondary amine hydrohalide, CO 2 , and CH 3 CH(OR) 2 . Solvent, byproducts, and excess reagents are easily removed by evaporation at reduced pressure. Moreover, the VOC group may be split off from the VOC-amide by mercuric ion induced hydrolysis with mercuric acetate in acetic acid.
Where the N-dealkylating agent is a group giving rise to the halo or polyhaloalkoxy carbonyl moiety, for example the 2,2,2-trichloroethoxy carbonyl group (TOC) the 14-acyloxy-N-TOC compound is dissolved in a lower alkanol or lower alkanoic acid or combination thereof, suitably in the presence of water, for example in aqueous acetic acid and treated with an electron donor, suitably metallic zinc.
The thus obtained acid salts of 14-acyloxymorphinans (4) are then further reacted in accordance with the ultimate intention of the synthetic sequence. Thus, where it is desired to form the corresponding 14-hydroxy unsubstituted secondary amino compound (5), for example, noroxymorphone in the naloxone synthesis and noroxycodone in the naltrexone synthesis, the salts (4) are treated with aqueous mineral acid under moderately vigorous conditions. It is preferred to take up the acid salt (4) in moderately strong aqueous mineral acid. An aqueous solution containing between about 15 and about 50% by weight of acid is suitable, sulfuric or hydrochloric acids being especially preferred. Suitably, there are utilized about 1 part by weight of the 14-acyloxy compound (4) to 10 parts by weight of acid. This ratio is in no way considered to be limiting; however, an excess of acid is desirable. For the best results, the hydrolysis is carried out in an inert atmosphere, suitably in a nitrogen atmosphere, under reflux. The reaction may run from between about two to about twenty hours, reaction times of between five and ten hours are generally preferred. The reaction mixture is then cooled, suitably to ice bath temperatures, and basified to a pH of between 8 and 10, suitably between 8.5 and 9.0, by addition of aqueous base, suitably concentrated ammonium hydroxide. Under certain circumstances, it is desirable to permit the solution to warm to ambient temperature (15° to 25° C.), acidify to about pH 2 to about pH 3 followed by extraction with a substantially water immiscible strong polar organic solvent, suitably a halogenated hydrocarbon such as chloroform. The organic extract is discarded and the aqueous solution rebasified as set forth hereinabove. In certain cases, for example, where the product is noroxymorphone, the addition of the base forms a precipitate which is effectively insoluble in common organic solvents. In this case, the precipitate is merely separated by filtration, washed with cold, suitably ice water, and dried under reduced pressure. In other cases, the basified solution is extracted with a strong polar substantially water immiscible solvent such as a halogenated hydrocarbon, suitably chloroform or methylene chloride. The organic extract is then dried, the solvent removed, and theresidue purified, suitably by passing through a short alumina column in the same or other polar substantially water-immiscible solvent.
Where the ultimately desired product is one wherein the realkylation of the ring nitrogen does not operate with high efficiency, for example the nalbuphine synthesis, the 14-acyloxy group originally chosen, for example cyclobutylcarbonyl, is caused to rearrange from a 14-O-acyl compound to an N-acyl compound by treatment of (4) with base, suitably mild base, followed by reduction of the carbonyl group to the corresponding methylene group. Where the starting compound (4) carries a keto moiety at the 6 position, this must, of course, be protected prior to the reduction step or else reoxidized if converted to the 6-alcohol during reduction. These procedures are set forth in greater detail in Applicants' co-pending application filed concurrently herewith.
As stated hereinabove, the conversion of the compound (5) formed in the manner set forth above to the desired N-substituted compound (6) is achieved by methods which will vary in accordance with the total structure of the compound, and the group which it is desired to place as a tertiary substituent upon the ring nitrogen. Thus, for example, where it is desired to form naloxone (7a) or other N-allyl analogs thereof having a 3,14-dihydroxy substitution pattern, compound (5) for example, noroxymorphone (5a), is allylated in the usual manner by reaction with allyl bromide in the presence of an acid scavenger, for example, sodium bicarbonate in an alkanolic medium, suitably absolute ethanol under an inert atmosphere, for example, a nitrogen atmosphere, by heating under reflux for between fifty and seventy hours. Despite the occurrence of phenol allylation which accounts for some yield loss, it has been found satisfactory to proceed in this direct manner.
On the other hand, where it is desired to prepare naltrexone (7b), it was found desirable to proceed via N-cyclopropylmethylnoroxycodone (6b) where this problem does not arise since the phenolic hydroxy at the 3-position is methylated. Thus, it is possible to force the cyclopropylmethylation at the nitrogen which will give substantially better yield of the end product than it was heretofore available. Under the methods of the art, it was customary to alkylate -- i.e., cyclopropylmethylate -- noroxymorphone which was not as efficient a process as desired due to the cyclopropylmethylation of the phenolic hydroxy group.
The N-cyclopropylmethylnoroxycodone (6b) is then O-demethylated, suitably by the high temperature pyridine hydrochloride method or one of the other methods used in the art, (e.g. BBr 3 ) for the conversion of oxycodone to oxymorphone.
It has been our surprising finding that making naltrexone via noroxycodone and N-cyclopropylmethylnoroxycodone is more efficient (circa 54% overall from oxycodone) than proceeding via noroxymorphone to naltrexone even when produced by the novel procedures of the present invention (43% overall from oxycodone via oxymorphone). Both procedures are more than twice as efficient as the procedures of the art which produce noroxymorphone from oxycodone via oxymorphone (Seki, Takamine Kenkyusho Nempo, 12, 56 (1960)), which proceed in an overall yield of about 21%. A third procedure for the synthesis of naltrexone is set forth in Applicant's co-pending application filed concurrently herewith.
Where it is desired to form the other compounds within the scope of the present invention wherein the N-substituent is other than methyl, the ether bridge between positions 3 and 5 has been replaced by hydrogen substituents, and the group at position 6 is either oxo or two hydrogen atoms one may proceed by either the route set forth for the synthesis of naloxone or the route set forth for the synthesis of naltrexone.
The foregoing discussions and the following experimental examples should be considered merely as illustrative of the invention and in no way limiting thereof. In the following Examples, all temperatures are in ° C. Silica Gel GF 254 plates with 90% methylene chloride -10% methanol (v/v) as the eluent were used for tlc analyses to obtain the R f reference values.
EXAMPLE I
3,14-DIACETYLOXYMORPHONE (2a)
Oxymorphone (1a) (3.01 g, 0.01 mole) in 25 ml of acetic anhydride was heated under nitrogen with stirring for two hours at 100° C. The volatiles were then removed in vacuo and the product was vacuum dried (0.2 torr) for two days to yield 3,14-diacetyloxymorphone (2a) as an off-white powder; mp 215°-219° C. (Lit.: Lewenstein residue (Brit. Pat. No. 955,493) (1964) mp 220° C., Seki residue (Takamine Kenkyusho Nempo, 12, 56 (1960) mp 209°-213° C., Seki ethanol recrystalized mp 214°-215° C.); yield 3.90 g (100%); tlc: single spot of R f 0.51. Although the compound could be recrystallized from ethanol (with significant loss by hydrolysis), its purity as determined by NMR analysis and tlc made this purification step superfluous.
IR(μ): 3.54 (w), 3.60 (m), 3.63 (w), 5.69 (s), 5.75 (sh), 5.79 (s), 6.15 (m); CH 2 Cl 2 .
NMR(δ): 6.9-6.5 (m), 4.62 (s), 4.3-4.1 (m), 3.5-1.2 (m), with large spikes of equal area at 2.32, 2.29, and 2.16; ratio 2:1:1:19; CDCl 3 .
MS(m/e): 385.1543 (P, 18%, Calc. 385.1524), 343.1428 (P-CH 2 CO, 68%, Calc. 343.1419), 284 (33%), 43 (100%)
In accordance with the above procedures but starting in place of oxymorphone (1a) with N-methyl-3,14-dihydroxymorphinan (1e) or N-methyl-3,14-dihydroxy-6-oxomorphinan (1f) there is obtained N-methyl-3,14-diacetoxymorphinan (2e) or N-methyl-3,14-diacetoxy-6-oxomorphinan (2f).
EXAMPLE II
14-ACETYLOXYCODONE (2b)
(Method of Freund and Speyer, J. Prakt Chem. 94, 135 (1916)).
Oxycodone (1b) (15.8 g, 0.05 mole) was refluxed in freshly distilled acetic anhydride (75 ml) (Baker) for 45 minutes. After cooling, the solution was poured onto ice (300 g) and stirred while allowed to warm to room temperature to hydrolyze residual anhydride. The solution was again cooled to ca. 15° C. and then kept at this temperature while cold concentrated aqueous ammonium hydroxide was added to raise the pH to 9 and precipitate the product. The mixture was further cooled to 0° C. before the product was filtered off, washed with cold water (75 ml), and vacuum dried; 14-acetyloxycodone (2b) is given as white powder of mp 207°-213° C.; yield 17.9 g (100%); tlc: single spot of R f 0.50 (the R f of oxycodone in this system was 0.46). Recrystallization from 95% ethanol gave pure white needles; mp 213°-215° C. (Lit. Freund and Speyer 215°-216° C.).
IR(μ): 3.53 (w), 3.57 (w), 3.59 (w), 5.74 (sh), 5.79 (s), 6.11 (w), 6.21 (w); CH 2 Cl 2 .
NMR(δ): 6.9-6.5 (m), 4.69 (s), 4.3-4.1 (m), 3.94 (s), 3.5-1.2 (m, with large spikes at 2.36 and 2.20); ratio 2:1:1:3:16; CDCl 3 .
MS(m/e): 357 (P, 100%), 314 (P-Ac, 52%).
Only 89% of the product was recovered from the recrystalization: thus, the white powdered reaction product was ordinarily used in subsequent reactions.
EXAMPLE III
14-CYCLOBUTYLCARBONYLOXYCODONE (2c)
A solution of oxycodone (1b) (7.88 g, 0.025 mole) and cyclobutanecarboxylic acid anhydride (9.11 g, 0.05 mole) in dry dioxane (30 ml) was heated (under nitrogen) at 100° C. for 18 hours. After cooling, the solvent was removed at reduced pressure and the residue, an orange oil, was diluted with water (100 ml). Aqueous 20% hydrochloric acid (3 ml) was added to dissolve the amine and the mixture was stirred for two hours to hydrolyze the remaining anhydride. The solution was then cooled (ice bath) and taken to ca. pH 11 with cold concentrated aqueous ammonium hydroxide. Next, the precipitated product was filtered off, washed with cold water (50 ml), and vacuum dried; pale yellow grannular solid; mp 140.5°-144.5° C.; yield 9.93 g (100%); tlc: single spot of R f 0.60.
Recrystalization from ethanol gave 14-cyclobutylcarbonyloxycodone (2c) as fine white needles; mp 149.7°-150.3° C.; analysis sample mp 150.9°-151.1° C.
Only 78% of the product was recovered from the ethanol recrystalization steps; thus, the recrystalization was omitted in the preparation of material for use in the following N-demethylation reaction.
Calc. for C 23 H 27 NO 5 : C, 69.50%; H, 6.85%; N, 3.52%; Found: C, 69.41%; H, 6.81%; N, 3.66%.
IR(μ): 3.56 (w), 3.60 (m), 3.64 (w), 5.73-5.91 (s), 6.12 (w), 6.21 (m): CH 2 Cl 2 .
NMR(δ): 6.8-6.5 (m), 4.63 (s), 4.3-4.1 (m), 3.87 (s), 3.5-1.2 (m, with large spike at 2.31); ratio 2:1:1:3:20; CDCl 3 .
MS(m/e): 397.1875 (P, 100%, Calc. 397.1889), 314.1392 (P-cyclobutylcarbonyl, 51%, Calc. 314.1392), 298 (18%), 55 (27%).
In accordance with the above procedure but where in place of oxycodone there is used as starting material 3-propyloxymorphone, 3-cyclopropyloxymorphone, 3-cyclopentyloxymorphone, 3-ethoxy-14-hydroxy-6-oxomorphinan and the like, there is obtained the corresponding 3-propyl-14-acetyloxy morphone, 3-cyclopropyl-14-acetyloxymorphone, 3-cyclopentyl-14-acetyloxymorphone, 3-ethoxy-14-acetyloxy-6-oxo-morphinan and the like.
EXAMPLE IV
CYCLOBUTANECARBOXYLIC ACID ANHYDRIDE
Cyclobutanecarboxylic acid (Aldrich) (24.0 g, 0.24 mole) in 25 ml of ether was added (10 minutes) to a cooled, mechanically stirred solution of pyridine (Fisher) (18.9 g, 0.24 mole) in ether (200 ml). After 15 minutes, the ice bath was replaced by an ice-salt bath (-8° C.) and cyclobutanecarboxylic acid chloride (Aldrich) (28.4 g, 0.24 mole) in 25 ml of ether was slowly added (45 minutes) with vigorous stirring. During the addition, another 50 ml of ether was added to facilitate the stirring of the mixture as it thickened with precipitated pyridine hydrochloride. The cooling bath then was removed and the mixture was stirred for another hour. After removal of the amine salt by filtration, the product was isolated from the filtrate by vacuum distillation; bp 77°-79° C. at 0.6 torr (Lit. Freund and Gudeman, Chem. Ber. 21, 2692, (1888) 160° C.) yield 37.9 g (88%).
IR(μ): 5.51 (s), 5.73 (s); CCl 4 .
NMR(δ): 3.5-2.9 (m), 2.6-1.6 (m); ratio 2:12; CCl 4 .
EXAMPLE V
N-VOC-3,14-DIACETYLNOROXYMORPHONE (3a)
A flask containing unpurified 3,14-diacetyloxymorphone (2a) (3.90 g, 0.01 mole) was evacuated for three hours (0.3 torr) in a 90° C. oil bath. After the oil bath had cooled to 65° C., the vacuum was replaced by a dry nitrogen atmosphere and 1,2-dichloroethane (15 ml) was added to the flask. Next, vinyl chloroformate (0.03 mole) was syringed into the stirred, pale yellow solution. After 23 hours at 65° C. and one hour at reflux, the volatiles were removed and the residue, a pale yellow foam, was vacuum dried. The foam was then dissolved in ethyl acetate (100 ml) and washed with 0.3 N hydrochloric acid (30 ml), water (30 ml), aqueous 1% sodium bicarbonate (30 ml), and water (30 ml). The dried (over sodium sulfate) solution was evaporated at reduced pressure affording an off-white foam of N-VOC-3,14-diacetylnoroxymorphone (3a); yield 4.44 g (100%); tlc: single spot of R f 0.74. This material was not further purified but taken on directly to noroxymorphone (5a) as described in the following Example.
An analysis sample was prepared by eluting a chloroform solution of reaction product through a short silica gel 60 column followed by evaporation of the total eluate and recrystalization (twice) from methylene chloride pentane: mp 210.5°-211.5° C.
Calc. for C 23 H 23 NO 8 : C, 62.58%; H, 5.25%; N, 3.17%. Found: 62.89%; H, 5.15%; N, 3.37%.
IR(μ): 5.66 (s), 5.73 (s), 5.81 (sh), 5.85 (s), 6.08 (m), 6.18 (w); CH 2 Cl 2 .
NMR(δ): 7.4-6.5 (m), 5.7-5.4 (broad), 5.1-1.3 (m, with small spike at 4.65 and two large spikes of equal area at 2.28 and 2.10); ratio 3:1:19; CDCl 3 .
MS(m/e): 441.1452 (P, 3%, Calc. 441.1422), 398.1238 (P-acetyl), 10%, Calc. 398.1239), 339 (27%), 314 (8%), 312 (10%), 296 (14%), 270 (10%), 43 (100%).
Starting 3,14-diacetyloxymorphone (3a) was recovered from the pooled aqueous wash solutions from the first experiment above by basification (with sodium carbonate) and extraction into chloroform (3 × 30 ml). After washing with water (30 ml) the dried (over sodium sulfate) extract was evaporated to an off-white solid; yield 0.12 g (3%); tlc: one spot of R f 0.51 (starting material) plus a trace at R f 0.47 (monoacetyl compound).
EXAMPLE VI
N-VOC-14-ACETYLNOROXYCODONE (3b)
A flask containing 14-acetyloxycodone (2b) (7.15 g, 0.02 mole) was evacuated for one hour (0.2 torr) in a 65° C. oil bath. After substitution of a dry nitrogen atmosphere for the vacuum, dry 1,2-dichloroethane (20 ml) was added to the cooled flask (ice bath). Next, vinyl chloroformate (0.06) mole in 1,2-dichloroethane (10 ml) was dripped into the stirred white suspension (10 minutes). During the next hour, the mixture was gradually warmed up to 65° C. and then left at that temperature for 23 hours. An hour's reflux preceded rotary evaporation of the volatiles. The residue, a white foam, was partitioned between water (50 ml) and 4:1 ethyl acetate-ether (125 ml). The aqueous layer was separated and the organic layer then washed with 0.3 N hydrochloric acid (2 × 20 ml), 0.1 N hydrochloric acid (20 ml), water (20 ml), aqueous 1% sodium bicarbonate (20 ml), and water (20 ml). Back extraction of the combined aqueous washes with fresh ethyl acetate (50 ml) preceded drying over anhydrous sodium sulfate and vacuum evaporation which gave a white granular solid; mp 181°-182.5° C.; yield 7.73 g (94%); tlc: single spot of R f 0.64. Recrystalization from methanol or methylene chloride-pentane afforded N-VOC-14-acetyloxycodone (3b), mp 182.5°-183.5° C.
Calc. for C 22 H 23 NO 7 : C, 63.92%; H, 5.61%, N, 3.39%. Found: C, 63.76%, H, 5.83%; N, 3.47%.
IR(μ): 3.50 (w), 5.73 (s), 5.78 (s), 5.84 (s), 6.07 (m), 6.14 (w); CH 2 Cl 2 .
NMR(δ): 7.4-7.0 (m), 6.9-6.6 (m), 5.7-5.5 (broad), 5.1-3.8 (m, with small spike at 4.68 and large spike at 3.89), 3.4-1.3 (m, with large spike at 2.12); ratio 1:2:1:7:12; CDCl 3 .
MS(m/e): 413.1466 (P, 73%, Calc. 413.1473), 354.1324 (P-OAc, 28%, Calc. 354.1340), 353.1266 (P-HOAc, 100%, Calc. 353.1262), 328 (47%), 326 (54%), 310 (94%), 284 (81%).
The aqueous solution from the above extractions was made basic with sodium carbonate and then extracted with chloroform (3 × 50 ml). The unreacted 14-acetyloxycodone was recovered as a white solid by evaporation of this dried over sodium sulfate solution. White needles were obtained by recrystalization from 95% ethanol; mp 212°-214° C. (lit. 215°-216° C.); yield 0.3 g (4%).
In accordance with the above procedure but where in place of 14-acetyloxycodone, there is utilized N-methyl-3,14-diacetoxymorphinan (2e) or N-methyl-3,14-diacetoxy-6-oxomorphinan (2f), there is obtained the corresponding N-VOC-3,14-diacetoxymorphinan (3e) and N-VOC-3,14-diacetoxy-6-oxomorphinan (3f).
Similarly, but where in place of vinyl chloroformate there is used 2,2,2-trichloroethyl chloroformate, or phenyl chloroformate, there are obtained the corresponding N-TOC-(i.e., N-trichloroethoxycarbonyl) or N-POC-(i.e., N-phenoxycarbonyl) compounds, respectively.
EXAMPLE VII
N-VOC-14-CYCLOBUTYLCARBONYLNOROXYCODONE (3c)
A reaction flask containing 14-cyclobutylcarbonyloxycodone (2c) (5.96 g, 0.15 mole) prepared in accordance with Example III was evacuated for an hour at 0.4 torr in an 80° C. oil bath. Next, the vacuum was replaced by a dry nitrogen atmosphere, and when the oil bath had cooled to 63° C., dry 1,2-dichloroethane (20 ml) was syringed into the flask. Vinyl chloroformate (0.045 mole) in 1,2-dichloroethane (5 ml) was then dripped into the stirred homogeneous reaction mixture (10 minutes). After 23 hours at this temperature, the mixture was refluxed for an hour and the volatiles were then removed at reduced pressure. The off-white foamy residue was next partitioned between 4:1 ethyl acetate-ether (100 ml) and water (20 ml). After separation, the organic layer was washed with 0.3 N hydrochloric acid (20 ml), water (20 ml), aqueous 1% sodium bicarbonate (20 ml), and water (20 ml), then dried over sodium sulfate and evaporated in vacuo, to yield N-VOC-14-cyclobutylcarbonylnoroxycodone (3c) as a white foam (6.42 g, 94%) which could not be crystalized; its spectral properties and behavior in subseqent reactions indicated the presence of only one compound; tlc: single spot of R f 0.74. A sample was prepared for combustion analysis by eluting a chloroform solution of the compound through a short silica gel 60 column followed by vacuum evaporation of the total eluate and vacuum drying of the glass at 70° C.
Calc. for C 25 H 27 NO 7 : C, 66.21%; H, 6.00%; N, 3.09%. Found: C, 66.15%; H, 6.21%; N, 2.86%.
IR(μ): 3.56 (w), 5.71-5.92 (s), 6.08 (m), 6.12 (sh), 6.22 (w); CH 2 Cl 2 .
NMR(δ): 7.4-7.0 (m), 6.9-6.5 (m), 5.8-5.5 (broad), 5.1-3.7 (m, with small spike at 4.68 and large spike at 3.92), 3.5-1.3 (m); ratio 1:2:1:7:16; CDCl 3 .
MS(m/e): 453.1763 (P, 78%, Calc. 453.1785), 366 (44%), 353.1224 (P-cyclobutanecarboxylic acid, 100%, Calc. 353.1262), 310.1054 (P-cyclobutanecarboxylic acid-vinyloxy, 58%, Calc. 310.1078), 284 (53%), 254 (25%), 240 (32%), 226 (24%), 212 (37%).
Unreacted 14-cyclobutylcarbonyloxycodone (2c) was recovered by basification (solid sodium carbonate) and chloroform extraction of the combined aqueous washes. The tan solid obtained after drying over sodium sulfate and evaporation of the extract was recrystalized from 95% ethanol; off-white needles of mp 148.5°-149.5° C.; yield 0.30 g (5%).
EXAMPLE VIII
N-(2,2,2-TRICHLOROETHOXYCARBONYL)-14-CYCLOBUTYLCARBONYLNOROXYCODONE (3d)
A flask containing 14-cyclobutylcarbonyloxycodone prepared in accordance with Example III (1.19 g, 0.003 mole) was immersed in a 90° C. oil bath and evacuated (0.3 torr) for two hours. The vacuum was replaced by a dry nitrogen atmosphere and when the oil bath had cooled to 65° C., 1,2-dichloroethane (8 ml) was syringed into the flask. Next 2,2,2-trichloroethyl chloroformate (Aldrich, stored over potassium carbonate) (1.27 g, 0.006 mole) in 1,2-dichloroethane (2 ml) was added (10 minutes). After 23 hours at 65° C. and one hour at reflux, the volatiles were removed and the red oily residue was evacuated overnight. It was then dissolved in ethyl acetate (50 ml) and washed with 0.3 N hydrochloric acid (15 ml), water (15 ml), aqueous 5% sodium bicarbonate (15 ml), and water (15 ml). The organic layer dried over sodium sulfate was evaporated to a light brown foam which was taken up in chloroform (5 ml) and eluted through a short silica gel 60 column (chloroform as eluant) to remove the color. Evaporation of the total eluate afforded N-2,2,2-trichloroethoxycarbonyl-14-cyclobutylcarbonylnoroxycodone (3d) as a substantially pure white foam which was kept at 0.3 torr for two days at 60° C.; tlc: single spot of R f 0.68. From NMR and IR analysis, the product (1.40 g) was estimated to contain ca. 6% 2,2,2-trichloroethyl chloroformate as a contaminant; corrected estimated product yield 79%. Since the contaminant did not interfere in the next reaction, further purification of this material was not attempted.
IR(μ): 5.75 (sh), 5.77 (s), 5.84 (s), 6.11 (w); CH 2 Cl 2 ; 2,2,2-trichloroethyl chloroformate at 5.61 (w).
NMR(δ): 6.9-6.5 (m), 5.9-5.4 (broad), 5.1-1.3 (m, with small spike at 4.82, medium spike at 4.66, and large spike at 3.85); ratio 2:1:23; CDCl 3 ; 2,2,2-trichloroethyl chloroformate at 4.89.
MS(m/e): 559.0746 (P, 12%, Calc. 559.0745), 557.0726 (P, 13%, Calc. 557.0774), 459 (45%), 457 (46%), 366 (5%), 326 (5%), 284 (9%), 240 (13%), 211 (16%), 133 (14%), 131 (14%), 84 (23%), 55 (100%), 35 (18%).
The aqueous wash solutions were combined, basified with sodium carbonate, and extracted with methylene chloride (4 × 15 ml). The extract was washed with water (20 ml), dried over sodium sulfate, and evaporated to a reddish solid residue. By recrystalization from 95% ethanol, unreacted 14-cyclobutylcarbonyloxycodone (3d) was recovered as white needles; mp 148.5°-149.5° C.; yield 0.23 g (19%).
In a similar N-demethylation reaction carried out for 65 hours at 70° C. and five hours at reflux, the estimated yield of product was 73% and only 10% of the starting material was recovered.
Unpurified N-[2,2,2-trichloroethoxycarbonyl]-14-cyclobutylcarbonylnoroxycodone (9'b) (1.36 g. containing ca. 10% 2,2,2-trichloroethyl chloroformate) (0.0022 mole) was dissolved in aqueous 90% acetic acid (45 ml). Zinc dust (Fisher) (1.44 g, 0.022 mole) was added in six portions at 10 minute intervals and the mixture then was stirred for three hours. After filtration, the filtrate was taken to dryness at reduced pressure (25° C., 1 Torr) to yield, 14-cyclobutylcarbonylnoroxycodone acetic acid salt in the presence of zinc acetate and zinc chloride. These inorganic contaminents are generally not removed as they do not interfere with subsequent stages of the reaction sequence.
The NMR spectrum of the above material was found to be substantially identical (except for excess acetate absorption from zinc acetate) to the spectrum of material derived from 14-cyclobutylcarbonylnoroxycodone hydrochloride (from Example II).
EXAMPLE IX
3,14-DIACETYLNOROXYMORPHONE HYDROCHLORIDE (4a) AND NOROXYMORPHONE (5a)
Hydrogen chloride (Matheson, technical, passed through calcium chloride) was bubbled through a stirred solution of the foamy N-VOC-3,14-diacetylnoroxymorphone (3a) (4.44 g), in methylene chloride (60 ml) at ca. 20 cc per minute for 75 minutes. The solvent was removed in vacuo and the leftover pale yellow foam (the hydrogen chloride adduct) was heated under nitrogen at 55° C. for 45 minutes in 60 ml of absolute methanol. Evaporation of the volatiles gave 3,14-diacetylnoroxymorphone hydrochloride (4a) as a pale yellow foam which was dried overnight at 0.3 torr.
IR(μ): 3.5-4.1 (m, broad), 5.67 (s), 5.72 (sh), 5.74 (s): CH 2 Cl 2 .
NMR(δ): 10.9-9.0 (very broad), 7.1-6.6 (m), 5.2-4.5 (broad, with small spike at 4.74), 4.2-1.2 (m, with two large spikes at 2.44 and 2.30); ratio 2:2:2:16; CDCl 3 .
In accordance with the above procedures but where in place of N-VOC-3,14-diacetylnoroxymorphone there is utilized N-VOC-3,14-diacetoxymorphinan (3e) or N-VOC-3,14-diacetoxy-6-oxomorphinan (3f), there is obtained 3,14-diacetoxymorphinan hydrochloride (4e) and 3,14-diacetoxy-6-oxo-morphinan hydrochloride (4f).
Subsequent reflux of 3,14-diacetylnoroxymorphone hydrochloride (4a) for five hours (reaction is not complete by tlc after 3.5 hours) in aqueous 25% sulfuric acid (45 ml) afforded the acid salt of noroxymorphone (5a) which was neutralized to give 5a and precipitated by taking the cooled (ice bath), stirred, burgundy reaction mixture to pH 8.8 (pH meter) with concentrated aqueous ammonium hydroxide. The filtered product was washed with ice water (30 ml) and dried in vacuo to yield noroxymorphone (5a) as a gray powder with no mp; darkened above 260° C.; complete char at 360° C. (lit.: Lewenstein supra no mp, lit.: Seki supra 310°-313° C.); yield 2.73 g (95% based on oxymorphone without subtraction of recovered 3,14-diacetyloxymorphone in preceding Example). Noroxymorphone (5a) is virtually insoluble in common organic solvents.
When the reaction sequence was performed on a smaller scale with recrystalized N-VOC-3,14-diacetylnoroxymorphone, the hydrolysis solution ended up pale yellow instead of burgundy and the noroxymorphone (5a) (95% yield, still no mp) was off-white in color.
IR(μ): 2.8-4 (s, broad), 5.84 (s), 6.15 (m); KBr.
MS(m/e): 287.1169 (P, 100%, Calc. 287.1157), 207 (61%).
In accordance with the above procedure, but where in place of 3,14-diacetylnoroxymorphone (4a) there is subjected to the acid hydrolysis 3,14-diacetoxymorphinan hydrochloride (4e) or 3,14-diacetoxy-6-oxomorphinan hydrochloride (4f) there are obtained the corresponding 3,14-dihydroxymorphinan (5e) and 3,14-dihydroxy-6-oxomorphinan (5f).
EXAMPLE X
14-ACETYLNOROXYCODONE HYDROCHLORIDE (4b)
Hydrogen chloride (Matheson, technical, passed through calcium chloride ) was bubbled through a stirred solution of N-VOC-14-acetylnoroxycodone (3b) (1.00 g, 0.0024 mole) in methylene chloride (20 ml) at a moderate rate (20 cc per minute) for 15 minutes and then slowly (5 cc per minute) for another 45 minutes. The solvent was evaporated in vacuo and the leftover white foam was heated at 50° C. for 30 minutes in absolute methanol (20 ml). Evaporation of the solvent at reduced pressure gave 14-acetylnoroxycodone hydrochloride (4b) as a white granular solid which was recrystalized from methanol ether; mp 214°-216° C. dec; yield 0.82 g (89%); analysis sample mp 215°-217° C. dec.
Calc. for C 19 H 22 NO 5 Cl: C, 60.08%; H, 5.84%; N,, 3.69%; Cl, 9.33%. Found: C, 59.89%; H, 6.08%; N, 3.70%; Cl, 9.36%.
IR(μ): 3.56 (sh), 3.55-3.94 (m), 5.69-5.83 (s, 5.76 max.), 6.13 (w), 6.21 (w); CH 2 Cl 2 .
NMR(δ): 10.8-9.4 (very broad), 6.78 (s), 5.2-4.8 (broad), 4.74 (s), 3.91 (s), 3.7-1.4 (m, with large spike at 2.46); ratio 2:2:1:1:3:13; CDCl 3 .
MS(m/e): 343.1451 (P-HCl, 100%, Calc. 343.1419), 300.1236 (P-HCl-Ac, 19%, Calc. 300.1235), 201 (22%), 43 (45%), 35 (20%).
EXAMPLE XI
14-CYCLOBUTYLCARBONYLNOROXYCODONE HYDROCHLORIDE (4c)
Hydrogen chloride (Matheson, technical, passed through calcium chloride) was bubbled (ca. 20 cc per minute) through a stirred solution of N-VOC-14-cyclobutylcarbonylnoroxycodone (3c) (2.72 g, 0.006 mole) prepared in accordance with Example VII in methylene chloride (40 ml) for 2.5 hours. The methylene chloride was removed in vacuo and the remaining white foam was refluxed for an hour in methanol (40 ml). Vacuum evaporation of the volatiles gave a white granular solid; mp 212.5°-213.5° C. dec; yield 2.52 g (100%). The reaction product was recrystalized from methanol-ether to further purify the 14-cyclobutylcarbonylnoroxycodone hydrochloride (4c), mp 214°-215° C. dec; yield 2.01 g (80%); second crop: mp 211.5°-212° C. dec; yield 0.09 g (4%); analysis sample mp 217° C. dec.
Calc. for C 22 H 26 NO 5 Cl: C, 62.93%; H, 6.24%; N, 3.34%; Cl, 8.44%. Found: C, 63.11%; H, 6.49%; N, 3.39%; Cl, 8.58%.
IR(μ): 3.56 (sh), 3.54-3.99 (m), 5.73-5.82 (s, 5.77 max.), 6.13 (w), 6.22 (w); CH 2 Cl 2 .
NMR(δ): 10.6-9.4 (very broad), 6.77 (s), 5.2-4.9 (broad), 4.73 (s), 4.0-1.2 (m, with large spike at 3.91); ratio 2:2:1:1:20; CDCl 3 .
MS(m/e): 383.1743 (P-HCl, 100%, Calc. 383.1732), 300 (43%), 277 (28%), 216 (28%), 212 (22%).
EXAMPLE XII
NOROXYCODONE (5b) FROM N-VOC-14-ACETYLNOROXYCODONE (3b) WITHOUT ISOLATION OF 14-ACETYLNOROXYCODONE HYDROCHLORIDE
Hydrogen chloride (Matheson, technical, passed through calcium chloride) was bubbled through a stirred solution of crude N-VOC-14-acetylnoroxycodone (3b) (11.88 g, 0.0287 mole) in methylene chloride (200 ml) for 100 minutes at a moderate rate (20 cc per minute). The solvent was removed in vacuo; and after overnight drying (0.3 torr), the off-white foam was gently refluxed for 30 minutes in 200 ml of absolute methanol. Evaporation of the solvent gave 14-acetylnoroxycodone hydrochloride (4b) as a white, granular solid which was dissolved in aqueous hydrochloric acid (225 ml) and heated for four hours at 100° C. The solution was cooled, basified with concentrated ammonium hydroxide, and allowed to warm to room temperature. Acidification of the solution to pH 2-3 with concentrated hydrochloric acid was followed by extraction with chloroform (3 × 50 ml). The aqueous solution was then rebasified with concentrated aqueous ammonium hydroxide and extracted with chloroform (9 × 75 ml). The dried (over sodium sulfate) extract was concentrated to a greenish-brown solid which was dissolved in chloroform (25 ml) and passed through a short basic alumina column (15 g, chloroform as eluant) where the reddish color was removed. Vacuum evaporation of the total eluate gave noroxycodone (5b) as off-white microneedles of mp 164°-166° C. foaming, then 305° C. dec (lit.: Seki supra, 160° C. foaming, then 310° C. dec); yield 7.09 g (82%); tlc: single spot of R f 0.06. The compound was not crystalized before use since previous published attempts to recrystalize it had failed. According to Seki(vide supra), the compound analyzes satisfactorily without further purification.
IR(μ): 2.96 (sh), 2.95-3.05 (w), 3.56 (w), 5.79 (s), 6.13 (w), 6.22 (m): CH 2 Cl 2 .
NMR(δ): 6.8-6.4 (m), 4.61 (s), 3.9-1.2 (m, with large spike at 3.87); ratio 2:1:16; CDCl 3 .
Ms(m/e): 301 (P, 100%), 216 (52%), 201 (14%), 188 (26%), 175 (18%), 126 (22%), 115 (21%).
EXAMPLE XIII
CYCLOPROPYLCARBINYL BROMIDE
This compound was prepared from cyclopropyl carbinol (Aldrich) and phosphorous tribromide (Baker) according to Meek (J.A.C.S. 77 6675 (1955)); bp 108.5°-110° C. (lit. 101.5°-102° C. at 627 torr).
NMR (δ): 3.30 (d, J=7), 1.6-0.2 (m); ratio 2:5; CCl 4 .
EXAMPLE XIV
N-CYCLOPROPYLMETHYLNOROXYCODONE (6b)
A suspension of noroxycodone (5b) (6.03 g, 0.02 mole), cyclopropylcarbinyl bromide (8.10 g, 0.06 mole), and sodium carbonate (3.18 g, 0.03 mole) in 120 ml of 1:1 95% ethanol/chloroform was stirred (under nitrogen) at 60° C. for 3.5 days. Volatiles were evaporated and the remaining solid was partitioned between chloroform (150 ml) and water (150 ml). After separation, the aqueous layer was extracted with more chloroform (2 × 100 ml). The total extract was washed with water (100 ml), dried over sodium sulfate, and concentrated to ca. 25 ml which was then passed through a short silica gel 60 column (hot chloroform as eluant) where most of the brown color was removed. Evaporation of the total eluate gave a pale yellow foam identified as N-cyclopropylmethylnoroxycodone (6b) which crystalized from ether/pentane to give white "angel hair" crystals of mp 98.4°-99.1° C.; yield 5.85 g (82%); tlc: single spot of R f 0.54 versus R f 0.06 for noroxycodone. By concentration of the filtrate, a second crop of off-white crystals was obtained; mp 97.3°-98° C.; yield 0.32 g (5%); tlc: single spot of R f 0.54; analysis sample mp 99.1°-99.3° C. Though the last filtrate residue (0.31 g) was mostly product, a less polar contaminant (R f 0.76) was also present.
Calc. for C 21 H 25 NO 4 : C, 70.96%; H, 7.09%; N, 3.94%. Found: C, 70.75%; H, 7.29%; N, 4.05%.
IR(μ): 2.94-3.07 (w), 3.58 (m), 5.78 (s), 6.11 (w), 6.22 (m); CH 2 Cl 2 .
NMR(δ): 6.8-6.4 (m), 4.7-4.3 (broad, with small spike at 4.63), 3.89 (s), 3.4-0.0 (m); ratio 2:2:3:18; CDCl 3 .
MS(m/e): 355.1776 (P, 100%, Calc. 355.1784), 314.1390 (P-cyclopropyl, 22%, Calc. 314.1392), 110 (19%), 55 (50%).
In accordance with the above procedure, but where in place of noroxycodone (5b) there is utilized 3,14-dihydroxy-6-oxomorphinan (5f) there is obtained N-cyclopropylmethyl-3,14-dihydroxy-6-oxomorphinan (7f).
EXAMPLE XV
N-ALLYLNOROXYCODONE (6g)
Noroxycodone (5b) (7.13 g, 0.0237 mole), allyl bromide (Aldrich, redistilled) (5.72 g, 0.0473 mole), and sodium bicarbonate (3.98 g, 0.0473 mole) in 200 ml of 1:1 ethanol-chloroform was heated with stirring (under nitrogen) for 5 days at 60° C. After evaporation of the volatiles, a white residue remained. This was partitioned between water (50 ml) and chloroform (150 ml), and after separation, the aqueous layer was extracted with more chloroform (2 × 30 ml). Then the total chloroform solution was washed with water (50 ml), dried over sodium sulfate, and concentrated to an off-white solid. This was recrystalized from ethanol to yield N-allylnoroxycodone (6g) as white oblong crystals of mp 137°-137.5° C. (lit. Sankyo.Belg.Pat. No. 615,009 (1962) 132°-134° C.); yield 7.08 g (88%); tlc: single spot of R f 0.61, the R f of noroxycodone was 0.06; analysis sample mp 137.2° -137.9° C.
Calc. for C 20 H 23 NO 4 : C, 70.36%; H, 6.79%; N, 4.10%. Found: C, 69.94%; H, 6.92%; N, 4.05%.
IR(μ): 2.94-3.08 (w), 3.57 (m), 5.79 (s), 6.14 (w), 6.22 (m); CH 2 Cl 2 .
NMR(δ): 6.8-6.4 (m), 6.1-5.5 (m), 5.4-4.5 (m, with small spike at 4.61), 3.87 (s), 3.3-1.3 (m); ratio 2:1:4:3:13; CDCl 3 .
MS(m/e): 341.1614 (P, 100%, Calc. 341.1626), 300.1268 (P-allyl, 12%, Calc. 300.1235), 256 (18%), 96 (15%), 70 (15%), 41 (30%).
EXAMPLE XVI
NALOXONE (7a) FROM NOROXYMORPHONE (5a)
A suspension of noroxymorphone (5a) (2.73 g, 0.0095 mole), allyl bromide (Aldrich, redistilled) (1.26 g, 0.0104 mole), and sodium bicarbonate (Fisher) (1.20 g, 0.0143 mole) in 200 ml of absolute ethanol was heated (under nitrogen) with stirring for 60 hours at 70° C. The volatiles then were removed in vacuo and the remaining brown solid was dissolved in hydrochloric acid (50 ml, 0.5 N). The solution was filtered to remove a brown flocculence, extracted with chloroform (2 × 20 ml), refiltered, and taken to pH 13.5 (pH meter) with aqueous potassium hydroxide (30%). In order to remove any O-allyl product, this solution was extracted with chloroform (3 × 40 ml). After another filtration to remove a trace flocculence, the pH of the solution was lowered to 8.8 (pH meter) with aqueous hydrochloric acid (20%) and the desired N-allylnoroxymorphone (7a) was extracted into chloroform (8 × 50 ml). The total extract was washed with water (75 ml), dried over sodium sulfate (anhydrous), and concentrated to ca. 25 ml. This dark brown solution was passed through a short silica gel 60 column (hot chloroform as eluant) where all of the brown color was removed. Evaporation of the total eluate afforded a white solid which was recrystalized from ethyl acetate to give naloxone (7a) as white needles, mp 181.5°-182° C. (lit.: Lewenstein supra, 184° C., lit.: Sankyo, Belg. Pat. No. 615,009 (1962) 177°-178° C.); yield 1.75 g (56%); tlc: single spot of R f 0.51. By concentration of the filtrate, a second crop of white needles was obtained; mp 180°-181.5° C.; yield 0.45 g (15%); tlc: single spot of R f 0.51. The main component (ca. 2/3) of the filtrate residue (0.33 g) was naloxone. Tlc indicated the presence of a single, faster moving contaminant (R f 0.75) whose NMR spectrum exhibited excess allyl absorption. (The NMR spectrum of the chloroform extract of the pH 13.5 solution above also contained excess allyl absorption and its tlc indicated the presence of naloxone and the R f 0.75 compound). The analysis sample of naloxone was prepared by recrystalization from ethyl acetate; mp 181°-182° C.
Calc. for C 19 H 21 NO 4 : C, 69.71%; H, 6.47%; N, 4.28%. Found: C, 69.69%; H, 6.63%; N, 4.27%.
IR (μ): 2.85 (sh), 2.90-3.18 (m), 3.58 (m), 5.81 (s), 6.11 (w), 6.20 (m); CH 2 Cl 2 .
NMR(δ): 6.8-6.4 (m), -6.2-4.9 (m, with medium broadened spike at 5.41), 4.69 (s), 3.7-1.2 (m); ratio 2:5:1:13; CDCl 3 .
MS (m/e): 327.1457 (P, 33%, Calc. 327.1470), 58 (32%), 43 (100%).
Alkylation of noroxymorphone with cyclopropylcarbinyl bromide in hot ethanol using sodium bicarbonate as the acid scavenger similarly yielded N-cyclopropylmethylnoroxymorphone (same physical and spectral properties as those given in Example XVII below).
EXAMPLE XVII
N-CYCLOPROPYLMETHYLNOROXYMORPHONE (7b)
The crystalized N-cyclopropylmethylnoroxycodone (6b) (0.71 g, 0.002 mole) and pyridine hydrochloride (2.31 g, 0.02 mole) were thoroughly mixed in a small flask equipped with a micro distilling head. The flask was then immersed in an oil bath and heated with stirring (under nitrogen) to 193° C. and left at that temperature for 25 minutes. Then the temperature was raised to 210° C. over a ten minute period and kept at that temperature for five minutes. Next, the reaction vessel was withdrawn from the oil bath and allowed to cool. During the heating process, a small amount of pyridine distilled over. The syrup at high temperature became a semisolid mass when cooled. This was dissolved in 20 ml of water and the solution taken to pH 6-6.5 with aqueous 30% potassium hydroxide. After chloroform extraction (3 × 5 ml), the pH of the aqueous layer was raised to 13.5 with additional 30% potassium hydroxide. This solution was extracted with chloroform (3 × 8 ml) to remove any unreacted N-cyclopropylmethylnoroxycodone (6b). (After concentration, 0.04 g, 6%, of the starting material was recovered from this chloroform extract.) Next, the aqueous phase was acidified to pH 1 with concentrated hydrochloric acid, decolorized with Nuchar (Eastman, ca. 0.1g), filtered, and taken to pH 8.8 (pH meter) with concentrated aqueous ammonium hydroxide. The solution then was extracted with methylene chloride (3 × 50 ml) followed by chloroform (3 × 50 ml). The total, dried (over sodium sulfate) organic extract was evaporated at reduced pressure. The naltrexone (7b) thus isolated as an off-white solid was recrystalized from acetone; mp 173.5°-174.5° C. (lit. 168°-170° C.); yield 0.50 g (73%); tlc: single spot of R f 0.42; analysis sample mp 174.5°-175° C.
Calc. for C 20 H 23 NO 4 : C, 70.36%; H, 6.79%; N, 4.10%. Found: C, 70.02%; H, 6.88%; N, 4.16%.
IR(μ): 2.84 (w), 2.94-3.15 (m), 3.58 (m), 5.79 (s), 6.11 (w), 6.19 (m); CH 2 Cl 2 .
NMR(δ): 6.8-6.4 (m), 6.02 (broadened s), 4.73 (s), 3.4-0.0 (m); ratio 2:2:1:18; CDCl 3 .
MS(m/e): 341.1628 (P, 100%, Calc. 341.1626), 300.1213 (P-cyclopropyl, 26%, Calc. 300.1235), 110 (21%), 55 (50%).
EXAMPLE XVIII
N-ALLYLNOROXYMORPHONE (NALOXONE) (7a/7g) BY O-DEMETHYLATION
N-allylnoroxycodone (6g) (1.71 g, 0.005 mole) and pyridine hydrochloride (5.78 g, 0.05 mole) were thoroughly mixed in a 25 ml flask equipped with a stir bar and a short path distillation head. The flask was immersed in an oil bath and heated (under nitrogen) with stirring to 195° C. and left at that temperature for 20 minutes. The temperature was then raised to 205° C. over a five minute period and kept there for another five minutes. A few drops of pyridine distilled over during the heating process. Next, the semisolid mass from the cooled reaction vessel was dissolved in 40 ml of water. This solution was taken to pH 8.5-9.0 with concentrated ammonium hydroxide and then extracted with ether (6 × 50 ml). The ether solution was extracted first with aqueous sodium hydroxide (pH 13.1, 5 × 40 ml) and then with water (40 ml). Unreacted N-allylnoroxycodone, 0.09 g (5%), mp 134°-135° C., was recovered from the ether solution by concentration and recrystalization from ethanol. Next, the pH of the aqueous solution was lowered to 8.8 (pH meter) with aqueous 20% hydrochloric acid and the precipitated product was extracted into methylene chloride (6 × 40 ml). The methylene chloride solution was washed with water (50 ml), dried over sodium sulfate, and evaporated to a brown solid. This was dissolved in hot chloroform (10 ml) and passed through a short silica gel 60 column (hot chloroform as eluant) where most of the color was removed. Evaporation of the total eluate gave an off-white solid which was recrystalized from ethyl acetate; white needles of mp 181°-182° C. (lit.: Lewenstein supra 184° C., lit.: Seki supra 177°-178° C.); yield 0.48 g (29%); tlc: single spot of R f 0.51. By concentration of the filtrate a second crop was obtained; off-white needles of mp 179.5°-181.5° C.; yield 0.18 g (11%); tlc: single spot of R f 0.51. The filtrate residue (0.11 g) showed a single tlc spot of the same R f ; analysis sample mp 181°-182° C.; analytical and spectral data correspond with those obtained in Example XVI supra.
EXAMPLE XIX
CYCLOPROPANECARBOXYLIC ACID ANHYDRIDE
This was prepared from cyclopropanecarboxylic acid (Aldrich) and cyclopropanecarboxylic acid chloride (Aldrich) by the method given (Example IV) for the preparation of the cyclobutyl analogue and purified by vacuum distillation; bp 95°-100° C. at 6 torr (lit.: Castro and Dormoy, Bull. Soc. Chem. Fr. 8, 3034 (1971) bp 102°-104° C. at 8 torr); IR anhydride C═O stretch absorptions at 5.53 and 5.74μ.
EXAMPLE XX
14-CYCLOPROPYLCARBONYLOXYCODONE
This was prepared from oxycodone (6.31 g, 0.02 mole) and cyclopropane carboxylic acid anhydride (6.16 g, 0.04 mole) using the procedure outlined in Example III. After adjusting the pH to 11, the precipitated solid product was filtered, washed with cold water, dried in vacuo at room temperature and used without further purification; yield 7.73 g (99%); crude mp 169°-173° C. cor.; tlc: single spot of R f 0.60.
IR(μ): 3.56 (w), 3.61 (w), 3.65 (w), 5.76-5.87 (s, broad), 6.15 (w), 6.22 (m); CH 2 Cl 2 .
EXAMPLE XXI
N-VOC-14-CYCLOPROPYLCARBONYLNOROXYCODONE
This was prepared from the crude 14-cyclopropylcarbonyloxycodone (3.83 g, 0.01 mole) and vinyl chloroformate (0.03 mole) by the procedure given in Example VII. The crude title compound was obtained as an off-white foam which was used without further purification; weight 4.08 g, tlc: single spot of R f 0.72.
NMR(δ): 7.2-7.6 (m), 6.7-7.1 (m), 5.6-5.8 (broad), 3.9-5.1 (m with small spike at 4.82 and large spike at 4.00), 0.8-3.6 (m); ratio 1:2:1:7:14; CDCl 3 .
Starting 14-cyclopropylcarbonyloxycodone (0.33 g) was recovered from the aqueous extracts.
EXAMPLE XXII
14-CYCLOPROPYLCARBONYLNOROXYCODONE HYDROCHLORIDE
Treatment of the crude N-VOC-14-cyclopropylcarbonylnoroxycodone (3.95 g, 0.009 mole) with anhydrous hydrogen chloride in methylene chloride according to the procedure in Example XI gave a tan foam which was refluxed for an hour in absolute methanol. Solvent evaporation at reduced pressure afforded the crude title compound as a tan solid; yield 3.62 g (99%). The remaining steps in the synthesis of naltrexone outlined in the accompanying patent application were performed using this material without further purification.
IR(μ): 3.56 (sh), 3.53-4.02 (m, broad), 5.74-5.84 (s, with 5.78 max), 6.12 (w), 6.22 (w); CH 2 Cl 2 .
NMR(δ): 10.9-9.4 (very broad), 6.95 (s), 5.2-4.8 (m, with spike at 4.90), 4.2-0.2 (m, with large spike at 4.01); ratio: 2:2:2:18, CDCl 3 .
EXAMPLE XXIII
14-CYCLOPROPYLCARBONYLNOROXYCODONE ACETIC ACID SALT
Unpurified 14-cyclopropylcarbonyloxycodone (1.15 g, 0.003 mole) was heated in a 92° C. oil bath at 0.3 torr for two hours. Then the vacuum was replaced by a nitrogen atmosphere and after the oil bath had cooled to 65° C., 2,2,2-trichloroethyl chloroformate (0.006 mole) and 1,2-dichloroethane (10 ml) were added. The stirred, yellow solution was heated for 23 hours at 65° C. and then refluxed for an hour. The reddish glass obtained after vacuum evaporation was dissolved in ethyl acetate (75 ml), washed with 3 N hydrochloric acid (15 ml), water (15 ml), 5% aqueous sodium bicarbonate (15 ml), brine (15 ml), and dried over sodium sulfate. Rotary evaporation gave a tan foam which was dissolved in 5 ml of chloroform and eluted through a short silica gel 60 column using chloroform as the eluant. Evaporation of the eluate gave an off-white foam which was kept under vacuum at 60° C. for 40 hours at 0.4 torr. The tan solid which remained analyzed as a mixture of N-(2,2,2-trichloroethoxycarbonyl)-14-cyclopropylcarbonylnoroxycodone (tlc: single spot at R f 0.65) contaminated by trichloroethyl chloroformate.
IR (μ): 3.56 (w), 5.76 (sh), 5.80 (s), 5.86 (s), 6.13 (w); CH 2 Cl 2 (chloroformate at 5.64[w]).
NMR(δ): 7.1-6.6 (m), 5.9-5.5 (broad), 5.2-0.7 (m with large spike at 4.01 and small spikes at 4.98 and 4.80); ratio: 2:1:21; CDCl 3 (chloroformate at 5.00).
All the unpurified N-trichloroethoxycarbonyl compound above was dissolved in 45 ml of aqueous 90% acetic acid. Zinc dust (1.44 g, 0.022 mole) was added in seven portions over a one hour period to the stirred mixture, to remove the N-trichloroethoxycarbonyl group and give the acetic acid salt of 14-cyclopropylcarbonylnoroxycodone (contaminated by zinc acetate and zinc chloride) on removal of the solvent acetic acid under high vacuum.
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There is provided a novel, high yield, method of dealkylating N-alkylated 14-hydroxymorphinans and derivatives thereof including, inter alia, oxymorphone and oycodone. There are thus provided, inter alia, more efficient routes for the formation of naloxone, naltrexone, and nalbuphine. In the principal step of the process, the dealkylation using certain oxycarbonyl halides (or haloformates) is carried out on the N-alkyl-14-acyloxy-morphinan which it is desired to dealkylate.
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FIELD OF THE INVENTION
[0001] The present invention relates to a technology for forming a copper film on a substrate such as a semiconductor wafer by using an organic compound of copper as a material.
BACKGROUND OF THE INVENTION
[0002] In a recent wiring technology, copper lines are replacing aluminum lines to improve performance of a semiconductor device. In a manufacturing process of the semiconductor device, a technology for forming a copper film on a surface of a semiconductor wafer (hereinafter, referred to as a “wafer”) is important. A chemical vapor deposition method (hereinafter, referred to as “CVD”) using a copper organic compound as a material has been known as one of technologies for forming a copper film on the wafer.
[0003] When a copper film is formed on the wafer by using CVD, a copper organic compound, e.g., Cu(hexafluoroacetylacetonate)trimethylvinylsilane (hereinafter, referred to as “Cu(hfac)TMVS”) serving as a source gas is supplied to a processing chamber in a vacuum state, and the Cu(hfac)TMVS is thermally decomposed on the heated wafer to form the copper film on the wafer.
[0004] However, since copper atoms tend to be diffused into the insulating film, the copper film is mostly formed on a diffusion barrier film (hereinafter, referred to as a “base film”) called a barrier metal, which is formed in advance on the substrate, instead of being directly formed on the wafer.
[0005] The base film employs titanium, tantalum, nitride thereof or the like. However, the barrier metal of the base film reacts with an organic material from the copper organic compound, thereby producing organic impurities at an interface between the copper film and the barrier metal.
[0006] In this case, adhesiveness between the base film and the copper film is weakened due to an organic impurity layer and a resistance between an upper copper line and a lower copper line increases. Accordingly, electrical characteristics deteriorate or the copper film is peeled off while processing the wafer, resulting in a reduction in production yield. Further, since the organic impurity layer has poorer wettability than the base film, copper can be easily aggregated to thereby reduce buriability of the copper in a trench having a high aspect ratio, thereby causing a formation defect of the copper line.
[0007] In order to solve the problem that the adhesiveness between the copper film and the base film is reduced due to formation of the organic impurity layer, Japanese Laid-open Application No. 2002-60942 (see, particularly, paragraphs [0037], [0038] and [0057]) discloses a technology using water vapor. In accordance with the technology disclosed in the above-mentioned document, water vapor is supplied in advance to the processing chamber containing the wafer, and both the water vapor and Cu(hfac)TMVS are supplied to the processing chamber for, e.g., 0.5 second. Then, only the supply of water vapor is stopped to prevent formation of the organic impurity layer, thereby obtaining the copper film having improved adhesiveness to the base film.
[0008] However, in the CVD using Cu(hfac)TMVS as a material, it is known that the water vapor causes a demerit of abnormal growth of the copper film in a needle shape though it prevents formation of the organic impurity layer. From this point, in the technology disclosed in the above-mentioned document, since the water vapor still remains in the processing chamber even though the supplies of these gases are stopped, it is difficult to immediately stop the abnormal growth of the copper film. In this case, since a gap develops between the base film and the copper film, it is difficult to improve adhesiveness.
SUMMARY OF THE INVENTION
[0009] The present invention is devised in view of the above-mentioned problems. An object of the present invention is to provide a film forming method and a film forming apparatus capable of obtaining a copper film having excellent adhesiveness to a base film by preventing the formation of an organic impurity layer and the abnormal growth of the copper film.
[0010] In accordance with a first aspect of the present invention, there is provided a film forming method comprising: a substrate placing step of placing a substrate in an airtightly sealed processing chamber; a first film forming step of forming an adhesion layer of copper on the substrate by supplying water vapor and a source gas containing an organic compound of copper to the processing chamber; a discharging step of discharging the water vapor and the source gas out of the processing chamber; and a second film forming step of forming a copper film on the adhesion layer by resupplying only the source gas to the processing chamber.
[0011] In accordance with the first aspect of the present invention, since the adhesion layer is formed under an atmosphere containing water vapor, although the base film on which the adhesion layer is formed is made of metal such as titanium having a high oxidation tendency, it is possible to prevent formation of the organic impurity layer and improve adhesiveness between the base film and the adhesion layer. Further, the processing chamber is evacuated after formation of the adhesion layer and, then, the Cu(hfac)TMVS gas is resupplied to form the copper film, thereby suppressing an abnormal growth of the copper film due to the water vapor.
[0012] In accordance with a second aspect of the present invention, there is provided a film forming method comprising: a substrate placing step of placing a substrate in an airtightly sealed processing chamber; a first film forming step of forming an adhesion layer of copper on the substrate by supplying water vapor and a source gas containing an organic compound of copper to the processing chamber; a discharging step of discharging the water vapor and the source gas out of the processing chamber; and a second film forming step of forming a copper film on the adhesion layer by resupplying the source gas and the water vapor to the processing chamber, wherein an amount of the water vapor supplied in the second film forming step is smaller than an amount of the water vapor supplied in the first film forming step.
[0013] In accordance with the second aspect of the present invention, since the adhesion layer is formed under an atmosphere containing water vapor, although the base film on which the adhesion layer is formed is made of metal such as titanium having a high oxidation tendency, it is possible to prevent formation of the organic impurity layer and improve adhesiveness between the base film and the adhesion layer. Further, the processing chamber is evacuated after formation of the adhesion layer and, then, the Cu(hfac)TMVS gas and a small amount of water vapor are resupplied to form the copper film, thereby suppressing an abnormal growth of the copper film due to the water vapor.
[0014] In the first film forming step, the supply of the source gas may start in a delayed manner after starting the supply of the water vapor. For example, in the first film forming step, the supply of the source gas may start after stopping the supply of the water vapor.
[0015] Further, in the first film forming step, the supply of the water vapor and the supply of the source gas may be simultaneously performed.
[0016] Further, preferably, the substrate is heated to a temperature within a range from 100° C. to 150° C.
[0017] Further, preferably, a base film made of metal selected from titanium and tantalum, a base film made of a compound obtained by combining the metal with one or two elements among nitrogen, carbon and oxygen, or a base film made of ruthenium or oxide thereof is formed in advance on the substrate, and the copper film is formed on the base film.
[0018] In accordance with a third aspect of the present invention, there is provided a film forming apparatus comprising: an airtightly sealed processing chamber including a stage for mounting a substrate thereon; a water vapor supply unit for supplying water vapor to the processing chamber; a source gas supply unit for supplying a source gas containing an organic compound of copper to the processing chamber; an exhaust unit for evacuating the processing chamber; a temperature control unit for maintaining a temperature of the substrate within a range from 100° C. to 150° C.; a controller for controlling the units to perform a step of forming an adhesion layer of copper on the substrate by supplying water vapor and a source gas containing an organic compound of copper to the processing chamber, a step of discharging the water vapor and the source gas out of the processing chamber, a step of forming a copper film on the adhesion layer by resupplying only the source gas to the processing chamber.
[0019] In accordance with a fourth aspect of the present invention, there is provided a film forming apparatus comprising: an airtightly sealed processing chamber including a stage for mounting a substrate thereon; a water vapor supply unit for supplying water vapor to the processing chamber; a source gas supply unit for supplying a source gas containing an organic compound of copper to the processing chamber; an exhaust unit for evacuating the processing chamber; a temperature control unit for maintaining a temperature of the substrate within a range from 100° C. to 150° C.; a controller for controlling the units to perform a step of forming an adhesion layer of copper on the substrate by supplying water vapor and a source gas containing an organic compound of copper to the processing chamber, a step of discharging the water vapor and the source gas out of the processing chamber, a step of forming a copper film on the adhesion layer by supplying the source gas and a smaller amount of water vapor than the water vapor supplied in the step of forming an adhesion layer to the processing chamber.
[0020] In accordance with a fifth aspect of the present invention, there is provided a computer-readable storage medium for storing a control program for performing the film forming method by controlling a film forming apparatus which includes: an airtightly sealed processing chamber including a stage for mounting a substrate thereon; a water vapor supply unit for supplying water vapor to the processing chamber; a source gas supply unit for supplying a source gas containing an organic compound of copper to the processing chamber; an exhaust unit for evacuating the processing chamber; and a temperature control unit for maintaining a temperature of the substrate within a range from 100° C. to 150° C.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIGS. 1A to 1D schematically show cross sectional views of a wafer W corresponding to the steps of a semiconductor device manufacturing method using a film forming method of a copper film in accordance with an embodiment of the present invention.
[0022] FIG. 2 schematically shows a cross sectional view of a CVD apparatus for forming the film forming method in accordance with the embodiment of the present invention.
[0023] FIG. 3 illustrates an example of a process sequence for performing the film forming method in accordance with the embodiment of the present invention.
[0024] FIGS. 4A and 4B show a modification example of the process sequence of FIG. 3 .
[0025] FIGS. 5A and 5B are enlarged photographs of a cross section of the wafer to evaluate a formation state of an organic impurity layer.
[0026] FIGS. 6A and 6B are enlarged photographs for evaluating morphology of the surface of the copper film.
[0027] FIGS. 7A and 7B are enlarged photographs of a cross section of the wafer to evaluate buriability of copper in a trench formed on the surface of the wafer.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0028] A semiconductor device manufacturing method using a film forming method of a copper film in accordance with an embodiment of the present invention will be described with reference to FIGS. 1A to 1D . FIGS. 1A to 1D are cross sectional views of a wafer W in a process for manufacturing a semiconductor device formed on a surface portion of the wafer W.
[0029] FIG. 1A illustrates a state before a trench is formed in an interlayer insulating film. For simplicity of description, copper is assumed to be buried by employing a single damascene method. In the drawings, reference numerals ‘ 80 ’ and ‘ 81 ’ designate SiOC films (carbon-containing silicon oxide films) serving as interlayer insulating films, and a reference numeral ‘ 82 ’ designates an SiN film (silicon nitride film).
[0030] In this case, a method for forming the SiOC films 80 and 81 and the SiN film 82 is explained. These films are formed by, e.g., a plasma film forming process. Specifically, the wafer W is placed in a vacuum chamber evacuated to a vacuum state, and a specific film forming gas is supplied to the vacuum chamber to be converted to a plasma, thereby performing film formation.
[0031] In the wafer W, first, the SiOC film 81 is etched in a specific pattern shape by using, for example, a CF 4 gas or C 4 F 8 gas as an etching gas. In this case, the SiN film 82 , which is a base film of the SiOC film 81 , serves as an etching stopper. Accordingly, for example, as shown in FIG. 1B , a trench 800 having a line width equal to or smaller than, e.g., 120 nm, preferably, 80 nm, is formed in the SiOC film 81 to bury copper for wiring therein.
[0032] Subsequently, for example, as shown in FIG. 1C , a barrier metal layer (base film) 83 made of, e.g., titanium or tantalum is coated on a surface of the SiOC film 81 including the trench 800 . Further, after a copper film is formed such that copper is buried in the trench 800 , a chemical mechanical polishing (CMP) process is performed. Consequently, for example, as shown in FIG. 1D , the copper and the barrier metal layer 83 outside the trench 800 are removed, thereby forming a copper line 84 in the trench 800 .
[0033] Next, a film forming method of a copper film in accordance with the embodiment of the present invention will be described in detail.
[0034] In the film forming method, a gas containing an organic compound of copper, such as a Cu(hfac)TMVS gas, is supplied as a source gas to a processing chamber of a CVD apparatus, thereby forming a copper film. In this case, both the Cu(hfac)TMVS gas and water vapor are simultaneously supplied at a specific timing, thereby forming an adhesion layer having less organic impurities.
[0035] Then, the supplies of these gases are stopped and residual gases in the processing chamber are evacuated. Accordingly, it is possible to prevent an abnormal growth of the copper film. Then, those gases are resupplied so that the copper film can be formed at a relatively low temperature.
[0036] Next, an apparatus for performing the film forming method is explained. FIG. 2 illustrates a cross sectional view showing an example of a CVD apparatus for forming the film forming method in accordance with the present invention. The CVD apparatus 1 includes a processing chamber (vacuum chamber) 10 made of, e.g., aluminum. The processing chamber 10 includes an upper large-diameter cylindrical part 10 a and a lower small-diameter cylindrical part 10 b connected to each other.
[0037] A heating unit (not shown) is provided in the processing chamber 10 to heat an inner wall of the processing chamber 10 . Further, a stage 11 for horizontally mounting the wafer W thereon is provided in the processing chamber 10 . The stage 11 is supported by a support member 12 installed at a bottom portion of the small-diameter cylindrical part 10 b.
[0038] The stage 11 is provided with a heater 11 a serving as a temperature control device of the wafer W. Further, the stage 11 is provided with, for example, three elevating pins 13 capable of vertically moving the wafer W while being protruded from a surface of the stage 11 and retracted into the stage 11 , thereby performing a delivery of the wafer W to/from a transfer unit provided outside the processing chamber 10 . The elevating pins 13 are connected to an elevating mechanism 15 located outside the processing chamber 10 through a support member 14 .
[0039] A bottom portion of the processing chamber 10 is connected to one end of an exhaust pipe 16 , and a vacuum pump 17 is connected to the other end of the exhaust pipe 16 . Further, a transfer port 19 which is opened and closed by using a gate valve 18 is formed at a sidewall of the large-diameter cylindrical part 10 a of the processing chamber 10 .
[0040] An opening 21 is formed at a ceiling portion of the processing chamber 10 . A gas shower head 22 is provided to close the opening 21 and face the stage 11 . The gas shower head 22 has two gas chambers 25 a and 25 b and two type gas supply holes 27 a and 27 b . A gas supplied to the gas chamber 25 a is supplied to the processing chamber 10 through the gas supply holes 27 a and a gas supplied to the gas chamber 25 b is supplied to the processing chamber 10 through the gas supply holes 27 b.
[0041] A source gas supply line 31 is connected to the lower gas chamber 25 a . A source tank 32 is connected to an upstream side of the source gas supply line 31 . The source tank 32 contains Cu(hfac)TMVS in a liquid state, which is a copper organic compound (complex) serving as a material (precursor) of a copper film. The source tank 32 is also connected to a compressor 33 . An inside of the source tank 32 is compressed by an Ar gas or the like supplied from the compressor 33 such that the Cu(hfac)TMVS is pushed toward the source gas supply line 31 .
[0042] A liquid mass flow controller (hereinafter, refereed to as “LMFC”) 34 and a vaporizer 35 for vaporizing Cu(hfac)TMVS are provided in the source gas supply line 31 sequentially from its upstream side. The vaporizer 35 vaporizes the Cu(hfac)TMVS by contact-mixing it with a carrier gas (hydrogen gas) supplied from a carrier gas supply source 36 . In FIG. 2 , a reference numeral ‘ 37 ’ designates a mass flow controller (MFC) for controlling a flow rate of the carrier gas, reference numerals ‘V 1 ’ to ‘V 5 ’ designate valves.
[0043] Next, a gas supply system of water vapor is explained. The upper gas chamber 25 b is connected to a water vapor supply line 41 . A water vapor supply source 42 is connected to an upstream side of the water vapor supply line 41 through an MFC 43 . In FIG. 2 , reference numerals ‘V 6 ’ and ‘V 7 ’ designate valves.
[0044] Further, gas supply controllers (represented by dotted lines) provided in a gas supply system of the Cu(hfac)TMVS gas and a gas supply system of water vapor, a pressure controller (not shown) provided in the exhaust pipe 16 , the heater 11 a , the elevating mechanism 15 and the like are controlled by a controller 50 for controlling an entire operation of the CVD apparatus 1 .
[0045] The controller 50 includes, for example, a computer having a program storage part (not shown). The program storage part stores a computer program including steps (commands) of an operation or a process (film forming process) for loading/unloading the wafer W to/from the processing chamber 10 . Further, the controller 50 controls the entire operation of the CVD apparatus 1 based on a computer program read from the program storage part. Further, the computer program is stored in the program storage part by being stored in a storage unit such as a hard disk, a compact disk, a magneto-optical disk, a memory card or the like.
[0046] FIG. 3 illustrates an example of a process sequence for performing the film forming method in accordance with the embodiment of the present invention. In FIG. 3 , (a) represents a time sequence of a temperature of the wafer W on which a film forming process is performed, wherein a solid line represents a temperature (° C.) of the wafer W. Further, (b) of FIG. 3 represents a time sequence of a pressure in the processing chamber 10 , wherein a solid line represents an absolute pressure in the processing chamber 10 , and (c) of FIG. 3 represents a time sequence of a gas supply amount of Cu(hfac)TMVS, wherein a solid line represents a supply amount (g/min; mass conversion) of Cu(hfac)TMVS. Further, (d) of FIG. 3 represents a time sequence of a water vapor supply amount, wherein a solid line represents a flow rate (sccm) of water vapor, and (e) of FIG. 3 represents a time sequence of a flow rate of a carrier gas (hydrogen) for carrying the Cu(hfac)TMVS gas, wherein a solid line represents a flow rate (sccm) of the carrier gas.
[0047] In accordance with the process sequence of FIG. 3 , the wafer W having a surface state shown in FIG. 1C , in which the barrier metal layer 83 is formed on the SiOC film 81 , is placed in the processing chamber 10 and the processing chamber 10 is controlled to have a pressure of, e.g., about 133 Pa (1 Torr). At a time T 1 , a carrier gas is supplied at a flow rate of, e.g., 200 sccm, and the pressure in the processing chamber 10 rises to, e.g., 5 Torr. Further, at a time T 2 before the supply of the Cu(hfac)TMVS gas is started, the water vapor is supplied at a flow rate of, e.g., 5 sccm.
[0048] Then, at a time T 3 , the pressure in the processing chamber 10 is adjusted to 2 Torr by the pressure controller (not shown). After that, while the water vapor is continuously supplied, at a time T 4 , the Cu(hfac)TMVS gas begins to be supplied at, e.g., 0.5 g/min to thereby form an adhesion layer of copper on the surface of the barrier metal layer 83 . Further, after, e.g., 5 to 60 seconds, particularly, 30 seconds, at a time T 5 , the supplies of the Cu(hfac)TMVS gas and the water vapor are stopped.
[0049] In the mean time, the supply of the carrier gas and the vacuum evacuation by using the vacuum pump are continuously performed. Accordingly, residual Cu(hfac)TMVS gas and water vapor are discharged out of the processing chamber 10 .
[0050] Then, at a time T 6 after residual gases in the processing chamber 10 are sufficiently discharged, the Cu(hfac)TMVS gas begins to be resupplied. At this time, the water vapor also begins to be resupplied at a small amount, for example, 0.1 sccm or less, which is sufficiently small enough to reduce a process temperature (wafer temperature) of CVD while hardly causing an abnormal growth of the copper film. Further, at a time T 7 when the copper film is formed to have a desired thickness, the supplies of the Cu(hfac)TMVS gas and the water vapor are stopped, thereby completing the process sequence.
[0051] As the CVD apparatus 1 is operated based on the above-mentioned process sequence, the copper film of a desired thickness can be formed on the wafer W having the trench 800 formed therein and the barrier metal layer 83 coated thereon, as described with reference to FIGS. 1A to 1D .
[0052] In the sequence shown in FIG. 3 , in the process after the time T 4 when the Cu(hfac)TMVS gas begins to be supplied to the processing chamber 10 which has been supplied with the water vapor, a reaction for forming the adhesion layer of copper on the barrier metal layer 83 shown in FIG. 1C is performed. Since the supply of the water vapor is started in the processing chamber 10 from the time T 2 before starting the supply of the Cu(hfac)TMVS gas, water molecules are sufficiently adsorbed to the surface of the wafer W. Accordingly, the reaction for forming the adhesion layer can be easily performed while suppressing formation of the organic impurity layer.
[0053] Then, after the supplies of the water vapor and the Cu(hfac)TMVS gas are stopped, the residual gases are discharged out of the processing chamber 10 . Accordingly, formation of the adhesion layer is stopped, and an abnormal growth of copper is suppressed to a minimum. First of all, since water vapor exists in the process for forming the adhesion layer, there is a possibility of causing an abnormal growth of copper. However, the Cu(hfac)TMVS gas is supplied for a very short period of time to the processing chamber 10 containing the water vapor, and the processing chamber 10 is evacuated right thereafter, thereby immediately stopping the abnormal growth. Thus, there is no chance that the copper film is grown in a needle shape, and it is considered that the water vapor has almost no influence on adhesiveness between the barrier metal layer 83 and the adhesion layer.
[0054] Then, after the time T 6 after the evacuation is completed, the Cu(hfac)TMVS gas begins to be resupplied to the processing chamber 10 such that the copper film is grown on the surface of the adhesion layer.
[0055] Further, a small amount of water vapor, small enough not to cause an abnormal growth of the copper film, is supplied in a period from the time T 6 to the time T 7 in the process sequence shown in FIG. 3 . Accordingly, the copper film can be grown at a low process temperature (wafer temperature) ranging from 100° C. to 150° C., for example, 130° C. because water molecules serve as catalyzers.
[0056] In accordance with the above-described embodiment of the present invention, following effects can be obtained. That is, since the adhesion layer is formed under an atmosphere containing water vapor, although the barrier metal layer (base film) 83 on which the adhesion layer is formed is made of metal such as titanium having a high oxidation tendency, it is possible to prevent formation of the organic impurity layer and improve adhesiveness between the base film and the adhesion layer. Further, the processing chamber 10 is evacuated after formation of the adhesion layer and, then, the Cu(hfac)TMVS gas is resupplied to form the copper film, thereby suppressing an abnormal growth of the copper film due to the water vapor. Further, since the steps are continuously performed, it is possible to suppress a demerit (abnormal growth) due to the supply of water vapor to a minimum while maintaining a merit (prevention of formation of the organic impurity layer) due to the supply of water vapor. As a result, it is possible to form the copper film having excellent adhesiveness on the barrier metal layer 83 . Thus, it is possible to prevent troubles such as peel-off of the copper line 84 in processing of the semiconductor device, thereby improving a production yield in the manufacture of semiconductor devices.
[0057] Further, since the water vapor is supplied to the processing chamber 10 in formation of the adhesion layer, a process temperature (wafer temperature) for forming the copper film can be reduced to a temperature ranging, for example, from 100° C. to 150° C. As a result, it is possible to improve morphology of the surface of the copper film and a void is hardly formed in the copper line 84 , thereby improving a production yield. Further, since the process temperature is reduced, it is possible to promote energy saving.
[0058] Also in the process for forming the copper film on the surface of the adhesion layer, a very small amount of water vapor, for example, 0.001 sccm to 0.1 sccm (less than an amount of water vapor supplied between the time T 2 and the time T 5 ), is supplied so that it hardly causes an abnormal growth of the copper film. Accordingly, the process temperature can range from 100° C. to 150° C. Also in this process, it is possible to improve morphology and promote energy saving.
[0059] Further, the process sequence of the film forming method in accordance with the present invention is not limited to that shown in FIG. 3 . For instance, as shown in FIG. 4A , the supply of water vapor for reducing the process temperature may not be performed while the copper film is formed on the surface of the adhesion layer. Further, as shown in FIG. 4B , the water vapor may be supplied for a short period of time at the same timing as the supply of the Cu(hfac)TMVS gas without performing the supply of water vapor in advance.
[0060] Although both the Cu(hfac)TMVS gas and the water vapor are supplied to the processing chamber 10 while the adhesion layer is formed in the above embodiment, it is not limited thereto. For example, after the water vapor is supplied in advance and the supply of water vapor is stopped, only the Cu(hfac)TMVS gas may be resumed to be supplied to the processing chamber 10 to form the adhesion layer. In this case, the vacuum pump 17 may be temporarily stopped until the supply of the Cu(hfac)TMVS gas is stopped to prevent the water vapor from being discharged.
[0061] Further, the barrier metal layer (base film) 83 on which the adhesion layer is formed may be made of tantalum instead of titanium. The barrier metal layer may be formed of a compound obtained by combining titanium or tantalum with one or two elements among nitrogen, carbon and oxygen. Moreover, the barrier metal layer may be formed of ruthenium or oxide thereof.
EXAMPLES
Experiment 1
[0062] In accordance with the film forming method of the embodiment of the present invention, an adhesion layer and a copper film were formed on a base film made of titanium. Then, cross sections of the films were observed.
Example 1-1
[0063] The copper film was formed on the surface of a barrier metal of titanium coated on the wafer W in accordance with the process sequence shown in FIG. 3 . Further, the process temperature was maintained at 130° C. and the supply of water vapor was stopped during the period of time between the time T 6 and the time T 7 . The cross sections of the obtained copper film and the base film were photographed by SEM and the result thereof is shown in FIG. 5A .
Comparison Example 1-1
[0064] In the same way, a copper film was formed on the surface of the barrier metal of titanium in accordance with a process sequence obtained by partially varying the process sequence shown in FIG. 3 . In the process sequence of Comparison example 1-1, the supply of water vapor was not performed in a period between the time T 1 and the time T 7 .
[0065] This fact is different from Example 1-1. Further, the process temperature was maintained at 130° C. The cross sections of the obtained copper film and the base film were photographed by SEM and the result thereof is shown in FIG. 5B .
[0066] (Consideration of Experiment 1)
[0067] As shown in FIG. 5A , in Example 1-1 of forming the copper film with the supply of water vapor, an organic impurity layer was formed to have a thickness of 1.5 nm and, namely, the organic impurity layer was hardly formed. On the other hand, in Comparison example 1-1 performed without the supply of water vapor, as shown in FIG. 5B , an organic impurity layer was formed to have a thickness of 6 nm, which is four times that in the case performed with the supply of water vapor. The formation of the thick organic impurity layer is considered to deteriorate adhesiveness between the base film and the copper film.
Experiment 2
[0068] In accordance with the film forming method of the embodiment of the present invention, a copper film was formed. Then, the surface of the film was observed.
Example 2-1
[0069] The copper film was formed under the same conditions as those of Example 1-1. Then, the surface of the copper film was photographed by SEM and the result thereof is shown in FIG. 6A .
Comparison Example 2-1
[0070] The copper film was formed under the same conditions as those of Comparison example 1-1. Then, the surface of the copper film was photographed by SEM and the result thereof is shown in FIG. 6B .
[0071] (Consideration of Experiment 2)
[0072] From the result of Example 2-1, as shown in FIG. 6A , it can be seen that small prominences and depressions are formed on the surface of the copper film and the copper film has good morphology. On the other hand, from the result of Comparison example 2-1 without the supply of water vapor to the processing chamber 10 , as shown in FIG. 6B , it can be seen that large prominences and depressions are formed on the surface of the copper film and the copper film has poor morphology. From the results, it can be seen that it is possible to improve morphology of the surface of the copper film by reducing the process temperature with the supply of water vapor in CVD using the Cu(hfac)TMVS gas as a material.
Experiment 3
[0073] The copper film was formed on the wafer W having a trench on its surface in accordance of the film forming method of the present invention, and buriability of copper in the trench was investigated.
Example 3-1
[0074] The copper film was formed in accordance with the process sequence shown in FIG. 3 , and copper was buried in the trench having a width of 120 nm and a depth of 500 nm (aspect ratio of 4.2). The base film of titanium was formed on the surface of the trench in advance to have a thickness of 15 nm by ionized PVD. Then, the cross section of the trench was photographed by SEM and the result thereof is shown in FIG. 7A .
Example 3-2
[0075] The copper film was formed in the same way, and copper was buried in the trench having a width of 80 nm and a depth of 500 nm (aspect ratio of 6.3). The base film of titanium was formed on the surface of the trench in the same way as in Example 3-1. Then, the cross section of the trench was photographed by SEM and the result thereof is shown in FIG. 7B .
[0076] (Consideration of Experiment 3)
[0077] As shown in FIGS. 7A and 7B , in both Examples 3-1 and 3-2, since the organic impurity layer was hardly formed and the wettability of the surface of the trench was not reduced, the buriability of copper in the trench was good.
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A film forming method is provided with a substrate placing step wherein a substrate is placed in a process chamber in an airtight status; a first film forming step wherein the process chamber is supplied with water vapor and a material gas including an organic compound of copper, and an adhered layer of copper is formed on the substrate; an exhaust step wherein the water vapor and the material gas in the process chamber are exhausted; and a second film forming step wherein the process chamber is resupplied with only the material gas and a copper film is further formed on the adhered layer.
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BACKGROUND OF THE INVENTION
This invention relates to an apparatus and method for cooking cereal grains and particularly to the use of a recycling step as well as use of a vertical cooker for continuously, evenly cooking a grain product while maintaining plug flow.
It is well known in the cooking art to employ vertical cylindrical continuous cookers. A problem the prior art attempts to solve is even cooking of material added to cookers. Cookers of this type have a conical baffle disposed near the bottommost portion of the vertical cooker. In these prior art devices, grain is added to the top of the vertical cooker, which is circular in cross section, and removed from the bottom of the vertical cooker. The temperature of the water in a typical vertical cooker is maintained by a controller, and by use of direct steam injection or use of a steam jacket about the cooker, and the level of water in the cooker is also ordinarily controlled.
In particular, it is known to use a vertical continuous cooker having a cone disposed near a bottom portion thereof.
There are several teachings in the prior art of continuous process methods using vertical cookers as a part thereof. In one of these references, U.S. Pat. No. 2,638,838 issued to Talmey et al., an apparatus is shown for heating granular material in a continuous process.
Talmey teaches a method of treating granular material, in a pressurized vessel, including grain, including steps of soaking, de-watering, cooking, again de-watering, dehydrating, and cooling. A float controlled valve is used to maintain constant head of water in tanks. Heated water of 200° F. is used in a mixer. Water is added along the sides of the tanks during cooking. Water separation occurs in the casing of the conveyor, not in the cooker, by way of a perforated section that is surrounded by an auxiliary jacket. The pressure cookeris vertical and has a baffle. Steam jets are supplied to the material as it gravitates downwardly in the cooker. The steam condenses and collects in the bottom of the cooker, the bottom having perforated openings so as to allow water to be drawn off by a pipe to a pump. This vessel is not, however, full of water, but rather steam which condenses and collects at the bottom. Furthermore, since direct steam injection is used, plug flow would be disrupted in this type of device. The water so collected is reinjected into the top of the cooker by a spray nozzle. However, there is no teaching or suggestion or injecting steam into the return water, nor of separating condensed water from the granular material within the vertical cooker, nor of maintaining plug flow within the vertical cooker. Furthermore, although additional treatment steps are shown, none relates to separating the final product and returning that condensate to the vertical cooker to aid cooking and ensure plug flow of the mixture of water and granular material through the vertical cooker. Such plug flow, if relatively uniform, would ensure even cooking of all grains in the cooker.
Another patent, U.S. Pat. No. 3,778,521 to Fisher et al., shows a process for the continuous production of bulgur.
The Fisher et al. patent shows the mixers having conical baffles therein used for the heating and mixing of wheat with water. A variety of control elements and use of steam are shown. However, steam injection appears to occur primarily in horizontal conveyor passage ways, and not in the vertical mixing devices. This differs significantly from the present invention, which doesn't use steam injection within the vertical cooker at all. Such steam injection would also disrupt plug flow if used in a vertical cooker. Moreover, the use of a separator to return liquid to a vertical cooker is not shown or suggested in Fisher nor is true plug flow taught therein.
Another type of continuous process is taught in U.S. Pat. No. 3,132,948 to Smith et al., which teaches a process of producing bulgur. A multi-stage process is shown, including moistening wheat with excess water, tempering, cooking, and drying the product. U.S. Pat. No. 2,884,327, to Robbins, shows a methodof processing wheat. The wheat is subjected to heat and moisture while moving the wheat. These patents fail to teach plug flow using a vertical cooker as part of a process of cooking.
Other patents, while not appearing to be as relevant as the foregoing, are also of interest.
The U.S. Pats. Nos. 911,408, 1,067,342, 129,906, 3,684,526, and 3,944,678, all relate to the controlling of moisture in flour or wheat products. Each of these references relate to a vertical chamber in which a product is received and from which the product exits. The most relevant of these references is to Lowery, U.S. Pat. No. 3,684,526, showing a pipe 36 for injecting a spray mist, not disclosed to be steam, at point 39 so as to slightly moisten the flour to a moisture level of 1.9%. However, there is no suggestion in any of these patents of using water and granular material in pre-mixed form for introduction into a vertical cooker to avoid uneven cooking and to ensure plug flow.
SUMMARY OF THE INVENTION
It is accordingly one object of the present invention to provide a continuous process apparatus and method for uniformly cooking cereal grains, including a vertical cooker for cooking grain, a method of recirculating and reheating the cooking water, and a separator for separating the grain from cooking water, including recycling of the cooking water so separated to the mixture of grain and water entering the vertical cooker.
A further object is to cook grain evenly and uniformly in plug flow in a vertical continuous cooker.
Another object of the present invention is to provide a continuous process apparatus and method for cooking cereal grains including a vertical cooker receiving a pre-heated mixture of granular material and water, for continuous cooking in true plug flow to ensure even, uniform cooking; granular material such as wheat or the like being fed into the cooker by a continuous feeder, a separator including a sieve which receives recycled water combined with the water being separated and exiting from the vertical cooker, with a wheat and water mixture being separated at a sieve portion, water from the sieve being recycled to be mixed with the wheat input to the vertical cooker.
It is another object of the present invention to provide an improved continuous process apparatus and method for cooking cereal grains, including a separator, a vertical cooker having a conical baffle to ensure plug flow, steam injection for heating the water, a water level controller, wheat level controller, and temperature controller for the vertical cooker, a metering pump to control the flow of grain exiting from the vertical cooker, recycling separated water from the vertical cooker by a sieve in the vertical cooker, the sieve being for separating the wheat and water.
The improved continuous process apparatus and method for cooking cereal grains is used as follows.
The invention is a continuous process method for cooking cereal grains. A vertical cooker is used for cooking a grain product. The cooker is filled with hot cooking water maintained at the desired cooking temperature and at a desired level within the cooker. The cooker is vertically oriented and has a conical baffle so as to ensure plug flow so that grain is neither undercooked nor overcooked. The cone angle used can be varied for different materials, as a result of routine experimentation if so desired. In the instant invention, the cooking water is maintained at a predetermined elevated temperature while drawing off a continuous stream of water through a sieve located near the lower portion of the conical baffle. The temperature of the water and wheat mixture added to the vertical cooker is maintained by a temperature controller, and the level fo water in the cooker is maintained by a level controller. A vibratory mechanism is used to ensure smooth plug flow of grain from the cooker, by vibrating the sieve and baffle members. Cooked grain exits from the bottom of the cooker under the action of a metering pump. The mixture of grain and water flows to a separator outside the vertical cooker. Grain is separated from the water by the separator, with water from the separator selectively returning to the cooker for recycling as needed.
Water is recycled from the cooker to be mixed with the grain entering the vertical cooker, thereby causing convection heat transfer from the water to the grain due to the higher velocity of water relative to the grain, which is retained and metered in flow by the metering pump. This ensures plug flow in the cooker since no liquid injection disturbs flow in the cookers; also, since no steam jacket is used, an even, generally uniform, heating of the grain is possible since the hot water is pre-mixed with the grain before entering the cooker, and the conical barrier and the sieve permit controlled plug flow through the vertical cooker to ensure even cooking.
Further details and advantages of the present invention appear from the following description of a preferred embodiment shown schematically in the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of a process according to the present invention;
FIG. 2 is an elevational view of the vertical cooker partly broken away toshow the conical baffle and sieve members of the vertical cooker;
FIG. 3 is a sectional view taken long line 3--3 of FIG. 2, showing struts connecting the sieve member to the conical baffle, with areas of the sieve member being visible about the baffle portion shown.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a schematic diagram of the continuous process of the present invention. A raw grain supply bin 62 supplies raw grain to supply 60 which supplies grain at a temperature range of approximately 50° F. to 110° F., or any ambient temperature, by a raw wheat supply conduit 2 to a wheat use bin 401. The raw wheat supply coming from storage can of course be at an ambient temperature lower or higher than the usual range given, depending on local conditions and storage methods.
The wheat use bin 401 supplis grain to a continuous feeder 63, which supplies grain on a weighed basis as indicated at 114 to a mixer 101.
The mixer 101 receives a steady stream of recirculating water from conduit 115, and also can receive make-up water from a fresh water supply 50 by a conduit 113. The mixer assures wetting and moistening of the individual grains of the granular material received from the continuous feeder, by the recirculating water and by the fresh make-up water. Any conventional mixing device can be used, for example, a tank having a motorized stirrer; any commercial mixer; a ribbon blender; a screw conveyor; continuous paddle mixer; or the like. The grain and water mixture, referred to hereinafter as a slurry, exits the mixer by a conduit 116 at approximately 200° F., depending upon the initial temperature of the water and wheat entering the mixer 101.
The conduit 116 supplies the slurry to a heater 250. The heater 250 can be any type of heater, for example, a steam injection heater, a coiled-tube heater having a segregated heating fluid within the coils, any convection heater having a heating means associated therewith, or any other heater suitable for heating the slurry. The slurry is heated, in a preferred embodiment, to 210° F. by steam injuection. Any other heating means may obviously be used instead of steam injection.
In the preferred embodiment, steam is supplied from a steam supply 70 at any pressure, from any source, in this case for example, at approximately 25 psig through a conduit 117 to the steam injection heater 250. There, the slurry and steam are mixed to heat the slurry to approximately 210° F. A steam injection control valve 42 controls the amount of steam injected to the heater 250, preferably by a temperature sensor communication line 33 which senses slurry temperature in the conduit 118. A temperature controller 22 receives the temperature information from the temperature sensor communication line 33, and the temperature controller 22 sends a control signal, by a steam valve controller communication line 32, to the steam control valve 42. This permits maintaining of any predetermined slurry temperature, in this case of approximately 210° F. Of course, any temperature appropriate to the particulate material (and process) could be maintained where particulate material other than grain is being cooked or otherwise processed.
The conduit 118 carries the heated slurry from the heater 250 to the top 46 of the vertical cooker 20. The slurry falls to a grain level 701 below the water level surface 702, the grain level being controllable as desired. The liquid water level 702 is preferably maintained at a predetermined elevation above that of the grain level 701, although for other processes the liquid level can be maintained below the particulate level if such is desirable. This permits even distribution of the grain across the top of the cooker 20 to ensure plug flow.
Plug flow is defined as the first grain in to the top of the cooker 20 is the first grain out, which ensures even cooking of all individual grains. This permits careful control of cooking time since overcooking of some grains is not required to ensure that all grains are properly cooked. Also, due to the controllable mass flow rate of recirculating water, discussed further hereunder, together with the separation and removal of the water by a sieve member 35 at the bottom of the cooker 20, the recirculating water can be controlled to flow with a relative downward speed or relative upward speed to the individual particulate grains. This would tend to increase the rate of heat transfer to individual grains by the water, since heat transfer is higher from a fluid to a solid when there is a relative velocity between them. This would tend to reduce the cooking time required, and would not disturb plug flow, as discussed further hereunder.
A fill pipe 300 enters the top 46 of the cooker 20, and can be used to initially fill the system with water. The system can be cold-started in this manner without grain, so as to preheat the water to desired levels. A vent line 400 is provided at the top 46 of the cooker 20, to allow escape of vapor, air, or water if pressure builds up in the cooker 20. The cooker 20 in a preferred embodiment can operate at atmospheric pressure; however, the cooker 20 can be adapted, if desired, to be a pressure cooker, and the associated equipment would then be adapted for pressure operation also. For example, pressure could be built up by choice of an appropriate mixer 101 to pressurize the slurry in the line 116. A pressure relief valve could then be used atop the cooker 20 instead of the vent line 400, to permit a predetermined pressure level to be maintained in the cooker 20. The metering pump 145, together with valve 41, could be used to maintain system pressure. Then, the remaining components may optionally be adapted for high pressure use if desired, although from the preceding discussion it is readily apparent that no other additional pressurized equipment would be necessary. Atmospheric operation is an advantage over pressure cookers, since less structural cooker 20 material thickness and conduit thickness would be required for atmospheric operation. The vent line 400 for atmospheric operation can be an open conduit pipe, or any other type of vent means. The fill conduit 300 for atmospheric operation can be any conventional pipe or conduit means.
A water level sensor 109 is attached to the cooker 20 in the vicinity of the desired water level 702. A wheat level sensor 110 is attached to the cooker 20 in the vicinity of the desired wheat level 701. These sensors can be optically actuated with electronic light detecting means to determine the presence of water or wheat, or they may be mechanical pivoting arm float devices; or may be any other known level sensing devices such as acoustic sensors which can send an output signal to a level controller, known in the art. Such level control is not crucial to the present invention, however, and may be done manually if desired using human operators watching a sight glass, for example, and operating appropriate control valves or motor controllers. The use of controllers in the present invention is described more fully hereunder.
The vertical cooker 20 is shown in greater detail in FIG. 2. The cooker 20 has an upper cone baffle 502 connected to a lower cone baffle 501. The upper cone baffle 502 prevents "funneling" of grain through the central portion of the cooker 20, which funneling would prevent plug flow. A particular cone angle is successful for this purpose, which in the preferred embodiment is 45 degrees as measured at the cone apex.
The cone angle, however, may be any appropriate angle that results in generally plug flow of the specific particulate material used. The optimum cone angle, for plug flow, is believed to depend upon the specific particulate material properties involved, such as grain size, adhesion properties, the fluid property behavior of the fluid used (in the present preferred embodiment, water), and so on. Thus, the optimum cone angle can be determined experimentally if necessary for a particular particulate material chosen and for particular operating conditions. Furthermore, although a cone is used in the preferred embodiment, other shapes can be used based, for example, upon complex curved shapes (such as a parabolic, hyperbolic, or dish shapes) determinable mathematically for a given set of particulate material and fluid parameters. The only criterion required is that the resulting baffle (here, cone 502) cause generally plug flow of grain through the vertical cooker.
The lower baffle 501 prevents eddy current flow in what would otherwise be a "dead zone" which would otherwise exist beneath the upper baffle 502. This therefore further ensures plug flow, since no grains can be swirled, mixed, or trapped by eddy current flow in such a "dead zone".
A flexible expansion joint 500 connects the vertical cooker 20 to the bottom 36, as seen in FIGS. 1 and 2. In FIG. 2, showing the cooker 20 and the bottom portion 36 cut away to reveal the interior details of the cooker, the sieve member 35 is seen as running parallel to the bottom 36. A valve 37 is preferably provided to control or shut off flow through conduit 8. The sieve member 35 is formed of a sieve material structure to permit passage of water therethrough but not of the entrained grain such as wheat. A sieve material structure could include, for example, a plate having holes therein, the holes being sufficiently small to prevent passage of individual particles of the particulate material. In the preferred embodiment, the holes would be smaller than the wheat grains. Other materials usable include a mesh screen, a corrugated sheet having slots therein, or any other material which can serve to permit passage of fluid but not individual particles of the particulate material (here, in the preferred embodiment, wheat grains are the particulate material). It is noted from FIGS. 1 and 2 that, while the sieve member is generaly conically shaped so as to be more or less generally parallel to the lower cone portion 501, any shape generally having a uniform spacing (or a gradually tapering spacing) from the member 501 can be used, since this tends to maintain plug flow. This is so since portion 501 is not limited to a cone shape, but can have other shapes as well, including complex curved or angled surfaces, so long as plug flow is substantially maintained. Such modifications are contemplated as being within the scope of the present invention.
As seen in FIG. 2, a solid member 707 acts as a connector for members 36 and 35, and prevents leakage of water downward. This therefore prevents re-mixing of water (previously separated from the particulate material by the sieve 35) with the material flowing into conduit 8. The member 707 would appear generally disc-shaped if seen from the bottom of FIG. 2.
A vibratory unbalanced motor 605, being connected by at least one strut 606 to the bottom portion 36 preferably continuously vibrates the bottom portion 36, including the bottom 36 and sieve 35, to facilitate the flow of grain across the sieve 35 without disrupting plug flow as would occur if no vibratory effects were present. The vibratory action is not transmitted directly to, or absorbed by, the vertical cooker 20, due to the presence of an expansion joint 500, which is resiliently flexible, disposed circumferentially about the vertical cooker 20 where it joins the bottom 36 and sieve 35.
Struts 503 connect the upper baffle member 502 and lower baffle member 501 in spaced relationship to the sieve 35. The vibratory motion imparted to the lower portion, including the conical baffle members 501 and 502, is indicated as being generally horizontal by the arrows 504 in FIG. 2. However, such vibratory motion is not necessary to the present invention, and substantially plug flow (once started) would exist without in the cooker even in the absence of such vibratory motion.
Thus, as can be seen from the figures, plug flow is maintained by the presence of the preferred conical baffle members 501 and 502, together with the sieve member 35 and the vibratory action of the motor 605 connected to the bottom portion 36. Wheat exits from the bottom-most portion of the bottom member 36. At the very bottom of the bottom member 36 in FIG. 2, a solid barrier 707 exists connecting the bottom-most edges of the bottom member 36 to the bottom-most edges of the sieve 35 to prevent flow of water downward with the flow of the remaining wheat-water mixture. Referring back to FIG. 1, the flow of the wheat-water mixture, flowing from the bottom 36 of the cooker 20, flows through a conduit 8 and a valve 37, and then to a metering pump 145 controlled by variable speed motor 45. This determines the speed with which the wheat migrates through the cooker 20 in plug flow.
A level controller 105 controls the wheat level 701. The wheat level controller 105 senses the wheat level by a wheat level sensor communication line 106 connected to the wheat level sensor 110. The wheat level controller 105 sends a control signal along line 107 to the metering pump drive motor 45. This controls wheat residence time in the vertical cooker 20. Excess water removed by the sieve member 35 is recirculated through the system, the recirculated water being drawn off from the region between the sieve member 35 and the bottom member 36 by a conduit 119. A control valve 41 controls the flow of the recirculating water in the conduit 119, and is controlled by a level controller 21.
The level controller 21 controls the water level 702, which level is sensed by the water level sensor 109. A water level sensor communication line 31 communicates the water level to the level controller 21; the level controller 21 then controls the position of the valve 41 by means of a water level controller communication line 34. A conduit 121 conveys the recirculating water to a separator 200.
Due to the presence in the preferred embodiment of recirculating water in a flow volume and mass flow rate greater than that of the wheat, in turn due to the presence of the sieve member 35, water flows downward verticaly through the cooker 20 at a speed different from, and usually greater than, that of the grain. This results in greater convection heat transfer into the grain of heat from the water, so as to cook the grain completely to the interior of each grain particle.
The grain and water mixture is associated in approximately equal portions and flow through the conduit 8 to the metering pump 145. From there, the metered mixture is carried by conduit 10 to a separator 80. The separator 80 is driven by a motive means 144, which may be pneumatic air or electrical power or rotary mechanical power, for example. Any conventional separator can be used, such as a centrifugal separator, vertical rotary separator, or the like. In the preferred embodiment, a vertical rotary-type separator is used to separate the water from the grain. During the cooking process, the grain absorbs water, and therefore a continuous heavier weight of cooked grain is produced than the continuous original entering weight of the raw uncooked grain entering the system. The cooked grain leaves the separator at outlet 4 and is conveyed or moved to be further processed as indicated at 85.
The water separated from the cooked wheat exits the separator 80 along conduit 120, where conduit 120 joins with conduit 121 into an inlet conduit 122 to a fine solids separator 200. The separator 200 has a fine solids exit 201 and a water outlet 202, where the water has been sufficiently separated from wheat particles so as to be suitable for recycling in the system.
A standpipe 9, having an oversized conduit portion 301 to receive the water from outlet 202, is provided. The water from the standpipe 9 communicates along conduit 306 with the inlet of a pump 43. Overflow and excess water from the oversized conduit portion 301 passes in the preferred embodiment to a drain or sewage conduit 112 along overflow conduit 303 which permits overflow water to fall into an oversized conduit 302, which oversized conduit 302 communicates with the drain or sewage 112. This also prevents overflowing of the conduit portion 301, since overflow water will be drained off over conduit 303.
The fine solids collected from the separator 200 exit through conduit 201 and fall as indicated at 307 either alone or within a conduit, to a sludge receptacle as indicated at 111 as a car for hauling sludge which operates on wheels. These fine solids can be disposed of either as animal feed or as waste material which is unusable, or can be used in any other manner desired.
The recirculating pump has a conduit 115 having a control valve 305 therein. The control valve 305 is controlled by a manual or automatic controller 304. This allows manual or automatic setting of the amount of recirculating water used in the system. The conduit 115 then enters mixer 101, previously described. This completes the recirculating portion of the cycle.
As noted, the water level 702 in the preferred embodiment is maintained by a level controller 21 which controls valve 41 by way of the valve control communication line 34. The water level sensor communication line 31 communicates with the level controller to transmit the level sensed by level sensor 109.
The control valves may be any type of control valve, including electrically operated, electro-mechanical, electronic, pneumatically-actuated, or the like. Also, the level sensing devices may be acoustic, gamma ray, electro-mechanical, optical, or may include any other type of level sensing device.
An example of the operation of the system for a particular level of supply of grian is given hereunder.
Wheat is supplied from the wheat use bin 62 to the feeder, preferably a feeder 63 which in the present example feeds the grain on a continuous basis evenly into the mixer 101 at a nominal approximate rate of 4,336 lb/hr. The initial wheat conditions in this example are 13% moisture content at 50° F. Therefore, approximately 9 GPM of water enters with the wheat. The wheat path into the mixer 101 is indicated by conduit 114.
Recirculating water in the present exampel enters the mixer 101 along conduit 115, at a rate of 169 GPM at a temperature of approximately 205° F. Also, new supply water is added from the water supply 50 through conduit 113 into the mixer 101 at a rate of 9 GPM in the present example at a temperature of 114° F., which has been preheated to the stated temperature.
It will be understood that none of the temperatures, pressures, and flow rates stated in the present example limit the possible temperature ranges, pressures, and flow rates in any way. The present example illustrates merely one set of operating conditions possible with the present invention. Any temperatures, pressure, or flow rates can be used as appropriate to the process being used in the present apparatus.
The mixer 101 mixes the grains without crushing them, together with the recirculating water and new supply water. The mixture then flows through conduit 116 to the heater 250; at this point, a flow rate of 185 GPM water, at a temperature of 200° F., passes through the conduit 116.
The heater 250 receives the flow in conduit 116 as well as steam at a pressure of 25 PSIG and at a rate of 1,240 lb/hr from the steam supply 70. Any steam pressure or flow rate can be used; the present valves indicated are for illustration only of operation in one example of the use of the present invention. The steam travels through conduit 117, and the flow rate is controlled by a controller valve 42 which is controlled by the temperature controller 22.
The heated slurry exits from the heater along conduit 118, at a rate of 187 GPM, at a temperature of 210° F. of water, which has been heated by the steam supplied to the heater.
The heated slurry enters the top of the cooker 46, with the grain settling to the grain level 701 and the water settling to the water level 702. This results in even distribution of the grain across the level 701.
The grain descends in plug flow controlled by the metering pump 145. The upper conical baffle 502, together with the lower conical baffle 501, ensures plug flow.
Water flows through the sieve member 35 and is drawn off along conduit 119 at a rate of 161 GPM at a temperature of 209° F. and having 1.5% solids. The wheat mixture exits through conduit 8 at a rate of 7,000 lb/hr of wheat and including water at a rate of 26 GPM.
It will be understood that none of the temperatures, pressures, and flow rates stated in the present example limit the possible temperature ranges, pressures, and flow rates in any way. The present example illustrates merely one set of operating conditions possible with the present invention. Any temperature, pressure or flow rates can be used as appropriate to the process being used in the present apparatus.
This flow enters conduit 10 where a separator 80 separates the wheat from the water, the wheat going into conduit 4 at a rate of 7,000 lb/hr of wheat having 47% moisture content, at a temperature of 200° F. The water separated from the wheat exits the separator 80 along conduit 120 at a rate of 14 GPM, having a temperature of 200° F. and a solids content of 1.5%. These flows combine in conduit 122 for a combined flow rate of water of 175 GPM entering the separator 200, where the fine solids are to be removed.
The separator 200 removes approximately 300 lb/hr of sludge, at 205° F., moisture content of 92.5%, through outlet 201. This sludge enters the sludge cart 111 for disposal. The separated water flows through conduit 202 at a rate of 175 GPM at a temperature of 205° F. into the conduit 9. The conduit 303 carries approximately 6 GPM to the drain 302. This water then flows to a sewage conduit 112 (or to further wastewater processing).
The recirculating water pump 43, then returns the water to the mixture 101 along conduit 115 at a water flow rate of 169 GPM.
FIG. 3 is a view taken along line 3--3 of FIG. 2 showing the general arrangement of the parts in a top view which is partially in section. Here, the circular outline of the lower baffle member 501 is shown connected to the screen 35 by a plurality of struts 503. The textured nature of the screen 35 is generally indicated in FIG. 3 where the circular sectional portion in hatching of the screen 35 is shown with the remaining portion of the screen 35 visible. Also, the circular cross sectional outline of the bottom 36 is shown in FIG. 3 as well.
Recycling the cooking water, heating, and mixing it externally results in a very even internal cooker temperature as well as even and flow distribution in the cooker and greater uniformity. If this mixing and heating were done in the cooker 20, flow disruption of the plug flow of wheat would occur, as would temperature non-uniformities in the grain occur. Such plug flow disruption would be undesirable and would result in overcooking of some particles, and undercooking of other particles of grain. Therefore, the recycling and mixing steps taking place outside of the cooker 20 provide an important improvement over the prior art. Conventional steam heating, i.e. the providing of heat by heating of the outer jacket of the cooker 20, would result in an uneven heat distribution of grain within the cooker 20, also resulting in uneven cooking.
Also, the present cooker has no internal moving parts, and therefore is more reliable while at the sme time maintaining even cooking conditions and plug flow conditions of grain flow, which is critical to the success of this invention.
Each grain particle receives uniform treatment with regard to heating as well as cooking water penetration. There is less mechanical maintenance required than in the prior art devices, and is a sanitary design allowing for clean-in-place cleaning.
The step of removing water at the sieve 35 for recyling is essential, because the grain must be raised from a temperature of approximately 50° F. (or ambient temperature) to approximately 210° F. The grain must be held within the cooker 20 for a sufficient time to cook it fully. This time period will vary depending upon the type of grain used, and water temperature, such cooking times being generally known in the prior art.
Because external heating is used, heat is continuously added to the recycling water and grain mixture, and therefore the water is the only medium used because even heating results therefrom. Steam injection directly into the cooker would destroy the uniform plug flow of grain through the cooker.
As another example of the use of the present invention apparatus and process, a hypothetical set of values of water flow velocity and wheat flow velocity is calculated hereunder. This demonstrates how convection heat transfer can be controlled or increased in the vertical cooker 20 by control of the relative recirculating water flow rate to the wheat-and-water mixture flow rate in conduit 8. Assuring the flow rates in the preceding example, for an inner diameter of three feet of the vertical cooker 20, the water velocity an be calculated from the equation Q=VA, where Q=volume flow rate (which is calculated as mass flow rate divided by the material density); V=velocity (the variable to be determined); and A=effective cross-sectional area through which the material flows. It is assumed that the absolute density of water in the cooker is 62.27 lb/cubic foot; the absolute density of raw wheat is 81.0 lb/cubic foot; and the absolute density of cooked wheat is 75.9 lb/cubic foot.
At the top of the cooker 20, between levels 701 and 702, the minimum water velocity is found by assuming that there is no falling raw grain (if there were, the effective area for the water flow would be reduced and the water velocity, by the equation, would be increased.) For the water flow rate of 187 GPM; and a cross-sectional area of 7.07 square feet; the minimum water velocity between level 702 and 701 is at least 213 ft./hr.
A water and raw grain flows just below level 701, assuming for this example each effective area A (through which each material flows) is one-half the total available area, the velocities are as follows. The water velocity just below level 701 would be approximately 426 ft./hr.; the raw wheat velocity just below level 701 would be 23 ft./hr. Therefore, the velocity difference for heat transfer purposes is 403 ft./hr. in this hypothetical example.
Similarly, for the relative velocities of water and cooked wheat just above the top of cone 502 (in this hypothetical example) would be as follows, again assuming the effective area for flow is one-half the total cross-sectional area. The cooked wheat velocity (which cooked wheat has an increased moisture content over raw wheat) would be 43.4 ft./hr.; the minimum water velocity (disregarding increased velocity due to transverse flow about individual particles) would remain at approximately 426 ft./hr. The velocity difference for convection heat transfer is then approximately 383 ft./hr.
Other, more extreme examples could easily be calculated. For example, for a very dense particulate material, and for much greater recirculating fluid flow rates, greater convection heat transfer rates could be obtained if such is desired. Also, for the case of chemical reaction between the fluid and the particulate material, relative velocity would affect the reaction rate.
The improved continuous process apparatus and method for cooking cereal grains of the present invention is capable of achieving the above-enumerated objects and while preferred embodiments of the present invention have been disclosed, it will be understood that is is not limited thereto but may be otherwise embodied within the scope of the following claims.
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A vertical cooker vessel is used for cooking a grain product. The cooker is vertically oriented and has a conical baffle so as to ensure plug flow so that grain is neither undercooked nor overcooked. The cooking water fills the vessel and is maintained at a predetermined elevated temperature while a continuous stream of water is drawn off through a sieve in the bottom portion of the cooker, then recirculating the water, mixing with raw grain, and then heating, where steam is added to reheat the water and grain. The mixture is added to the top of the vessel. Cooked grain exits from the bottom of the cooker under control of a metering pump. Grain is separated from the water, with water from the separator returning to a mixer for mixing with the recycled water. A conical baffle is located near the sieve. This ensures plug flow of grain through the cooker. A lower second conical baffle prevents turbulent flow beneath the first conical baffle, which flow would otherwise disrupt plug flow.
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BACKGROUND OF THE INVENTION
The present invention relates to liquid injection molding machines and more particularly the present invention relates to runnerless molds for liquid injection molding machines.
Silicone compositions are well known. One particular type of a silicone composition is known as an addition curing silicone composition. Addition curing silicone compositions in a broader sense comprise a vinyl containing diorganopolysiloxane polymer of a viscosity varying anywhere from 100-500,000 centipoises at 25° C., a hydrogen containing polysiloxane having a viscosity from 5 to 1,000 centipoise at 25° C. and a platinum catalyst. This composition in the presence of the platinum catalyst will crosslink to form a silicone elastomer.
There has been various modifications to this composition, for example, adding a vinyl containing resin to increase the strength of the cured composition without increasing undesirably the uncured viscosity of the composition. An important part of the technology of such compositions is the use of inhibitors. Thus, in the uncured state, such compositions are normally packaged with a vinyl containing siloxane or with a hydride polymer and the vinyl polysiloxane in one package such that no package contains the vinyl siloxane, the hydride and platinum catalyst. If all three ingredients are in the same package, the composition cures to a silicone elastomer. Such a composition is normally packaged in two components. With the use of inhibitors the composition has a shelf life of anywhere from several hours to six months or more. One type of a mild inhibitor is a methyl vinyl polysiloxane. This is an inhibitor mixed into the composition in the parts per million level and inhibits the composition such that it does not cure for short periods of time at room temperature but cures rapidly at elevated tempertures, that is temperatures of above 100° C. A more effective inhibitor is allyl isocyanurate disclosed in a patent of Burger ad Hardman U.S. Pat. No. 3,882,083 which is hereby incorporated by reference. Such an inhibitor gives a slightly more extended shelf life to the mixed composition before it cures to a silicone elastomer. Another effective inhibitor that has been found is diallylmaleate. Diallylmaleate is disclosed in the patent of Eckberg U.S. Pat. No. 4,256,870 is hereby incorporated by reference. While the Ekberg inhibitor makes the composition with an extended shelf life of several days, nevertheless when the composition is heated at elevated temperatures at temperatures above 100° C. it cures in a matter of minutes and even seconds. However, there has been developed even more effective inhibitors which allow the three ingredients to be mixed without the compositions curing. One effective inhibitor for instance is the hydroperoxide compound of William J. Bobear disclosed in U.S. Pat. No. 4,061,609 which is hereby incorporated by reference. An effective amount of this hydroperoxide compound makes the composition stable in the mixed state, that is with the three ingredients mixed together and whatever other ingredients are necessary without curing for periods of six months or more. The composition cures at an elevated temperature in a matter of minutes or even seconds to a silicone elastomer. By elevated temperatures it is meant temperatures above 100° C.
It has been found that a properly inhibited addition curing composition can be very effective as a molding composition for liquid injection molding machines. Traditionally, liquid injection molding machines have been utilized with organic thermoplastic compositions. These thermoplastic compositions were taken at room temperature, force fed into the mold either by the reciprocating screw type of injection molding machine or the ram plunger injection molding machine, causing the plastic to be heated and melted and then the plastic being cooled in the mold to form a desired part. The organic plastic in the traditional injection molding machines was fed to the machine in pellets. The heat of the friction created by the plunger or ram, in the injection molding machine caused the plastic pellets to melt and forced the plastic liquid out of the nozzle into the mold. The mold was then cooled so that the part came out as a solid thermoplastic part. Thermoplastic parts are then utilized for whatever purposes it was desired.
Such organic plastic liquid injection molding machines have found wide use in industry. It was found highly desirable to utilize silicone compositions in such injection molding machines to produce silicone parts with good high and low temperature properties. Accordingly, various types of machines have been designed or modified to produce liquid injection molding machines for silicones. It should be noted that silicone compositions differ from the traditional organic plastic compositions in the way they function in the molding machine in that they are liquid when introduced into the ram or plunger of the molding machine and that they are solidified by heating the mold to temperatures above 100° C. which causes the silicone composition to jell and cross-link to a silicone elastomer as distinguished from the cooling of the mold in the organic plastic compounds. One example of a reciprocating screw molding machine which was adapted for silicone compositions can be found in the patent application of A. A. Laghi, Ser. No. 159,262 filed on June 13, 1980. This application discloses a valve means adapted to a reciprocating screw molding machine for introducing silicone compositions into the screw of the molding machine and for preventing the back pressure in the liquid feed tanks from affecting the pressure in the screw plunger action on the silicone composition fed into the mold. Further, there was disclosed a a seal modification on the screw plunger to keep the composition from leaking out from the backside of the screw plunger. These modifications were necessary in order to adapt the typical reciprocating screw plunger liquid injection molding machine so that it could utilize liquid compositions to form molded parts. In addition, the mold was heated so that the silicone composition was cured to a silicone elastomer.
Another type of a liquid injection machine that was modified to accept liquid silicone compositions was the plunger or ram type of liquid injection molding machine as disclosed in the patent application of A. A. Laghi, Ser. No. 183,620 filed Sept. 2, 1980, now abandoned, which is hereby incorporated by reference. As this patent application discloses, there were made various modifications to a plunger or ram type of liquid injection molding machine so that it could utilize silicone compositions and such that the machine could feed even shots of composition into the silicone mold. Again, the mold was heated for silicone compositions. True runnerless molds are known for organic plastics; but until the present time, true runnerless molds were not known for silicone compositions. It should be noted that molds for silicone compositions work differently from molds for organic plastics in that in silicone compositions, the mold has to be heated to cure the part whereas in organic plastic compositions, the mold is cooled to cure the part. Accordingly, the waste associated with prior liquid injection molding machines was eliminated by the advent of the molds of the present invention.
It is an object of the present invention to provide a runnerless mold for silicone liquid molding composition.
It is an additional object of the present invention to provide a mold for silicone injection molding compositions which does not waste material and which does not need the additional expense of a finishing operation to remove unwanted cured compositions from the molded part.
It is still an additional object of the present invention to provide a method for making a molded part from a silicone injection molding composition utilizing a runnerless mold.
It is yet an additional object of the present invention to provide a unique cut-off or shut-off means for a mold utilized in a liquid injection molding machine which is suited for silicone molding compositions.
These and other objects of the present invention are accomplished by means of the invention set forth in the enclosed figures:
FIG. 1--A partly schematic, partly perspective cross sectional view of a mold made in accordance with the present invention.
FIG. 2--A top cross sectional view of a mold or part of a mold apparatus made in accordance with the present invention.
FIG. 3--A cross-sectional view of the shut-off means of the mold of the present invention.
FIG. 4--A partly cross sectional view of the shut-off pin means and nozzle means of the molds of the present invention.
FIG. 5--A cross sectional top view showing the operation of the mold of the present invention.
FIG. 6--A top cross sectional view showing the operation of the shuttle plate in the mold of the present invention.
The above figures, as well as other aspects of the present invention will be explained by means of the disclosure set forth herein below.
SUMMARY OF THE INVENTION
In accordance with the above objects there is provided by the present invention, a mold apparatus for liquid injection molding compositions which is particularly suited for silicone liquid injection molding composition comprising:
a frame;
support posts means mounted on said frame having a front end and a rear end;
a conduit for liquid molding composition slidably mounted on the forward end of said frame and on forward end of said mold frame means having a front end and a rear end;
a first plate means having passage means therein for the passage of liquid composition fixedly mounted on the forward end of said conduit and adapted to slide within said support posts means and within said mold frame means and located adjacent to said forward end of said frame;
nozzle means at the end of said passage means and said plate means adjacent to the rear end of said mold frame means away from said conduit means; pin means slidably mounted in said mold frame means adapted to open and close the nozzle means; and
mold cavity means slidably mounted on said support means adapted to move toward and away from said nozzle means. It should be noted that the present mold apparatus is not solely limited to the utilization of silicone compositions. There can be utilized in the present mold any composition which is heated to effect cure. It should also be appreciated that compositions that are cooled to cure them can also be utilized in the present mold, such as organic plastics. However, the advantages of the instant mold lie in the utilization of compositions which are heated in the mold to cure them to the finish molded part such as for instance, silicone composition and particularly, the addition type of silicone composition discussed previously.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As has been noted, there is preferably utilized in the molds of the instant invention a silicone addition curing compositon. By silicone addition curing it is meant, compositions which contain as the basic ingredient 100 parts of a vinyl containing polysiloxane polymer and preferably a vinyl terminated polysiloxane polymer where the organic groups are selected from monovalent hydrocarbon radicals and wherein the polymer has a viscosity varying from 100-500,000 centipoise at 25° C. With this vinyl containing polymer, there is preferably utilized from 0.1 to 50 parts by weight of an organohydrogenpolysiloxane which can either be a hydride containing silicone resin or a hydride polysiloxane polymer. Examples of either hydride polysiloxane polymers or the hydride resin can be found in the patent of Jeram U.S. Pat. No. 4,041,010 which is hereby incorporated by reference. The hydride containing silicone resin can be either a resin composed of a monofunctional siloxy units and tetrafunctional siloxy units or can be a resin composed of monofunctional siloxy units, tetrafunctional siloxy units and difunctional siloxy units. The hydride polysiloxane may be a hydride polysiloxane containing hydrogen groups in the terminal positions of the polymeric chain as well as in the internal positions in the polymeric chain.
The hydride polysiloxane polymer has a viscosity in the neighborhood of 10-1,000 centipoise at 25° C. and more preferably has a viscosity varying from 10-100 centipoise at 25° C. The catalyst for such compositions is a platinum catalyst and preferably anywhere from 1-200 parts per million of a platinum catalyst is utilized Any type of platinum catalyst, such as solid platinum deposited on charcoal or on gamma aluminum or it can be solubilized platinum complex such as disclosed in Lamoreoux U.S. Pat. No. 3,313,773. However, any useful platinum catalyst can be utilized in such reactions. The solubilized patent catalyst such as that disclosed in the foregoing Lamoreoux Patent is preferred since it is more active than the solid platinum catalyst. In addition to the above ingredients, there can be in the composition vinyl containing resins, such as that disclosed in U.S. Pat. No. 3,436,366 which is hereby incorporated by reference. It should be noted that the basic polymers as well as the organohydrogenpolysiloxane may contain fluorine substituents such as 3,3,3, trifluoropropyl which gives the final cured silicone elastomer exceptional solvent resistence as well as the usual properties of silicones. Examples of such fluorosilicone addition curing compositions can be found in the foregoing general patents which are incorporated by reference.
In addition to the vinyl containing polymer the hydride polysiloxane and the platinum catalyst, there may be incorporated into the composition vinyl containing resins as reinforcing agents disclosed in the foregoing general patents. There can also be incorporated fillers, and specifically, reinforcing fillers. There may also be incorporated vinyl fluids which are terminated on one end with a vinyl unit and terminated on the other end of the polymer chain with a triorganosiloxy unit where in the organic group is saturated hydrocarbon groups such as methyl. The composition is usually packaged into a two packaged state in which the hydride and vinyl siloxane may appear in the same package but the platinum catalyst does not appear in that package. That is, there is no single package in which there is present both the vinyl containing polymer, the hydride polysiloxane and the platinum catalyst. If this occurs, then the composition cures to a silicone elastomer.
A compositon cannot be packaged and stored in that manner unless there is utilized a good inhibitor. Accordingly, in the addition curing compositions to be utilized in liquid injection molds both of the one component type and two component type, there is preferably utilized an inhibitor. Inhibitors of various types are disclosed in the patents set forth in the background of the invention. The invention is not limited to any specific inhibitor. Any type of additon curing composition may be utilized in which there is an inhibitor present such as to give the addition curing composition in the uncured state a good shelf life so that it may be pumped into the mold and cured therein at elevated temperatures without curing prematurely in the conduits of the mold prior to reaching the appropriate position for cure. Accordingly, there may be produced a two packaged composition or a one packaged composition having any suitable inhibitor such as allyl isocyanurate inhibitor, a maleate inhibitor or hydroperoxide compound inhibitor depending on the properties which are desired for the addition curing composition.
It should also be noted, the molds of the present invention are not limited to being utilized solely with silicone compositions. They may be utilized with other types of composition and they may be modified so that the composition in the mold cavity is cooled instead of heated so that the molds of the invention can be utilized with organic plastics. However, as noted previously, the molds of the present invention are best suited for compositons which cure in the mold cavity by heating the mold and are particularly advantageous for utilization with silicone compositions and more specifically, addition curing silicone compositions as has been described above.
FIG. 1 shows a top partial cross sectional view of the apparatus showing tie bars 10 which are held in place by the frame 12. On the other end of the tie bar 10 movable plate 14 is moved by motors 20 through motor shafts 22 against mold cavity plates 30. Plate 14 which moves on tie bar 10 through motors 20 is attached to cavity plates 30 which are held together through bolts 40 as shown in FIGS. 5 and 6. Motors 20 are attached to the frame of the mold of the apparatus 42. At the front end of the mold apparatus of FIG. 1, tie bars 10 are held in place by nuts 50 which go on plates 12 and 42. The machine plate 12 are generally rectangular in shape or square in shape and are solidly connected to the machine frame. The front end of the mold 8 comprises a series of plates as seen in FIG. 1; plates 60, 62, 64, 66, 68, 70, and 72 which are held together in a stationary manner with respect to each of them and to plates 12 by bolts 80. Adjacent to plate 12 and next to plate 60, there is a central sleeve 90 in which slides conduit 92. Conduit 92 has a passageway 94 through which passes the silicone or other composition which is to form the molded part. The silicone composition being generally indicated as 100 in FIG. 1. Conduit 92 throughly engages movable plate 102, plate 102 being fixed to plate 104 which moves integrally with plate 106 to which is attached insulative layer 108. An insulative layer may be needed for proper insulation.
There is formed in plate 102 passageway 112 and in plate 104 passageway 114 which is integral with the other passageway and in plate 106 passageway 120 which is integral with a further passage 130 in insulative layer 108. The silicone composition passes from passageway 100 to passageway 114, passageway 120 and passageway 130 where it is allowed to pass into the mold as will be explained hereinafter. Plates 102, 104, 106 and 108 move integrally within the cavity indicated in the stationary plates 60, 62, 64, 66 and 68.
As more clearly seen in FIGS. 2, 5 and 6, hydraulic motor 140 moves plates 142 which moves integrally with plate 146 which are held together by bolt 150 so as to raise and lower the forward end 162 of pin 163 so as to open and close opening 170 so as to allow liquid composition to form the molded parts to pass through the passageways 100, 112, 114, 120, 130 which for simplicity shall be indicated in other figures as passageway 18 out through opening 170 forward end 162 of pin 163 is retracted as shown in FIG. 2. When the forward end 162 of pin 163 abuts the opening of 170 in passageway 130, then no liquid composition can enter the mold cavity. The forward end of this opening will be more fully explained in FIG. 4. In plate 180, which is stationary, there is nozzle 200, sleeve 202 which fits in bearing surfaces 204 and 206 which are present in plate 140 and in insulative layer 108 and in plate layer 104 and 106. The forward end 162 of pin 163 abuts the opening 170 in nozzle 200 to open and close the nozzle to allow liquid composition to pass through passageway 130 into the mold cavities 240 as more generally shown in FIG. 2 and which construction will be explained hereinafter.
As seen in FIG. 3, the lower forward end 162 of pin 163 just fits the opening 170 of nozzle 200 and accordingly, when the forward end 162 abuts 170, no composition can leak out of nozzle 200 and thus cause dripping. Also as seen in FIGS. 2, 5 and 6, bolt 212 holds plates 102, 104, and 106 together so that they move intregrally with insulative layer 108. Members 141 and 230 are mounted on the side of the mold frame. The entire plates held together by bolt 212 are moved upward/downward by barrel 92 such that nozzle 200 is brought into contact with a mold 240 as shown in FIG. 2 or away from the mold cavity as shown in FIG. 6.
Motor 140 and connecting members 141 and 230 are intended to operate shut off piece 163. The motor frame 140 is slidably connected to the embodiment of plates held together by bolt 212. The position of the motor 140 is connected to plates 142 and 146 through connecting member 141. Plates 146 and 142 are operated by motor 140 so as to close and open the shut off valve 200 by moving downward/upward the shut off piece 163. Mold cavity 240 is located in plates 260, 262, 272, 282 with insulative layer 292 and plate 294. Plate 260 is the shuttle plate which removes the finished piece from the mold compendium of plates as seen in the figure. Plates 262, 272, 282, 292 and 294 are held together by bolts such as bolt 300 so that they move in unison. Shuttle plate 260 along with plates 262, 272 and 282 form opening 302 which is filled with the proper mold forming material such as hardness steel or titanium or other metals or plastics etc. and which forms the outer surfaces of the cavity 240 for the desired part. Surfaces 301 in opening 302 can be utilized to form the configuration for a particular type of molded part that is desired to mold in opening 302. Accordingly, the material so constructed as stated above can be utilized to form a particular type of mold cavity 240 so that a particular type of molded part can be formed in opening 302. It should be noted that the cavity 302 shown in FIG. 2 has a filler material in the different plates which forms the particular type of section that is desired the mold cavity form. In this manner, the entire mold need not be exchanged but only the filler material when it is desired to mold a part of a different configuration. In summary, all that is changed is the material 301 in opening 302 to form a different type or part that is desired to be molded other than the part that is shown in the figures of the instant case.
It should also be noted in FIG. 6, shuttle plate 260 is moved by means not shown away from plates 262 and 180 by means not showing which move it sideways.
Further, the force of the frictional resistance of the part 240 prevents it from detaching from the mold cavity as seen in FIG. 6 and from moving it from the cavity in shuttle plate 260 which force is greater than the force required to move it from its cavity in plate 262. Accordingly the part remains attached to plate 260 when plate 260 separates from plate 262. The means of the operation of the shuttle plate 260 will not be considered in the present case other than what has been given above. It should be noted that bottom plates 262, 272, 282, and 294 as well as shuttle plate 260 are aligned by guide pins 350 which are present in each corner of the mold. Guide pin 350 not only align the plates 262, 272, 282, 292 and 294 but also align shuttle plate 260 with above plates since the shuttle plate is not fixed to the bottom plates which move integrally. It should be noted that there are sleeves 352 in the opening in the foregoing plates for allowing pins 350 to move smoothly therein. There is a sleeves 360 in the opening in the shuttle plate 260 in which the opening through which pin 350 moves so as to align shuttle plate 260 with the rest of the plates. It should be noted that in the movement of shuttle plate 260, the entire plates of 262, 272, 282, 292 and 294 are moved back by motor 20 so as to remove pin 350 from the opening in plate 180 as well as opening in shuttle plate 260 so as to allow the shuttle plate 260 to move sideways so as to release the molded part 240. The opening in plate 180 through which shaft 350 passes also has a sleeves 380. The movement of the lower cavity plates 30 by motor 20 so as to allow shuttle plate 260 to move sideways to release the molded part 320 forms no part of the present invention and accordingly will not be discussed as stated previously. This invention will be disclosed in the patent application of A. A. Laghi, Ser. No. 272,424 filed June 10, 1981 and now U.S. Pat. No. 4,402,657. The part is removed from its mold cavity 302 as explained in FIG. 6 and is utilized for whatever purpose it was intended.
However, respective of this aspect of the present invention, the general configuration of the mold forms the process of this invention. The invention of the instant disclosure is the use of the pin 163 and the use of the movable conduit along with the plates 180, 102, 104, 106 and insulative layers 108 to move intregally therewith along with the coordinated movement of pin 163 so as to produce a runnerless injection mold. It should be noted that plates 180, 260, 262, 270, 272, 282, and 292 have channels therein 400 to which either flow heating fluids such as, for instance; hot oil, steam, or other media or heating is obtained by electric cartridges placed in the same heating channels. Heating media are utilized to heat the silicone molded composition in mold cavity 240 to form the molded part 320.
In addition, plates 102, 104, 106 contain cooling conduits 402 therein through which passes a cooling fluid for cooling the silicone composition that passes through the mold or other types of composition that passes through the passageway 112 in the plates so as to prevent premature curing. It should be noted that generally, by this cooling fluid such as the water, the temperature of composition 100 in passageway 112 is maintained as low as possible so as to prevent it from premature curing. Further, the heating fluid pass through heating channels 400 to raise the temperature of the mold cavity 240 in the neighborhood of 100° C. and above.
Now, considering the operation of the upper portion of the mold as seen in FIGS. 2, 4, 5 and 6, molding material such as silicone molding composition fluids pass through passageway 112 and it is kept from flowing forward by front end 162 of pin 163 which closes the opening 170 of nozzle 200 as shown in FIGS. 3 and 4. When the shuttle plate is moved back in alignment as shown in FIG. 3, then motor 20 moves the composition of plates 30 such that cavity 240 in shuttle plate 260 comes into contact with center plate 180. At that time, pin 350 passes through the opening in shuttle plate 260 and center plate 180 so as to align shuttle plate with the rest of the bottom plate 30. The machine barrel 92 moves the assembly of plates 102, 104 and 106 along with insulative layer 108 and carrying along with it nozzle 200 of cylinder 202 such that the opening 170 is in contact with the cavity 240 in shuttle plate 260. Nozzle 200 passes into opening 130 of plate 180. The hydraulic motor 140 through member 141 moves pin 163 and more particularly, moves the forward end 162 away from opening 170 so as to allow liquid composition to flow into mold cavity 240.
Through logic control of the apparatus when sufficient composition has been entered from passage 112 into cavity 240 through nozzle opening 170 or a predetermined amount of time has elapsed, then, hydraulic motor 140 through member 141 activates plates 142 and 146 so that they move pin 163 and particularly the forward part of 162 of pin 163 so as to contact with nozzle opening 170 so as to close the further passage of fluid silicone molding composition out of nozzle opening 170. It should be noted the pin 163 has the appropriate sleeve 500 and bearing surface 502 in plate 102 through which it passes. Accordingly, by this means, it is possible to have a runnerless operation for injection molding silicone composition into mold cavity 240. Going further on with the operation of the mold by logic control and hydraulic motor 140, forward end 162 of pin 163 closes nozzle opening 170 and machine barrel activates the compounds of mold plates 102, 104, and 106 so as to retract cylinder 202 and nozzle 200 away from opening 130 in plate 180. After curing time has elapsed, motor 20 moves the compound of lower plates 30 so that the shuttle plate 260 can operate to remove the molded part away from the mold. It should be noted that the upper set of mold plates as indicated in FIG. 2 also in the corner of the mold have pin 505 which slides in bores in the movable plates in 142, 146, 102, 104 and 106 and insulative layer 108 so as to properly align the movable plates with the stationary plates and to keep the plates and the channels in the movement of the individual plates from loosing alignment as they are moved by means of the barrel 92. It should be noted that the individual plates, as were the case with lower plates 30, also have sleeves such as sleeve 506 in plate 142 and plate 146.
The figures that are given show only one mold cavity 240. In the typical type of mold, in a single mold, there will be 16 such mold cavities and pins for controlling the flow into the mold cavity. Of course, there can be more or less but 16 has been found to be the convenient number such that the mold can be efficiently utilized to make 16 molded parts at a single time; thus, increasing the efficiency and output of the mold. Of course, the mold can be operated such that there is only one mold cavity and one pin in the mold. It should be noted that the figures as shown do not represent the cross sectional accordingly but only show partial cross sections so as to show the pertinent parts of the mold without showing the full 16 mold cavities and mold pins. For each such mold, there will be only central conduit 92. However, there will be a passageway 112 which will lead to 16 or more or less pins as the case may be and which will utilize the nozzle openings leading into 16 mold cavities or more or less as the case may be.
The principles of the present invention are set forth in the above figures.
As stated above, the above figures are not true cross sections of the entire molds but are done by taking sections along various lines to illustrate the necessary elements of the molds of the present case. For a fuller representation of the molds of these inventions one is referred to the figures in the co-pending application of Laghi, Docket 60 SO-485 which was referred to previously. Further, conduit 92 threadably attached and fixedly attached to plate 102 slidably movable in an opening in plate 12, 90, 142 and 146 and it moves integrally with a composition plates 102, 104, and 106 as well as insulative layer 108.
Accordingly by the utilization of the invention of this case, it is possible to produce a truly runnerless injection molded system for compositions which are heated to cure them to the molded part. This mold system can also be utilized with advantage for parts which are cooled to form the molded part. However, it has its most advantages in being utilized in which the composition is heated to form the molded part as in the case with silicone addition curing molding compositions.
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A mold apparatus for liquid injection molding machine which mold is dripless comprising a frame, four support posts mounted on the frame; a conduit for a liquid molding composition slightly mounted on the forward end of the frame having a front end and a rear end; a first plate means having passage means therein for the passage of the liquid molding composition and fixedly mounted on the forward end of said conduit and adapted to slide within support means and within said mold frame means located adjacent to the forward end of said frame, nozzle means at the end of said passage means of said first plate means at the rear end of said mold frame means and away from said conduit means and pin means slidably mounted in said mold frame means adapted to open and close said nozzle means and mold cavity means slidably mounted on said support means adapted to move toward and away from said nozzle means.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the priority benefit of provisional U.S. Patent Application No. 60/213,282, filed Jun. 22, 2000 entitled, NOVEL STEROIDAL ANTIANDROGENS AND USES THEREOF, the whole of which is hereby incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Part of the work leading to this invention was carried out with United States Government support provided under a grant from the National Institutes of Health, Contract Number 1R01CA81409. Therefore, the United States Government has certain rights in this invention.
BACKGROUND OF THE INVENTION
[0003] Antagonists to both estrogen and androgen receptors have been developed for the treatment of hormone-related conditions. For example, antiestrogenic agents are useful for the treatment of breast cancer and antiandrogenic agents are useful for the treatment of prostate cancer.
[0004] Breast cancer, at 182,000 cases per year, is the most common cancer diagnosis among women in the United States, accounting for over 40,000 deaths annually (Greenlee, 2000). It is estimated that one in eight women will develop breast cancer during their lifetime and one in three of those will die from the disease. Of those women diagnosed with breast cancer, approximately 60% have tumors that are classified as hormone-responsive, meaning that the tissue contains elevated levels of the estrogen receptor and the tumor cell proliferation is stimulated by circulating estrogens (Scott, 1991). Various available treatments include surgery (e.g., lumpectomy, mastectomy or modified radical mastectomy, which removes the breast and underlying muscle along with adjacent lymph nodes), radiation, chemotherapy or biological treatments.
[0005] Hormonal therapy characterized as either removal of estrogen producing tissues, inhibition of estrogen biosynthesis or blockade of estrogen receptors by antagonists (e.g., tamoxifen (Nolvadex®) and Faslodex®, raloxifene, and idoxifene), has been shown to produce a positive objective response (Beatson, 1896; Boyd 1900; Bhatanagar, 1999; Cole, 1971; and Lancet 351, 1998). Such interventions, however, are often accompanied by major side effects that are tolerated because of the particular risks associated with the primary disease. Over the past 10 years, studies with antiestrogens structurally related to tamoxifen have demonstrated that some of the side effects can be ameliorated, depending upon the features incorporated within the structure of the drug. Agents that may block cancer cell proliferation (antagonism) without eliminating the beneficial effects on bone density and cardioprotection have been termed Selective Estrogen Receptor Modulators (SERMs) (Grese; Levenson, 1999). Known non-steroidal antagonists that are tamoxifen-like and raloxifen-like display antiestrogen effects in some tissues and estrogen-like effects in others. These SERMs may be beneficial for the treatment of hormone responsive cancers (or potentially as prophylactic agents) without causing osteoporosis or increasing the risk for cardiovascular disease. However, their receptor affinity is generally less than that of estradiol, and because they have a non-steroidal structure, they often exhibit additional, non-hormonal effects. Additionally, hormone responsive cancers progress to a stage where they become hormone-independent, requiring a subsequent, more aggressive approach.
[0006] Prostate cancer is the most common cancer diagnosis among American men (29%) and the second leading cause of death due to cancer (13%) (Landis, 1999; Haas, 1997; Mettlin, 1997). Like breast cancer in women, most of the newly diagnosed cases are hormone responsive and patients experience a reduction in tumor growth or regression with antihormone (antiandrogen) therapy (Roach, 1999).
[0007] Hormonal therapy is often used in all phases of prostate cancer treatment to help block production or action of the male hormones that have been shown to fuel prostate cancer. Antiandrogens are divided into two groups: steroidal and non-steroidal. Among widely used approved hormone blockers, often used in combination, are Casodex (bicalutamide), Eulexin (flutamide), Anandron (nilutamide), LG 120907, which are nonsteroidal (see FIG. 9), and Lupron (leuprolide acetate), and Zoladex (goserelin acetate implant), which are peptides that block GnRH release. The nonsteroidal antiandrogens can be displaced by endogenous ligands, i.e., dihydrotestosterone. Therefore, these antiandrogens have not been as successful in the treatment of prostate cancer due to their reversability in binding to the androgen receptor. Some studies have suggested that dihydrotestosterone bromoacetate (DHT-BA) binds irreversibly to the androgen receptor (AR). However, other studies show that DHT-BA apparently binds to aldehyde dehydrogenase and not to the AR (McCammon, 1993). Therefore, DHT-BA is not as optimal in the treatment of prostate cancer.
[0008] Because the testicles produce male hormones, some men also undergo testicle removal to cut off the hormone supply. Advanced prostate cancer patients are usually treated with any number of chemotherapeutic drugs such as Novantrone (mitoxantrone), which do not cure the disease but often do ease pain and other symptoms. However, within one to three years of such therapy, there is often recurrence of disease in which the tumor has acquired hormone independence (Galbraith, 1997). At this point, antiandrogen therapy becomes much less effective and a more aggressive intervention is required (Ornstein, 1999). A second issue is that current antiandrogen therapy, even when effective, elicits a number of side effects (e.g., impotence, incontinence, loss of libido, gynecomastia, heat intolerance, or hot flashes) that compromise the patient's quality of life.
[0009] Therefore, the development of more therapeutically effective antiestrogenic and antiandrogenic agents that target hormone-dependent tumors would: (1) provide a substantial benefit for the initial reduction of disease, (2) provide a prolonged disease-free interval, (3) improve the long term prognosis, and (4) reduce the incidence and severity of the side effects.
BRIEF SUMMARY OF THE INVENTION
[0010] The present invention encompasses both prophylactic and therapeutic treatments for a mammal, preferably a human, at risk for a hormone-responsive disorder. In particular, the therapeutic compounds, compositions and methods of the present invention are directed to treatments for both existing estrogen- and androgen-mediated disorders and prevention thereof. Such disorders include, but are not limited to, prevention or treatment of osteoporosis, endometriosis, breast cancer, benign breast cancer, uterine cancer, ovarian cancer, polycystic ovarian disease, prostate cancer, benign prostatic hyperplasia (BPH), reduction of cardiac diseases, acne, seborrhea, alopecia, hirsutism, male pattern baldness, and infertility.
[0011] An embodiment of the therapeutic compound according to the invention is an antiestrogen compound having the structural formula, in the address/message construct described below:
[0012] a) an address unit having the structure:
[0013] wherein:
[0014] R 1 is H, CH 3 , CH 2 CH 3 , OH, OCH 3 , OCH 2 CH 3 , C 1 -C 6 alkyl, CH═CH 2 , CH═CHCH 3 , CH 2 -aryl;
[0015] R 2 is H, CH 3 , COCH 3 , CO(CH 2 ) n CH 3 , CO-aryl, alkyl, cycloalkyl (ether), ester, —COCH 3 ;
[0016] R 3 is CH 3 , CH 2 CH 3 , aryl, heteroaryl, alkyl C 1 -C 6 , alkyl (C 1 -C 6 ) amides, alkyl (C 1 -C 6 ) sulfide, alkyl (C 1 -C 6 ) sulfone, alkyl (C 1 -C 6 ) sulfoxide;
[0017] R 9 is H, OH, NH 2 ; and, attached to the 17α-position of the address unit,
[0018] b) a message unit having the structure:
[0019] wherein:
[0020] R 4 is H, alkyl (C 1 -C 4 );
[0021] R 5 is aryl, heteroaryl, fused aryl, —CO-aryl, CO-fused aryl, —CO-heteroaryl, —CO-fused heteroaryl, biaryl, CO-biaryl, ether-linked aryls, ether-linked heteroaryls, amine-linked aryls, amine-linked heteroaryls, aminoalkoxy arene hybrid, peptidyl hybrid, wherein any aryl, heteroaryl, fused aryl, fused heteroaryl, biaryl, CO-biaryl, ether-linked aryls, ether-linked heteroaryls, amine-linked aryls, amine-linked heteroaryls, aminoalkoxy arene hybrid, and peptidyl hybrid as used herein for groups exemplified in Table 1, rows 13-15, may optionally be substituted, independently, with H, CH 3 , OH, OCH 3 , OCF 3 , NCH 3 , NCOCH 3 , aryl, CO 2 CH 3 , CONH 2 , C 1 -C 4 alkyl, (CF 2 ) n F wherein n=1-4, Cl, Br, I, F, O(CH 2 ) n H wherein n=1-4, NO 2 , NH 2 , NHCOR 1 , CO 2 H, CO 2 R 4 , CONHR4, amyl, thioether, SR 6 , S(O)R 6 , SO 2 R 6 , SO 2 NR 6 R 7 ; wherein R 4 has the definition given above; wherein R 6 is H, C 1 -C 4 alkyl or perfluoroalkyl, aryl, heteroaryl, or optionally substituted allyl, arylmethyl, alkynyl, alkenyl; wherein R 7 is H, C 1 -C 4 alkyl or perfluoroalkyl, aryl, heteroaryl, optionally substituted allyl, arylmethyl, OR 8 or NHR 8 ; wherein R 8 is H, C 1 -C 6 alkyl or perfluoroalkyl, aryl, heteroaryl, optionally substituted allyl or arylmethyl, SO 2 R 6 or S(O)R 6 , wherein R 6 has the definition given above; and
[0022] wherein R 5 can be in either the E or Z configuration in relation to the 17α-position of the address unit.
[0023] Examples of the combined structural formula for the antiestrogen compounds of the present invention that includes both the address and the message units are as follows:
[0024] In another embodiment, the present invention is directed to antiandrogen compounds having the structural formula, in the address/message construct described below:
[0025] a) an address unit having one of the following different structures:
[0026] wherein:
[0027] R 10 is H, CH 3 ;
[0028] R 11 is H, C 1 -C 4 alkyl;
[0029] R 12 is O, (H, OH);
[0030] R 13 is H, OH, Cl, Br, I, CH 3 ;
[0031] R 14 is H, C 1 -C 4 alkyl;
[0032] R 15 is O, (H, OH);
[0033] R 16 is O, NH;
[0034] R 17 through R 18 each independently is H, CH 3 ; and, attached to the 17α-position of the address unit, and
[0035] b) a message unit having the structure:
[0036] wherein:
[0037] R 4 is H, alkyl (C 1 -C 4 );
[0038] R 5 is aryl, heteroaryl, fused aryl, —CO-aryl, CO-fused aryl, —CO-heteroaryl, —CO-fused heteroaryl, biaryl, CO-biaryl, ether-linked aryls, ether-linked heteroaryls, amine-linked aryls, amine-linked heteroaryls, wherein any aryl, heteroaryl, fused aryl, fused heteroaryl, biaryl, CO-biaryl, ether-linked aryls, ether-linked heteroaryls, amine-linked aryls, and amine-linked heteroaryls may optionally be substituted, independently, with H, CH 3 , OH, OCH 3 , OCF 3 , NCH 3 , NCOCH 3 , aryl, CO 2 CH 3 , CONH 2 , C 1 -C 4 alkyl, (CF 2 ) n F wherein n=1-4, Cl, Br, I, F, O(CH 2 ) n H wherein n=1-4, NO 2 , NH 2 , NHCOR 4 , CO 2 H, CO 2 R 4 , CONHR 4 , amyl, thioether, SR 6 , S(O)R 6 , SO 2 R 6 , SO 2 NR 6 R 7 ; wherein R 4 has the definition given above; wherein R 6 is H, C 1 -C 4 alkyl or perfluoroalkyl, aryl, heteroaryl, or optionally substituted allyl, arylmethyl, alkynyl, alkenyl; wherein R 7 is H, C 1 -C 4 alkyl or perfluoroalkyl, aryl, heteroaryl, optionally substituted allyl, arylmethyl, OR 8 or NHR 8 ; wherein R 8 is H, C 1 -C 6 alkyl or perfluoroalkyl, aryl, heteroaryl, optionally substituted allyl or arylmethyl, SO 2 R 6 or S(O)R 6 , wherein R 6 has the definition given above; and
[0039] wherein R 5 can be in either the E or Z configuration in relation to the 17α-position of the address unit.
[0040] Exemplary antiandrogen compounds containing both the address and the message units are as follows:
[0041] Exemplary R 5 groups of the present invention are as follows:
TABLE 1 EXEMPLARY R 5 GROUPS (o/m/p) n = 2 − 6 R = alkyl or cycloalkyl (C 4 -C 8 ) (o/m/p) amide bond L or D n = 1-4 R = alkyl or cycloalkyl (C 4 -C 8 ) (o/m/p) amide bond L or D n = 0 − 2 m = 0 − 3 R = alkyl or cycloalkyl (C 4 -C 8 )
[0042] The above exemplary structures can be substituted at the indicated positions with substituents as described above. Any aryl and heteroaryl groups can be substituted with one to five substituent groups, preferably one to three substituent groups. These substituent groups may include, independently, H, CH 3 , OH, OCH 3 , OCF 3 , NCH 3 , NCOCH 3 , aryl, CO 2 CH 3 , CONH 2 , C 1 -C 4 alkyl, (CF 2 ) n F wherein n=1-4, Cl, Br, I, F, O(CH 2 ) n H wherein n=1-4, NO 2 , NH 2 , NHCOR, CO 2 H, CO 2 R 4 , CONHR 4 , amyl, thioether, SR 6 , S(O)R 6 , SO 2 R 6 , SO 2 NR 6 R 7 ; wherein R 4 has the definition given above; wherein R 6 is H, C 1 -C 4 alkyl or perfluoroalkyl, aryl, heteroaryl, or optionally substituted allyl, arylmethyl, alkynyl, alkenyl; wherein R 7 is H, C 1 -C 4 alkyl or perfluoroalkyl, aryl, heteroaryl, optionally substituted allyl, arylmethyl, OR 8 or NHR 8 ; wherein R 8 is H, C 1 -C 6 alkyl or perfluoroalkyl, aryl, heteroaryl, optionally substituted allyl or arylmethyl, SO 2 R 6 or S(O)R 6 , wherein R 6 has the definition given above; and wherein R 5 can be in either the E or Z configuration.
[0043] Any aryl and heteroaryl groups with any combinations thereof for the compounds of the present invention can be substituted as elsewhere described, with one to five substituent groups. In a preferred embodiment, any aryl and heteroaryl groups with any combinations thereof can be substituted as elsewhere described with one to three substituent groups, where the preferred substituent positions are indicated elsewhere herein.
[0044] These compounds are capable of effectively binding to the estrogen or the androgen receptor, accordingly, to inhibit or modulate the actions of either estrogens or androgens.
[0045] In another embodiment, the present invention is directed to a therapeutic composition for prophylaxis or treatment of a hormone-responsive disorder containing the antiestrogenic and antiandrogenic compounds described above. The therapeutic composition is contained in a pharmaceutically acceptable inert carrier substance that is formulated for oral, topical, intravenous, intramuscular, subcutaneous, intra-vaginal, suppository or parental administration.
[0046] In another embodiment, the present invention is directed to a method of treating a patient suffering from or believed to be at risk of suffering from a hormone-responsive disorder by administering to the patient an effective amount of any of the therapeutic compositions described above for preventing or treating hormone-responsive disorders.
[0047] In a further embodiment, the therapeutic compositions of the present invention comprising the antiestrogen/antiandrogen compounds can be administered, if a low dosage is preferred, in a dosage of about 0.1 μg/kg (body weight) per day to 10 μg/kg/day, preferably 0.5 μg/kg/day to 5 μg/kg/day, and preferably 1 μg to 100 μg for local administration. An exemplary preferred high dosage amount may be in the range of about 0.10 mg/kg/day to about 40 mg/kg/day, more preferably of about 0.50 mg/kg/day to about 20 mg/kg/day, and more preferably of about 1.0 mg/kg/day to about 10 mg/kg/day. Optimal dosage and modes of administration can readily be determined by conventional protocols. The amount of administration is also dependent on the disease-state, on the patient being treated, the patient's body weight and the type of administration.
[0048] In a further embodiment, the present invention is directed to a kit comprising a therapeutic composition as described above and instructions for use thereof.
[0049] In a particular embodiment, the present invention is directed to a method for the prophylaxis or treatment of prostate disorders in a patient by administering an antiandrogenic compound described herein in an effective amount. While not being bound by any theory, it is believed that in particular, the antiandrogenic compounds of the invention change the structural conformation in the helix-12 of the androgen receptor to inhibit transcriptional response.
[0050] In another embodiment, the present invention is directed to an article of manufacture comprising a packaging material and a therapeutic composition of the present invention contained within the packaging material. The therapeutic composition is therapeutically effective for prophylactic or treatment of hormone-responsive disorders. The packing material also comprises a label with instructions for use, which indicates that the therapeutic composition can be used for phrophylaxis or treatment of hormone-responsive disorders.
BRIEF DESCRIPTION OF THE FIGURES
[0051] Other features and advantages of the invention will be apparent from the following description of the preferred embodiments thereof and from the claims, taken in conjunction with the accompanying drawings, in which:
[0052] [0052]FIG. 1 depicts the synthesis of the estradiol analogs according to the invention by coupling the 3-phenolic group of 17α-ethynyl estradiol to the carboxy polystyrene resin. The reagents and conditions used were as follows:
[0053] a—Jones reagent (H 2 Cr 2 O 4 , H 2 SO 4 , acetone);
[0054] b—n-BuLi, TMEDA, cyclohexane, 50° C.;
[0055] c—Dry ice, THF;
[0056] d—17α-Ethynyl estradiol, DCC, DMAP, CH 2 Cl 2 ;
[0057] e—HSnBU3, Et 3 B, THF, 50-60° C.;
[0058] f—17α-Ethynyl estradiol, HSnBU3, Et 3 B, THF, 50-60° C.;
[0059] g—DCC, DMAP, CH 2 Cl 2 ;
[0060] h—R-Aryl-X, Pd(PPh 3 ) 4 , BHT, toluene, N 2 , reflux;
[0061] i—5 N-NaOH in CH 3 OH-Dioxane (1:3);
[0062] j—5%-CH 3 COOH;
[0063] k—10%-NaHCO 3 ;
[0064] [0064]FIG. 2 depicts the synthesis of an exemplary address unit;
[0065] [0065]FIG. 3 depicts the synthesis of an exemplary message unit;
[0066] [0066]FIG. 4 depicts the synthesis of an address-message combination;
[0067] [0067]FIG. 5 depicts the E and Z isomers of 3-(trifluoromethyl)phenylvinyl estradiol;
[0068] [0068]FIG. 6 depicts the exemplary composite of both the address and message units;
[0069] [0069]FIG. 7 depicts prior art antihormones that incorporate functional groups at the 11β- or 7α-position of the steroid nucleus;
[0070] [0070]FIG. 8 depicts exemplary steroid nucleus (address component) and the nonsteroidal antagonist pharmacophore (message component);
[0071] [0071]FIG. 9 depicts prior art nonsteroidal ligands with antiandrogen message component (Helix-12 modulators);
[0072] [0072]FIG. 10 depicts the synthesis of message components using a modified combination of organotin chemistry and palladium-catalyzed coupling reactions; FIGS. 11 a - 11 c are graphs depicting the results of proliferation assays of MCF-7 cells with (ortho, meta, or para) 3-(trifluoromethyl)phenylvinyl estradiol;
[0073] [0073]FIG. 12 is a graph depicting the results of a three-day immature female rat uterotrophic growth assay with (ortho, meta, or para) 3-(trifluoromethyl)phenylvinyl estradiol;
[0074] [0074]FIG. 13 is a graph depicting the results of the estrogenicity of 17α-(ortho, meta, or para) 3-(trifluoromethyl)phenylvinyl estradiols in the immature female rat; and
[0075] [0075]FIG. 14 is a graph depicting the results of an antiestrogen assay of 17α-(ortho, meta, or para) 3-(trifluoromethyl)phenylvinyl estradiols in the immature female rat.
DETAILED DESCRIPTION OF THE INVENTION
[0076] Definition of Terms
[0077] The term “alkyl” used herein refers to a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. Preferred alkyl groups herein contain 1 to 12 carbon atoms. The term “lower alkyl” intends an alkyl group of one to six carbon atoms, preferably one to four carbon atoms. The term “cycloalkyl” intends a cyclic alkyl group, typically of 3 to 6 carbon atoms, more preferably 4 to 5 carbon atoms. The term “cyclooxyalkyl” intends a cyclic alkyl group containing a single ether linkage, again, typically containing 3 to 6 carbon atoms, more preferably 4 to 5 carbon atoms.
[0078] The term “aryl” as used herein refers to a monocyclic aromatic species of 5 to 7 carbon atoms, and is typically phenyl. Optionally, these groups are substituted with one to five, more preferably one to three, lower alkyl, lower flouroalkyl, lower alkoxy, halo, nitro, amino, amide, carboxy, thioether, sulfide, sulfoxide, sulfamino, and/or sulfamide substituents. The aryl group may also comprise of di-, tri-, hexa-, penta-substituted phenyl with all positional (ortho, meta, para) variations. The term “lower flouroalkyl” intends an alkyl group of one to six carbon atoms, preferably one to four carbon atoms. The term “lower alkoxy” intends an alkoxy group with one to six carbon atoms, preferably one to four carbon atoms. The term “carboxy aryl” as used herein refers to a carboxy group attached to the aryl group.
[0079] The term “halo” or “halogen” refers to fluoro, chloro, bromo or iodo, and usually relates to halo substitution for a hydrogen atom in an organic compound.
[0080] The term “optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0081] The term “heteroaryl” as used herein refers to monocyclic aromatic species of three to seven carbon atoms, and is preferably one to six carbon atoms, and is more preferably one to five carbon atoms, and is typically phenyl. In particular, the heteroaryl comprises, for example, oxazole, thiazole, isoxazole, where these heteroaryls have nitrogen, oxygen, or sulfur atoms in the monocyclic ring. Optionally, these groups are substituted with one to five, more preferably one to three, lower alkyl, lower flouroalkyl, lower alkoxy, halo, nitro, amino, amide, carboxy, thioether, sulfide, sulfoxide, sulfamino, and/or sulfamide substituents. The aryl group may also comprise of di-, tri-, hexa-, penta-substituted phenyl with all positional (ortho, meta, para) variations. The term “carboxy-heteroaryl” as used herein refers to a carboxy group attached to a heteroaryl group.
[0082] The term “fused aryl” as used herein refers to bicyclic aromatic species of three to seven carbon atoms, and is typically phenyl. In particular, the fused aryl may comprise of naphthyl, benzothienyl, or benzofuryl. Optionally, these groups are substituted with one to five, more preferably one to three, lower alkyl, lower flouroalkyl, lower alkoxy, halo, nitro, amino, amide, carboxy, thioether, sulfide, sulfoxide, sulfamino, and/or sulfamide substituents. The aryl group may also comprise of di-, tri-, hexa-, penta-substituted phenyl with all positional (ortho, meta, para) variations. The term “carboxy-fused aryl” as used herein refers to a carboxy group attached to a fused-aryl group.
[0083] The term “biaryl” as used herein refers to two monocyclic aromatic species of four to seven carbon atoms, and is typically different configurations of a combination of a phenyl and a heteroaryl. Optionally, these groups are substituted with one to five, more preferably one to three, lower alkyl, lower flouroalkyl, lower alkoxy, halo, nitro, amino, amide, carboxy, thioether, sulfide, sulfoxide, sulfamino, and/or sulfamide substituents. The aryl group may also comprise of di-, tri-, hexa-, penta-substituted phenyl with all positional (ortho, meta, para) variations. The term “carboxy-biaryl” as used herein refers to a biaryl attached to a carboxy group.
[0084] The terms “ether-linked aryls” and “ether-linked heteroaryls” as used herein refer to two aryls/heteroaryls as defined above that are linked by an ether group. Optionally, these groups are substituted with one to five, more preferably one to three, lower alkyl, lower flouroalkyl, lower alkoxy, halo, nitro, amino, amide, carboxy, thioether, sulfide, sulfoxide, sulfamino, and/or sulfamide substituents. The aryl group may also comprise of di-, tri-, hexa-, penta-substituted phenyl with all positional (ortho, meta, para) variations.
[0085] The terms “amine-linked aryls” and “amine-linked heteroaryls” as used herein refer to two aryls/heteroaryls as defined above that are linked by an amine group. The terms aminoalkoxyl arene hybrids and peptidyl hybrids as used herein are referred to the groups exemplified in Table 1. Optionally, these groups are substituted with one to five, more preferably one to three, lower alkyl, lower flouroalkyl, lower alkoxy, halo, nitro, amino, amide, carboxy, thioether, sulfide, sulfoxide, sulfamino, and/or sulfamide substituents. Aryl group may also comprise of di-, tri-, hexa-, penta-substituted phenyl with all positional (ortho, meta, para) variations.
[0086] The term “effective amount” as used herein means a nontoxic but sufficient amount of a compound to provide the desired effect. The exact amount required will vary from patient to patient, depending on the species, age, and general condition of the patient, the severity of the condition being treated, and the particular compound and its mode of administration. Thus, it is not possible to specify an exact “effective amount.” However, an appropriate effective amount may be determined by one of ordinary skill in the art using only routine experimentation.
[0087] The term “pharmaceutically acceptable” as used herein means a material which is not biologically or otherwise undesirable, i.e., the material may be administered to a patient along with the selected compound without causing any undesirable biological effects or interacting in a deleterious manner with any of the other components of the pharmaceutical composition in which it is contained.
[0088] The present invention comprises the design, synthesis and development of a new class of chemotherapeutic agents for the treatment of hormone-responsive disorders. In the new class of chemotherapeutic agents, two components—a message subunit or pharmacophore, present in the nonsteroidal antagonists (e.g., antiandrogens, antiestrogens) and the address subunit found in the steroidal agonists (e.g., androgens, estrogens)—are combined into a single composite entity. In particular, specific compounds in this new class of chemotherapeutic agents target the estrogen and/or the androgen receptors. The general formula for the agents of the invention was determined based on the discovery that the interaction between androgen/estrogen with the receptor involves a two step process. There is an initial association of the hormone (address component) with a specific part of the receptor, called the hormone binding domain, followed by the induction of a conformational change in the receptor (message component) that generates the observed biological response.
[0089] Accordingly, the present invention incorporates the “address-message” concept to generate, for example, prostate cancer tissue affinity, selectivity, and efficacy, and employs transition metal catalysts/reagents to prepare the novel therapeutic compounds. As an embodiment, the present invention uses modified palladium catalysts for carbon-carbon (Stille, Suzuki reactions) and carbon-nitrogen/oxygen (Buchwald, Hartwig) coupling reactions. As another embodiment of the present invention, the use of 1D/2D-NMR (Nuclear Magnetic Resonance) and the molecular modeling in the evaluation of the conformational analysis of the target compounds provides the capability for biological and structural data.
[0090] The novel therapeutic compounds constitute a structurally unique class of steroidal derivatives, e.g., derivatives of, for example, 17α-(substituted)phenylvinyl-17β-estradiols as estrogens and antiestrogens, and corresponding (nor)testosterones and dihydro-derivatives. In particular, identification of the most potent and selective antagonists for prophylaxis and treatment provides for a more effective treatment of hormone-responsive disorders and thereby prolong the disease-free interval. The present invention provides for a more potent and effective agent which increases the initial response coupled with a slower progression to hormone independence. Additionally, the therapeutic compound of the present invention targets specifically and more selectively thereby reducing the incidence and/or severity of the side effects of anti-estrogen or anti-androgen therapy.
EXAMPLES
[0091] The following examples are presented to illustrate the advantages of the present invention and to assist one of ordinary skill in making and using the same. These examples are not intended in any way otherwise to limit the scope of the disclosure.
[0092] Preferred antiestrogens/antiandrogens for the prevention or treatment of its corresponding hormone-related disorder acting to inhibit estrogen/androgen action may be prepared accordingly as follows:
Example I Synthesis and Evaluation of Steroidal Antiestrogens at the 17α-Position of Estradiol
[0093] Solid Phase Synthesis of 17α-substitued Phenylvinyl Estradiols:
[0094] Materials
[0095] Reagents and solvents were obtained from commercial sources (Aldrich and Sigma) and were used without further purification. Wang resins and carboxylated polystyrene resins were obtained from Novabiochem. The loading capacities of the resins, 0.75 mmol g −1 for the Wang resin and 2.47 mmol g −1 for the polystyrene resin, were determined by the manufacturer.
[0096] General Methods
[0097] A specially designed flask which had a glass frit, through which the reaction mixture could be filtered by applying pressure, was used for the solid phase synthesis. Purifications for the intermediates were done by rinsing resins three times with the following solvents: CH 2 Cl 2 , THF, DMF, MeOH, CH 2 Cl 2 . The cleaved products were purified on a silica gel column chromatography using the appropriate solvents and were characterized by melting point, NMR, IR and electrical analysis. Melting points were determined in open capillary on an Electrothermal Melting Point Apparatus and were uncorrected. IR spectra were recorded on a Perkin-Elmer Model 1600 FT-IR spectrometer. 1 H and 13 C NMR spectra were obtained with a Varian XL-300 NMR spectrometer at 300 MHz in CDCl 3 , acetone-d 6 , or DMSO-d 6 as a solvent. Elemental analyses were performed by Atlantic Microlab, Inc. (Norcross, Ga.). As on-resin reaction monitoring methods, color tests and FT-IR methods were used. Bomoscresol green (0.5% in ethanol, pH=8) was used to assay for free carboxylic acids. 18 The color of the stock solution was dark blue and changed to yellow in the presence of free carboxy groups. Antimony (III) chloride solution (25% in CCl 4 ) was also used to determine whether the steroid (17α-ethynyl estradiol) was coupled to the resin and a positive test result for the presence of estradiol was indicated by the color purple (Carr, 1926; Blatz, 1972; Jork, 1990). In addition, a spectro-scopic method (FT-IR) was facilitated to detect chromophore change by reaction.
[0098] Preparation of the Carboxylated Resin
[0099] (Method A). The Wang resins (1 g, 0.75 mmol) were swelled in the CH 2 Cl 2 overnight and rinsed twice with THF, CH 3 OH, CH 2 Cl 2 and acetone. Acetone (5 mL) was added to the swelled resins. To the slurry was added 1 mL of Jones reagent (Bowden, 1946) in a dropwise manner. The mixture was allowed to stand at room temperature for 24 h. The resin mixture was rinsed twice with water-acetone (1:1), CH 3 OH, DMF, DMSO and CH 2 Cl 2 and dried in vacuo. The loading capacity after the carboxylation reaction was 0.4-0.6 mmol g −1 , which was determined with the coupling of 17α-ethynyl estradiol to the resin. The aliquot of the resins was characterized by FT-IR. FT-IR (KBr) v: 3000-3500 (OH, broad), 1690 (C═O, broad), 1603, 1492, 1452 (aromatic ring), 1279 (C—O). (Method B). The carboxylation of a polystyrene resin was accomplished using the method described by Farrall et al. (Farrall, 1976). FT-IR (KBr) v: 3420 (OH, broad), 1630 (C═O, broad), 1200-1400 (C—O, broad). Loading capacity: 1.5-1.9 mmol g −1 .
[0100] Coupling 17α-ethynyl Estradiol to the Resins
[0101] The carboxylated Wang resin (2.3 g) or polystyrene resin (2.5 g) was placed in the reactor equipped with a magnetic stirrer. The resin was swelled in the ch 2 cl 2 for 5 h and washed sequentially with THF, DMF, CH 3 OH, THF and CH 2 CL 2 . To the resin was added 0.23 g (1.1 mmol) of dicyclohexylcarbodiimide (DDC) and 5 ml of CH 2 CL 2 and the mixture was mildly stirred for 10 min. To the slurry was added 0.75 g (2.6 mmol) of 17α-ethynyl estradiol dissolved in 10 ml of CH 2 CL 2 -DMF (9:1) solvent and catalytic amount of 4-dimethylaminopyridine (DMAP). The reaction mixture was stirred for 5 min and then allowed to stand at room temperature for 24 h. The resin was washed three times with CH 2 CL 2 CH 3 OH, IPA (60° C.), THF and DMF (60° C.) (Morales, 1998). The rinsed resin was dried under vacuum for 5 h. The actual loading of the resin was determined by quantitative measurement of the material by cleavage from known weight of resin using 5 N-NaOH in CH 3 OH-dioxane (1:3). The resin-bound steroids were characterized by FT-IR and the cleaved compounds by H and
[0102] [0102] 13 C NMR before proceeding to the next step. The loading capacity of each resin was shown in Method A and B; FT-IR (KBr) v; 3437 (17β—OH), 3301 (17α-C≡C-H), 1735 (C═O), 1607, 1493, 1452 (aromatic ring), 1216(C—O).
[0103] Hydrostannylation
[0104] (Method A). The 17α-ethynyl estradiol coupled to the resin (0.49 g, 0.57 mmol g −1 ) was placed in a dry 25 mL reaction flask equipped with a reflux condenser and a magnetic stirrer and was swelled in THF for 1 h. To the slurry in the dry THF were treated triethylborane (0.7 mL) and tributyltin hydride (1 mL) (Nozaki, 1989). The mixture was allowed to stand at 60-70° C. for 48 h under a nitrogen atmosphere. The reaction mixture was washed three times each with CH 2 Cl 2 , CH 3 OH, DMF, CH 2 Cl 2 and ethyl acetate and the resultant resin was dried in vacuo. An aliquot of the resins was cleaved with 5 N NaOH in CH 3 OH—CH 2 Cl 2 (1:2) to afford a mixture of E- and Z-isomers. The mixture was separated by chromatography on the silica gel to give a 23% (0.13 mmol g −1 ) yield of products, consisting of 21% (0.12 mmol g −1 ) of the E-isomer and 2% (0.01 mmol g −1 ) of the Z-isomer. R f (Z-isomer=0.58 (hexane-ethyl acetate, 4:1); Rf (E-isomer)=0.44 (hexane-ethyl acetate, 4:1); Amorphous; 1 H NMR (CDCl 3 , 300 MHz, δ), 0.88 (s, 3H, C 18 -methyl-H), 1.2-2.4 (m, steroid envelope and tributyl-stannyl-H), 2.7-2.9 (m, 2H, C 6 —H), 6.06 (d, 1H, J=19.4 Hz, C 21 vinyl-H), 6.22 (d, 1H, J=19.4 Hz, C 20 vinyl-H), 6.79(d, 1H, J=2.4 Hz, C 4 —H), 6.84 (dd, 1H, J=2.6, 8.4 Hz, C 2 —H), 7.28 (d, 1H, J=8.8 Hz, C 1 —H); 13 C NMR (CDCl 3 ), 9.6 (C 22 , 4C), 13.7 (C 24 , 4C), 14.2 (C 18 ), 23.4 (C 15 ), 26.4 (C 11 ), 27.3 (C 25 , 4C), 27.4 (C 7 ), 29.2 (C 23 , 4C), 29.6 (C 6 ), 32.4 (C 12 ), 35.9 (C 16 ), 39.4 (C 8 ), 43.8 (C 9 ), 46.7 (C 13 ), 49.0(C 14 ), 85.6 (C 17 ), 112.6 (C 2 ), 115.2 (C 4 ), 124.6 (C 21 ), 126.5 (C 1 ), 132.7 (C 10 ), 138.3 (C 5 ), 152.4 (C 20 ), 153.3 (C 3 ), FT-IR (KBr) v: 3445 (17β-OH, broad, 1719 (C═O), 1653 (C═C), 1607, 1493, 1451 (aromatic ring), 1217 (C—O).
[0105] (Method B). The 17α-ethynyl estradiol (3 g, 10 mmol) was dissolved in THF and treated with triethylborane (2 mL, 17 mmol) and tributyltin hydride (3 g, 11 mmol). The mixture was stirred with a magnetic stirrer at 60° C. for 16 h. The crude mixture (7.73 g) was evaporated to dryness, redissolved in the CH 2 Cl 2 , and transferred to the swelled resin (5 g) in CH 2 Cl 2 in the presence of DCC. A catalytic amount of DMAP was added to the mixture, which was allowed to stand for 24 h. The resultant functionalized resin was treated as previously described. The total loading for both E- and Z-isomers was 0.59 mmol g−1 with 0.56 mmol g −1 of E-isomer and 0.03 mmol g −1 of Z-isomer, however, by the dry weight difference between pre- and post-reaction, the loading for both E- and Z-isomers was 1.55 mmol g −1 .
[0106] Electrophilic Destannylation on the Resin
[0107] The Stille reaction was used to couple the anchored E- and Z-stannylvinyl estradiol to aryl halides. The resin was added to the reaction flask, swelled in the CH 2 Cl 2 , subsequently treated with 10 mL of anhydrous toulene. To the resultant slurry was added a 3-4 fold excess of the functionalized aryl halide, 1-2 crystals of 3.5-di-t-butyl-4-hydroxytoulene (BHT), and Pd(PPh 3 ) 4 (Bowden, 1946; Farrall, 1976). The reaction was allowed to proceed at 90-100° C. for 24 h. After cooling, the resin was washed as previously described, dried in vacuo and weighed.
[0108] Cleavage
[0109] The resin was swelled in CH 2 Cl 2 (10 mL) containing 3 mL of 5 N-NaOH in CH 3 OH-Dioxane (1:3) and stirred for 1 h. This cleavage step was repeated three times. Most of the product was collected from the first attempt, a small amount by second hydrolysis, and almost none from the third trial. The fractions were combined, evaporated to dryness, and partitioned between ethyl acetate and water. Acetic acid (1 mL, 5%) was added. The organic phase was washed with 10% aqueous NaHCO 3 to remove the residual acetic acid, dried over MgSO 4 , filtered and evaporated to dryness. The crude product was purified by silica gel column chromatography or by recrystallization from the appropriate solvent.
[0110] 17α-20E-21-(2-Trifluoromethylphenyl)-19-norpregna-1,3,5(10),20-tetraene-3,17β-diol (17α-E-(2-trifluoromethylphenyl)-vinyl estradiol) (4a). Yield=38%; R t =0.19 (hexane-ethyl acetate, 4:1); mp 224-225° C.; 1 H NMR (300 MHz, Acetone-d 6 , 6) 1.02 (s, 3H, C 18 methyl-H), 1.2-2.4 (m, steroid envelope), 2.7-2.9 (m, 2H, C 6 —H), 3.98(s, 1H, 17P hydroxyl-H), 6.53 (d, 1H, J=2.3 Hz, C 4 —H), 6.58 (dd, 1H, J=2.6, 8.5 Hz, C 2 —H), 6.64 (d, 1H, J=15.7 Hz, C 20 vinyl-H), 7.0 (dd, 1H, J=2.5, 15.8 Hz, C 21 vinyl-H), 7.07 (d, 1H, J=8.7 Hz, C 1 —H), 7.42 (t, 1H, J=7.8 Hz, C 26 —H), 7.60 (t, 1H, J=7.3 Hz, C 25 —H), 7.69 (d, 1H, J=7.8 Hz, C 27 —H), 7.81 (d, 1H, J=8.3 Hz, C 24 —H), 7.98 (s, C 3 hydroxy-H); 13 C NMR (75.4 MHz, Acetone-d 6 , 8) 14.7 (C 18 ), 24.1 (C 15 ) 27.2 (C 11 ), 28.3 (C 7 ), (C 6 ), 33.4 (C 12 ), 37.5 (C 16 ), 40.7 (C 8 ); 44.6 (C 9 ), 48.4 (C 13 ), 50.0 (C 14 ), 84. 3 (C 17 ), 113.5 (C 2 ), 115.9 (C 4 ), 123.4 (C 21 ), 125.6 (q, J=273.2 Hz, C 28 :CF 3 ), 126.4 (q, J=5.8 Hz, C 24 ), 127.0 (C 1 ), 127.4 (q, J=29.4 Hz, C 23 ), 127.8 (C 26 ), 128.6 (C 27 ), 132.0 (C 25 ), 133.2 (C 10 ), 137.9 (C 22 ), 139.1 (C 5 ), 142.4 (C 20 ), 155.9 (C 3 ); Anal. Calcd for C 27 H 29 O 2 F 3 : C, 73.30; H, 6.56. Found: C, 73.04; H, 6.68.
[0111] [0111] 17 α-20E-21-(3-Trifluoromethylphenyl)-19-norpregna-1,3,5(10),20-tetraene-3,17β-diol (17α-E-(3-trifluoro methylphenyl)-vinyl estradiol) (5a). Yield=33%; R f (E-isomer)=0.19 (hexane-ethyl acetate, 4:1); mp 244-246° C.; 1 H NMR (300 MHz, Acetone-d 6 , 6), 1.01 (s, 3H, C 18 -methyl), 1.2-2.4 (m, steroid envelope), 2.7-2.9 (m, 2H, C 6 —H), 3.98 (s, 1H, 17β hydroxyl-H), 6.53 (d, 1H, J=2.6 Hz, C 4 —H), 6.58 (dd, 1H, J=2.6, 8.3 Hz, C 2 —H), 6.74 (d, 1H, J=16 Hz, C 21 vinyl-H), 6.84 (d, 1H, J=16 Hz, C 20 vinyl-H), 7.06 (d, 1H, J=8.3 Hz, C 1 —H), 7.54-7.56 (m, 2H, C 25 , C 27 —H), 7.75-7.79 (m, 2H, C 23 , C 26 —H), 7.93 (s, C 3 -hydroxy-H); 13 C NMR (75.4 MHz, Acetone-d 6 , δ), 14.7 (C 18 ), 24.1 (C 15 ), 27.3 (C 11 ), 28.3 (C 7 ), (C 6 ), 33.5 (C 12 ), 37.5 (C 16 ), 40.7 (C 8 ), 44.6 (C 9 ), 48.4 (C 13 ), 50.1 (C 14 ), 84.2 (C 17 ), 113.5 (C 2 ), 115.9 (C 4 ), 123.6 (q, J=5.6 Hz, C 25 ), 124.1 (q, J=3.7 Hz, C 23 ), 125.4 (q, J=271 Hz, C 28 :CF 3 ), 126.0 (C 26 ), 127.0 (C 1 ), 130.2 (C 21 ), 130.7 (C 27 ), 131.2 (q, J=32 Hz, C 24 ), 132.0 (C 10 ), 138.4 (C 5 ), 139.7 (C 20 ), 139.9 (C 22 ), 155.9 (C 3 );
[0112] Anal. Calcd for C 27 H 29 O 2 F 3 : C, 73.30; H, 6.56. Found: C, 73.42; H, 6.68.
[0113] 17α-20E-21-(4-Trifluoromethylphenyl)-19-norpregna-1,3,5(10),20-tetraene-3, 17β-diol (17α-E-(4-trifluoro methylphenyl)-vinyl estradiol) (6a). Yield=49%; R f =0.15 (hexane-ethyl acetate, 4:1); mp 215-217° C.; 1 H NMR (Acetone-d 6 , 300 MHz, 8), 1.02 (s, 3H, C 18 methyl-H), 1.2-2.4 (m, steroid envelope), 2.7-2.9 (m, 2H, C 6 —H), 3.90 (s, 1H, 17β hydroxyl-H), 6.53 (d, 1H, J=2.6 Hz, C 4 —H), 6.58 (dd, 1H, J=2.6, 8.4 Hz, C 2 —H), 6.73 (d, 1H, J=16 Hz, C 21 vinyl-H), 6.85 (d, 1H, J=16 Hz, C 20 vinyl-H, 7.07 (d, 1H, J=8.3 Hz, C 1 —H), 7.64 (d, 2H, J=8.7 Hz, C 23 , C 27 —H), 7.70 (d, 2H, J=8.6 Hz, C 24 , C 26 —H), 8.0 (s, C 3 -hydroxy-H); 13 C NMR (75.4 MHz, Acetone-d 6 , 6) 14.7 (C 18 ), 24.1 (C 15 ), 27.3 (C 11 ), 28.3 (C 7 ), (C 6 ), 33.5 (Cl 2 ), 37.6 (C 16 ), 40.7 (C 8 ), 44.6 (C 9 ), 48.5 (C 13 ), 50.2 (Cl 4 ), 84.2 (C 17 ), 113.5 (C 2 ), 115.9 (C 4 ), 125.4 (q, J=270.6 Hz, C 28 :CF 3 ), 126.0 (C 21 ), 126.2 (q, J=3.5 Hz, C 26 ), 126.2 (q, J=3.5 Hz, C 24 ), 127.0 (C 1 ), 127.6 (C 23 , C 27 ), 128.9 (q, J=32 Hz, C 25 ), 132.0 (C 10 ), 138.4 (C 5 ), 140.6 (C 20 ), 142.7 (C 22 ), 155.9 (C3);
[0114] Anal. Calcd for C 27 H 29 O 2 F 3 : C, 73.30; H, 6.56. Found: C, 73.36; H, 6.79.
[0115] 17α-20Z-21-(4-Trifluoromethylphenyl)-19-norpregna-1,3,5(10),20-tetraene-3,17α-diol (17α-Z-(4-trifluoro methylphenyl)-vinyl estradiol) (6b). Yield=17%; R f =0.29 (hexane-ethyl acetate, 4:1); 1 H NMR (300 MHz, Acetone-d 6 , 6) 0.97 (s, 3H, C 18 methyl-H), 1.2-2.4 (m, steroid envelope), 2.7-2.9 (m, 2H, C 6 —H), 3.89 (s, 1H, 17P hydroxyl-H), 6.12 (d, 1H, J=12.9 Hz, C 21 vinyl-H), 6.48-6.62 (m, 3H, C 2 , C 4 , C 20 vinyl-H), 7.11 (d, 1H, J=8.1 Hz, C 1 —H), 7.59 (d, 2H, J=8.4 Hz, C 23 , C 27 —H), 7.80 (d, 2H, J=8.4 Hz, C 24 , C 26 —H), 7.95 (s, C 3 hydroxy-H).
[0116] 17α-20E-21-(2-Methylphenyl)-19-norpregna-1,3,5(10), 20-tetraene-3,17β-diol (17α-E-(2-methylphenyl)-vinyl estradiol) (7a). Yield=38%; R t =0.18 (hexane-acetone, 4:1); mp 199-200° C.; 1 H NMR (Acetone-d 6 , 300 MHz, δ), 1.01 (s, 3H, C 18 methyl-H), 1.2-2.4 (steroid envelope), 2.34 (s, 3H, C 28 methyl-H), 2.7-2.9 (m, 2H, C 6 —H), 3.84 (s, 1H, 17β hydroxyl-H), 6.44 (d, 1H, J=16 Hz, C 21 vinyl-H), 6.52-6.63 (m, 2H, C 2 , C 4 —H), 6.83 (d, 1H, J=16 Hz, C 20 vinyl-H), 7.07 (d, 1H, J=8.3 Hz, C 1 —H), 7.10-7.15 (m, 3H, C 24 , C 25 , C 26 —H), 7.48 (d, 1H, J=6.8 Hz, C 27 —H), 7.97 (s, C 3 hydroxy-H); 13 C NMR (75.4 MHz, Acetone-d 6 , δ) 14.7 (C 18 ), 19.9 (C 28 , methyl), 24.1 (C 15 ), 27.3 (C 11 ), 28.3 (C 7 ), (C 6 ), 33.5 (C 12 ), 37.5 (C 16 ), 40.7 (C 8 ), 44.7 (Cg), 48.2 (C 13 ), 50.1 (C 14 ), 84.2 (C 17 ), 113.5 (C 2 ), 115.9 (C 4 ), 125.4 (C 26 ), 126.5 (C 25 ), 126.9 (C 24 ), 127.0 (C 1 ), 127.7 (C 21 ), 130.8 (C 27 ), 132.0 (C 10 ), 135.9 (C 20 ), 137.9 (C 22 ), 138.4 (C 5 ), 138.8 (C 23 ), 155.9 (C 3 ); Anal. Calcd for C 27 H 32 O 2 : C, 83.51; H, 8.25. Found: C, 83.79; H, 8.65.
[0117] 17α-20E-21-(3-Methylphenyl)-19-nonpregna-1,3,5(10), 20-tetraene-3,17β-diol (17α-E-(3-methylphenyl)-vinyl estradiol) (8a). Yield=75%; R t =0.17 (hexane-acetone, 4:1); mp 204-205° C.; 1 H NMR (300 MHz, Acetone-d 6 , 6), 1.00 (s, 3H, C 18 methyl-H), 1.2-2.4 (m, steroid envelope), 2.31 (s, 3H, C 28 methyl-H), 2.7-2.9 (m, 2H, C 6 —H), 3.74 (s, 1H, 17β hydroxyl-H), 6.52-6.63 (m, 4H, C 4 , C 2 , C 21 vinyl, C 20 vinyl-H), 7.03 (d, 1H, J=7.3 Hz, C 25 —H)., 7.07 (d, 1H, J=8.7 Hz, C 1 —H), 7.16-7.31 (m, 3H, J=7.4 Hz, C 23 , C 26 , C 27 —H), 7.93 (s, 1H, C 3 hydroxy-H); 13 C NMR (75.4 MHz, Acetone-d 6 , 6) 14.8 (C 18 ), 21.4 (C 28 ; methyl), 24.1 (C 15 ), 27.3 (C 11 ), 28.4 (C 7 ), (C 6 ), 33.5 (C 12 ), 37.4 (C 16 ), 40.8 (C 8 ), 44.7 (Cg), 48.3 (C 13 ), 50.2 (C 14 ), 84.2 (C 17 ), 113.6 (C 2 ), 116.0 (C 4 ), 124.4 (C 27 ), 127.0 (Cl), 127.7 (C 25 ), 127.8 (C 26 ), 128.5 (C 21 ), 129.2 (C 23 ), 132.2 (C 10 ), 137.0 (C 20 ), 138.4 (C 5 ), 138.7 (C 22 , C 24 ), 155.9 (C 3 ); Anal. Calcd for C 27 H 32 O 2 : C, 83.51; H, 8.25. Found: C, 83.23; H, 8.42.
[0118] 17α-20Z-21-(3-Methylphenyl)-19-norpregna-1,3,5(10), 20-tetraene-3,17β-diol (17α-Z-(3-methylphenyl)-vinyl estradiol) (8b). Yield=54% (0.01 g); R t =0.25 (hexane-acetone, 4:1); 1 H NMR (300 MHz, Acetone-d 6 , δ) 0.95 (s, 3H, C 18 methyl-H), 1.2-2.4 (m, steroid envelope), 2.31 (s, 3H, C 28 methyl-H), 2.7-2.9 (m, 2H, C 6 —H), 3.27 (s, 1H, 17P hydroxyl-H), 5.96 (d, 1H, J=13.1 Hz, C 21 vinyl-H, 6.44 (d, 1H, J=13.1 Hz, C 20 vinyl-H), 6.53 (d, 1H, J=2.6 Hz C 4 —H), 6.60 (dd, 1H, J=2.6, 8.3 Hz, C 2 —H), 7.03 (d, 1H, J=7.3 Hz, C 25 —H), 7.11 (d, 1H, J=8.3 Hz, C 1 —H), 7.17 (t, 1H, J=7.6 Hz, C 26 —H), 7.38-7.43 (m, 2H, C 23 , C 27 —H), 7.95 (s, 1H, C 3 hydroxy-H); 13 C NMR (75.4 MHz, Acetone-d 6 , 6) 14.58 (C 18 ), 21.42 (C 28 : methyl). 23.85 (C 15 ), 27.40 (C 11 ), 28.30 (C 7 ), (C 6 ), 32.97 (Cl 2 ), 38.4 (C 16 ), 40.9 (C 8 ), 44.7 (Cg), 48.8 (C 13 ), 50.1 (C 14 ), 84.3 (C 17 ), 113.6 (C 2 ), 116.0 (C 4 ), 127.1 (C 1 ), 127.8 (C 27 ), 128.1 (C25), 128.3 (C 26 ), 129.7 (C 21 ), 131.4 (C 23 ), 132.0 (C 10 ), 137.1 (C 20 ), 137.6 (C 24 ), 138.45 (C 5 ), 138.5 (C 22 ), 155.9 (C 3 ); Anal. Calcd for C 29 H 36 O 3 : C, 80.55; H, 8.33. Found: C, 80.00; H, 8.41
[0119] 17α-20E-21(4-Methoxyphenyl)-19-norpregna-1,3,5,(10), 20-tetraene-3,17β-diol (17α-E-(4-methoxyphenyl)-vinyl estradiol) (9a). Yield=36%; R t =0.23 (CHCl 3 —CH 3 OH, 99:1); 1 H NMR (300 MHz, Acetone-d 6 , δ) 0.99 (s, 3H, C 18 methyl-H), 3.68 (s, 1H, 17P hydroxy-H), 3.78 (s, 3H, C 28 :methoxy-H), 6.46 (d, 1H, J=16.1 Hz, C 21 —H), 6.51-6.59 (m, 3H, C 2 , C 4 , C 20 —H), 6.88 (d, 2H, J=8.8 Hz, C 24 , C 26 —H); 7.07 (d, 1H, J=8.3 Hz, Cl-H); 7.39 (d, 2H, J=8.8 Hz, C 23 , C 27 —H), 7.95 (s, 1H, C 3 hydroxy-H); 13 C NMR (75.4 MHz, Acetone-d 6 , δ) 14.7 (C 18 ), 24.1 (C 15 ), 27.3 (C 11 ), 28.3 (C 7 ), (C 6 ), 33.4 (C 12 ), 37.3 (C 16 ), 40.7 (C 8 ), 44.7 (Cg), 48.2 (C 13 ), 50.0 (C 14 ), 55.5 (C 28 :methoxy), 84.1 (C 17 ), 113.5 (C 2 ), 114.7 (C 24 , C 26 ), 115.9 (C 4 ), 127.0 (C 1 ), 127.0 (C 21 ), 128.3 (C 23 , C 27 ), 131.4 (C 22 ), 132.1 (C10), 134.9 (C 20 ), 138.4 (C 5 ), 155.9 (C 3 ), 159.9 (C 25 ).
[0120] In the above procedures, the Solid Phase Synthesis methodology was applied using carboxylated resins to generate a series of novel ER-LBD ligands, or estradiol derivatives. The purification steps were simplified and simultaneously produced both the E- and Z-isomers. Yield may be improved by modifications in both the coupling and cleavage steps for a chemically more sensitive Z-isomer.
[0121] One of the key elements of the synthetic scheme was the selection of a linker that could be both formed and cleaved under mild conditions. 17α-substituted estradiols were unstable under strongly acidic conditions such as those frequently used to release products from the resins. Therefore the resin of choice was carboxylated polystyrene which could be esterified under neutral conditions and ultimately cleaved with mild base. Compound 8a was prepared using the carboxylated resin obtained either by oxidation of a Wang resin using Jones reagent (Bowden, 1946) or by carboxylation of a polystyrene resin via lithiation with n-butyl lithium (Farrall, 1976). The reactions for both methods were easily monitored by the appearance of the 1700 cm −1 absorption in the FT-IR spectrum. The loading capacity of the carboxylated resins was determined by coupling 17α-ethynyl estradiol onto the resins using DCC in the presence of catalytic amount of DMAP and measuring its subsequently cleaved estradiol derivatives from the aliquot of the resins. The loading 1 of oxidized Wang resin was 0.4-0.6 mmol g −1 and that of carboxylated polystyrene was 1.5-1.9 mmol g −1 . Once the utility of coupling through the ester linkage using carboxy polystyrene resin was confirmed, the commercially available carboxy poolystyrene was used for the remainder of the work. The loading yield of the reaction using the resins with already known loading capacity (2.47 mmol g −1 ) was 82%. The yield was determined by ‘cleave and characterize’ methods.
[0122] As shown in FIG. 1, the synthesis of the analogs was initiated by coupling the 3-phenolic group of 17α-ethynyl estradiol to the carboxy polystyrene resin. The steroids on the resins were confirmed by an antimony (III) chloride assay (Carr, 1926; Blatz, 1972; Jork, 1990). Due to the absence of color change with bromocresol green, no free carboxylic acid groups remained on the resin (Gordon, 1972). The appearance of a peak at 3301 cm −1 in the IR spectrum, corresponding to the C—H stretch of the ethynyl group, also confirmed that the reaction and a shift of carbonyl absorption to higher frequency (from 1690-1734 cm −1 ) was also observed.
[0123] The subsequent hydrostannylation step incorporated either the use of hydrostannylation of bound ethynyl estradiol (Method A) or hydrostannylation of ethynyl estradiol in solution phase synthesis followed by coupling to the resin (Method B). The resin-bound 17α-ethynyl estradiol was hydrostannylated with tributyltin hydride using triethyl-borane as a radical initiator (Nozaki, 1989) to afford a mixture of the 17α-E/Z-tri-n-butylstannylvinyl estradiol in 20-30% (0.12 mmol g −1 of E, 0.01 mmol g-1 of Z) loading yields. Varying the reaction conditons, e.g. different solvents, temperatures, or reaction times, did not improve the yields. Therefore, a direct coupling of 17α-E/Z-tri-n-butylstannyl-vinyl estradiols was used to overcome the low efficiency of this step. 17α-Ethynyl estradiol was hydrostannylated to 60° C. and the crude mixture was directly transferred to the resin slurry in CH 2 Cl 2 . The mixture was treated with a 2-3 fold excess of DCC and a catalytic amount of DMAP was added. The loading yield for the coupling reaction was 0.59 mmol g −1 with a Z/E ratio=1:20. The low loading yield was due to the use of the acetic acid for the protonation of phenoxide ion after cleavage, subjecting the products to protiodestannylation and reducing the expected loading yield. Because the cleavage after hydrostannylation did not provide a precise loading yield, the dry weight difference between pre-and post-reaction was subsequently used to determine the loading yield. Using the dry weight difference method, the yield for the hydrostannylation reaction was 1.55 mmol g −1 for both E- and Z-isomers. Because hydrostannylation on the resin did not afford satisfactory yields. Method B was the method of choice. The ratio of E and Z isomers is a function of the reaction temperature, time and stoichiometric ratio of tributyltin hydride to alkyne. At 60° C. the reaction generated greater than 20:1 (E/Z) ratio bound to the solid phase. To increase the ratio of the Z-isomer, triethylborane was used as a radical initiator and the reaction was run at low temperature. The proportion of the Z-isomer (Z/E=1:10) was increased. However, the reaction required a longer time and the loading yield for the hydrostannylation was slightly lower than at higher temperature (1.44 mmol g −1 by the dry weight difference method) because of more unreacted 17α-ethynyl estradiol in the reaction mixture.
[0124] The resin-bound hydrostannnylated estradiol was subjected to the Stille coupling reaction (Stille, 1985) using a variety of substituted aryl halides to generate the target compounds (see Table 2). As shown in FIG. 1, Pd(PPh 3 ) 4 was used as the catalyst for the reaction and 3,5-di-t-butyl-4-hydroxytoluene (BHT) was added as a scavenger. The use of Pd(PPh 3 ) 4 generated an insoluble by-product that caused coloration of the resin, however, it was easily removed by rinsing it through the built-in filter (50-70 μm). After completion of all the reaction steps, the product was cleaved from the resin by saponification with 5 N NaOH dissolved in CH 3 OH-Dioxane (1:3).
TABLE 2 Compound R 1 (ortho) R 2 (meta) R 3 (para) Yield (%) 4a:E CF 3 H H 38 5a:E H CF 3 H 33 6a:E H H CF 3 49 6b:Z H H CF 3 17 7a:E CH 3 H H 38 8a:E H CH 3 H 75 8b:Z H CH 3 H 54 9a:E H H OCH 3 36
[0125] As shown in Table 2, the unoptimized yields of the Stille reactions on solid phase ranged from 17-75%, comparable to those observed for solution phase synthesis. Compounds 5a (para-trifluoromethylphenyl, E-isomer) and 5b (para-trifluoromethylphenyl, Z-isomer) were isolated from the Stille reaction in a ratio of 98:2. Compound 7a (meta-methylphenyl, E-isomer) and 7b (meta-methylphenyl, Z-isomer) were also obtained in a ratio of 96:4. Although the Z-tri-n-butylstannyl vinyl estradiol was initially present on the resin, no Z-isomers of compounds 3a, 4a, 6a, or 8a were isolated from the Stille coupling, instead, 17α-vinyl estradiol, resulting from protiodestannylation was recovered as a side product. Because an excess of reagent was used to drive the reaction to completion, unreacted hydrostannylated 17α-E/Z-(tri-n-butylstannyl)-vinyl estradiol was no detected after the Stille reaction. It is possible that the Z-isomers either isomerized to thermodynamically more stable E-isomers under the conditions required for the Stille reaction or underwent protiodestannylation. As previously observed, the Z-isomer is much more susceptible to protiodestannylation than the E-isomer and the appearance of the side product under either solid phase or solution phase synthesis was approximately the same.
[0126] The isolated product were characterized by standard spectroscopic methods (FT-IR, 1 H and 13 C NMR) and analytical methods. The data were consistent with the proposed structures. Stereochemical assignments for compounds 5a and 5b were based on the C 20 , C 21 olefinic proton coupling constants for which E=16 Hz and Z-12.9 Hz, respectively. For compounds 7a and 7b, the observed coupling constants were 18.2 Hz of the C 20 E-vinyl proton and 13.1 Hz for the C 20 Z-vinyl proton. In 13 C NMR, long range couplings were observed for the compounds 3a-5a and 5b containing the trifluoromethyl group. Coupling with strongly electronegative fluorine was found at the carbon directly attached to the fluorine (1J C-F ) and one ( 2 J C-F ) and two carbons distant ( 3 J C-F ). The carbons appeared as quartets and the coupling constants were approximately 1 J C-F =270 Hz. 2 J C-F =32 Hz. 3 J C-F =3-5 HZ respectively.
[0127] Variability of Ortho, Meta, Para-Substitutions
[0128] Ortho, meta, and para (trifluoromethyl)phenylvinyl estradiol isomers were evaluated for estrogen receptor-ligand binding domain (ER-LBD) affinity. The properties of the aryl substituent and its position on the ring (ortho/meta/para) affect receptor binding.
[0129] Trifluoromethyl group was introduced onto phenylvinyl estradiol either at the ortho, meta, or para positions. These compounds were examined for their ability to stimulate or inhibit estrogen responses in two assay systems. The initial system evaluated the ability of the ligand to stimulate the proliferation of MCF-7 cells and as the results in FIG. 11 indicate, the ortho-isomer produced a full agonist response comparable to that of estradiol. When the ligand was added to the cells in the presence of 1 nM estradiol, there was neither an enhancement nor a diminution of the proliferative response. The meta- and para-isomers gave substantially different profiles. The meta-isomer demonstrated a weak proliferative effect at doses greater than 1 nM and antagonized the effects of estradiol at the same doses. The para-isomer, however, did not elicit a proliferative response until a 10 nM dose was employed and decreases in the estradiol effects were observed below 1 nM. Therefore, the position of the trifluoromethyl group exerted a significant effect on the efficacy of the ligand.
[0130] These trifluoromethyl substituted compounds were also studied with an immature female rat uterotrophic growth assay; the results are shown in FIGS. 12, 13, and 14 . In the estrogenic assay, the ortho-isomer produced an effect comparable to estradiol at a 3 nM level and substantial estrogenic effects at 10 and 100 nM. The meta- and para-isomers, however, demonstrated little or no estrogenic effects, even at 10 and 100 nM. Therefore, the agonist responses observed in the in vitro cell proliferation assay were carried over to the intact animal as well. The antiestrogen assay evaluated the ability of the isomers to block the uterotrophic effect induced by 1 nM estradiol. Under these conditions, the ortho isomer produced an enhancement of the estrogenic response at both 10 and 100 nM. The meta-isomer demonstrated no significant effect on the estradiol response at either dose, however, the para isomer reduced the estrogenic response at the 100 nM level. Therefore, in both estrogen responsive cells and tissues these new ligands are producing differential responses in affinity and efficacy related to the site of trifluoromethyl substitution on the phenyl ring.
Example II
[0131] Development of Antiandrogens
[0132] The cellular target for antiandrogen therapy, the androgen receptor (AR), is a member of the nuclear receptor superfamily which has been studied extensively over the past decade (Tsai, 1994). Members of this receptor bear a strong structural similarity (homology) and utilize similar signaling pathways to express their biological actions. At the molecular level, the AR, like the other steroid hormone receptors, is composed of discrete domains that are responsible for specific functions. The hormone binding domain (HBD), the sequence of aminoacids near the N-terminus of the AR, recognizes and binds testosterone with high affinity but not other hormones or small endogenous molecules (Weatherman, 1999; Simons, 1998). This region of the receptor has been examined using X-ray crystallography to elucidate the aminoacid residues responsible for the recognition of specific hormones. The hormone binding domains on the estrogen receptor (ER), progesterone receptor (PgR) and retinoic acid receptor (RAR) provide a common fold for the endogenous hormone, which also strongly suggest the types of conformational changes that occur upon ligand binding (Brzozowski, 1997; Tannenbaum, 1998; Shiau, 1998; Williams, 1998; Renaud, 1995; Klaholz, 1998). The conformational changes, particularly those associated with helix-12, assist in the recruitment of specific coactivator proteins that appear to initiate the action of the general transcription apparatus (Resche-Rigon, 1998; McKenna, 1999; Klinge, 2000).
[0133] In accordance with the present invention, the steroidal nucleus is the address component, which directs the molecule to the HBD where, for agonists, the D-ring substituents direct helix-12 into a conformation that exposes the Activation Function-2 (AF-2) or message component. For known ER and PgR antagonists, the steroid nucleus present in most drugs provides the appropriate address. However, the incorporation of an additional functional group interferes with the movement of helix-12, and produces a full or partial antagonist response (message). Most of the antihormones known in the art incorporate that additional functional group at either the 11β- or 7α-position of the steroid (see FIG. 7). The present invention shows that antagonism can be generated through introduction of an appropriate 17α-substituent.
[0134] Significant research efforts have focused on the synthesis and evaluation of compounds designed to either mimic or block the effects of the endogenous androgen, testosterone. While many steroidal compounds can mimic testosterone, relatively few were able to block its effects in target tissues and virtually none were effective in treating hormone responsive prostate cancer (Teutsch, 1995). Nonsteroidal agents, however, such as (hydroxy)flutamide, nilutamide, and bicalutamide (Sciarra, 1990; Tucker, 1988, 1990), have demonstrated clinical efficacy for the treatment of prostatic carcinoma, even though their affinity for the AR is relatively low when compared to testosterone (Kokontis, 1999; Battmann, 1998). Recent publications have disclosed another class of nonsteroidal antiandrogens which have potential as clinically useful agents (Hamann, 1998; Edwards, 1999; Higuchi, 1999; Kong, 2000). Analogs of these compounds also demonstrate agonist/antagonist responses at other nuclear receptors (Pooley, 1998; Zhi, 1998, 1999, 2000). Because the nonsteroidal antiandrogens do not correspond to any current steroid hormone pharmacophore, it is possible that they may primarily effect only the message region (helix-12) of the AR-HBD. A potent interaction at that site would still compete with agonist ligand binding for the address region, not entirely unlike the situation for the dopamine transporter inhibitors where structurally diverse families of ligands not only inhibit dopamine and cocaine binding but also, by associating with overlapping sites, inhibit the binding of each other. Thus, the present invention combines features from both the steroid nucleus (address component) and the nonsteroidal antagonist pharmacophore (message component) (see FIG. 8).
[0135] Synthesis and Evaluation of Steroidal Antiandrogens at the 17α-Position of Testoterone
[0136] Synthesis of the Message Components, Characterization, and Conformational Analysis
[0137] A combination of organotin chemistry and palladium catalyzed coupling reactions is used for the synthesis of the message components (see FIG. 10). The 1-ethynyl-1-aminoperhydroindanes which would incorporate the C- and D-rings of the steroid nucleus is prepared from the corresponding 1-ethynyl-1-acetoxy analogs using a Cu(I)-assisted aminolysis. The ethynyl cycloalkyl alcohols or amines readily undergo hydrostannation to give the corresponding E- and Z-stannylvinyl intermediates which can be coupled with the requisite mono- or di-substituted aryl iodide under Stille coupling conditions (Farina, 1995; Casado, 1998). Three 3′- or 4′-substituted, three 3′-, 4′-disubstituted, and three 3′-, 5′-disubstituted phenyl iodides are used to generate a total of 18 compounds. While there are no obvious choices for the optimal substituents, the structure activity relationships (SAR) for antiandrogens suggest that electron withdrawing groups (e.g., —NO 2 , CF 3 ) enhance potency. Therefore, these groups are used with one electron releasing group in the first series (Tucker, 1988). Suzuki coupling reaction is used with vinylboronic acid (Suzuki, 1999). The E-vinylboronic acid is accessed directly by hydroboration of the alkyne with catecholborane followed by hydrolysis. The Z-isomer is obtained from the Z-vinylstannane via idododestannylation, followed by coupling with bispinacolatodiboron, and hydrolysis.
[0138] For the synthesis of the spirocyclic ether or amine message components, the coupling partner for the Z-vinylstannane (or boronic acid) requires an orthoiodo(bromo)phenol derivative. Halogenation of the commercially available 3′- or 4′-substituted phenol gives the intermediate which is initially protected as the silyl ether. The Z-vinyl arene is made by the standard Stille or Suzuki coupling methods. The conditions developed by Buchwald and Hartwig to effect the intramolecular aryl amine/ether formation may be used (Wolfe, 1998, 1999; Yang, 1999; Hartwig, 1998a,b) Deprotection of the phenol, conversion to the triflate, and coupling with an appropriate Pd catalyst, such as Pd 2 (dba) 3 , and an activating ligand, such as BINAP, will effect the cyclization. The final product is provided by the deprotection of the amine.
[0139] Each new compound synthesized is characterized by the standard spectrometric methods—high resolution mass spectrometry (HRMS), H-1/C-13-nuclear magnetic resonance spectrometry (NMR) to confirm the proposed molecular structures. Solution conformations is determined by using 1D- and 2D-NMR techniques, methods of which are described above. The use of both conformational analysis and computational methods, more probable solution conformations are identified, which provides information with regard to key structural features and how they influence molecular conformations.
[0140] Screening for Androgen Receptor Affinity, Efficacy and Selectivity
[0141] Compounds prepared containing the message components may be screened by a bioevaluation protocol already established through a commercially available company (e.g., MDS-Panlabs, located in Bothell, Wash.) to determine their AR affinity, efficacy and selectivity. Receptors from rat ventral prostate tissue may be used to determine the IC50 and Ki values. [H-3] mibolerone may be used as the radioligand. Synthesized hydroxyflutamide, nilutamide, bicalutamide and LG 120907 is evaluated as standard AR ligands. Those new compounds that demonstrate AR affinities >10% that of bicalutamide or LG 120907 will be evaluated for their affinities for the other nuclear receptors. Other sources for receptors and their radioligands include Erα-human recombinant from insect St9 cells, [H-3] estradiol, GR-human Jerkat cells, [H-3] dexamethasone, and PgR-bovine, [H-3] R-5020. Compounds that express a significant selectivity for AR (>10:1) is tested for their efficacy in the rat agonism/antagonism model. In vitro efficacy model for testing the compounds for antagonism is the use of cotransfection and whole cell receptor binding (Hamann, 1998).
[0142] Preliminary SARs is determined from the IC50 and Ki data from the screening of the new compounds. E- vs. Z-stereochemistry of the acyclic series of compounds is studied as well as the effects of mono- vs. di-substitution and 3- vs. 4-substitution. The cyclized compounds are compared with the acyclic series- to identify particular substituent trends. The QSAR-CoMFA module of SYBIL is used to clarify the individual parameters (Gantchev, 1994). The physicochemical parameters developed by Hansch may also be used to evaluate the data (Gantchev, 1994). The most potent ligands are analyzed for the lowest energy conformations using QUANTA-CHARMM/mm3 force fields (Wurtz, 1998) and compared with those from the NMR conformational studies to rationalize the initial SAR. This allows for better determination of which substituents are most effective in contributing to AR affinity, selectivity and antihormonal response. Subsequently, the selected substituents is used for incorporation into the address-message composite.
[0143] Synthesis of (Nor)Testosterone Derivatives with the Message Component at 17α-Position
[0144] 17α-ethynyl-(19nor)testoterone and its dihydroderivative (address component) is used as the starting material. The message components may be obtained from commercially available (or readily synthesized) mono- and disubstituted iodophenols. The same message components as with the estrogen study are used—the nilutamide/bicalutamide family of nonsteroidal antagonists and the more potent Ligand Pharmaceutical antagonists. For the message components analogous to flutamide and bicalutamide, the ethylene group is selected as an isosteric substitution for the amide bond (Luthman, 1996). The method for synthesis of the (nor)testosterone derivatives with the message component at the 17α-position is similar to the steps used for the synthesis of antiestrogens described herein. The antiandrogens of the present invention will include the steroid nucleus (A-D rings) and will provide functionality in the A-ring (3 C═O/—OH; 4,5-C═C). As an embodiment, these groups are prepared to protect them as ketals, esters or silyl/enol ethers (Hoyte, 1993; van den Bos, 1998).
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[0209] Equivalents
[0210] While the present invention has been described in conjunction with a preferred embodiment, one of ordinary skill, after reading the foregoing specification, will be able to effect various changes, substitutions of equivalents, and other alterations to the compositions and approaches set forth herein. It is therefore intended that the protection granted by Letters Patent hereon be limited only by the definitions contained in the appended claims and equivalents thereof.
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The present invention comprises the design, synthesis and development of a new class of chemotherapeutic agents for prophylactic and therapeutic treatments in a mammal, particularly a human, believed to be at risk of suffering from a hormone-responsive disorde. In an embodiment of the invention, such treatments include therapeutic compositions comprising novel steroidal antiestrogen and antiandrogen compounds. In a preferred embodiment, such a novel compound of the present invention has an address and a message component, which are made into a single composite entity for more aggressive intervention and effective treatment of hormone-responsive disorders, thereby prolonging the disease-free interval for the patient and reducing a number of side effects.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to impact resistant polyester/polycarbonate blend compositions formed from a polyester, a polycarbonate, an amine functionalized elastomer and a graph coupling agent. Another aspect of this invention relates to articles of manufacture formed totally or in part from the blends of this invention.
2. Prior Art
Blends of polyester and polycarbonates, and the use of same to fabricate articles such as molded parts are known. See for example, U.S. Pat. Nos. 4,522,797; 4,764,556; 4,897,448; 4,737,545; 4,629,760; and 4,753,980 and EPO 0 180 648.
The addition of carbodiimides or polycarbodiimides to various polymers such as polyesters, polyetheresters, acrylate-butylenediacrylate-diallyl maleate-methacrylate copolymers is known. See for example, U.S. Pat. Nos. 3,975,329; 4,071,503; 4,110,302; 4,689,372 and 4,465,839; and Chem. Abs. 85, 1785339 (1976); 78 17364C (1973); and 104, 150170K.
SUMMARY OF THE INVENTION
One aspect of this invention relates to a polymer blend comprising:
i. a polyester;
ii. a polycarbonate;
iii. an amine functionalized elastomer; and
iv. a graft coupling agent for grafting said elastomer to said polyester.
Yet another aspect of this invention relates to a polymer blend comprising:
i. a polyester;
ii. a polycarbonate;
iii. an amine functinalized elastomer;
iv. a graft copolymer of said polyester and said elastomer; and
v. residue of a graft promoter from the grafting of said polyester to said elastomer.
The blends of this invention exhibit several advantages. For example, the blends of this invention exhibit relatively high impact strengths both at room temperature (i.e. about 24° C.) and low temperatures (i.e. about -40° C.), and retain a substantial portion of both room and low temperature impact strengths after annealing or heat treatment. The blends of this invention also exhibit relatively low melt viscosities for good melt flow during melt processing. When these property advantages are combined with other properties of polyester/polycarbonate blends, such as chemical resistance and heat resistance, the blends of this invention provide significant value in molding applications.
Yet another aspect of this invention relates to the article of this invention comprising a body all or a portion of which is formed from the blend of this invention.
Still another aspect of this invention relates to the process of this invention which comprises:
melt blending a polyester, a polycarbonate and an amine functionalized elastomer in the presence of an effective amount of an effective graft coupling agent for grafting said elastomer to said polyester.
BRIEF DESCRIPTION OF THE DRAWINGS
In the Figures:
FIG. 1 is a bar graph of Notched Izod vs. Elastomer type showing the improved properties of the compositions of this invention.
FIG. 2 is a bar graph of Notched Izod vs. graft coupling agent concentration showing the improved properties of the compositions of this invention.
FIG. 3 is a bar graph of Notched Izod vs. graft coupling agent concentration showing the improved properties of the compositions of this invention.
FIG. 4 is a graph of Notched Izod vs. weight percent amine functionalized elastomer showing the improved properties of the composition of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The composition of this invention includes three primary ingredients. As a first primary component, the blend of this invention comprises an effective amount of a thermoplastic polyester. The particular thermoplastic polyester chosen for use can be a homopolyester or a co-polymers, or mixtures thereof as desired. Thermoplastic polyesters are normally prepared by the condensation of an organic dicarboxylic acid and an organic diol, and, therefore illustrative examples of useful polyesters will be described herein below in terms of these diol and dicarboxylic acid precursors.
Polyesters which are suitable for use in this invention are those which are derived from the condensation of an aliphatic, cycloaliphatic or aromatic diol with an aliphatic, aromatic and cycloaliphatic dicarboxylic acid illustrative of useful cycloaliphatic diols are those having from about 5 to about 8 carbon atoms such as 1,4-dihydroxy cyclohexane;
1,4-dihydroxymethylcyclohexane,1,3-dihydroxycyclopentane, 1,5-dihydroxycycloheptane, 5-dihydroxycyclooctane, 1,4-cyclohexane dimethanol, and the like. Illustrative of suitable aliphatic diols are those having from about 2 to about 12 carbon atoms and preferably those having from about 2 to about 6 carbon atoms such as ethylene glycol, 1,5-pentane diol, 1,6-hexane diol, 1,4-butane diol, 1,12-dodecane diol and geometrical isomers thereof.
Suitable dicarboxylic acids for use as monomers for the preparation of useful thermoplastic polyesters are linear and branched chain saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids and cycloaliphatic dicarboxylic acids. Illustrative of aliphatic dicarboxylic acids which can be used in this invention are those having from about 2 to about 50 carbon atoms, as for example, oxalic acid, malonic acids, dimethyl-malonic acid, succinic acid, octadecylsuccinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, suberic acid, azelaic acid and dimeric acids (dimerization products of unsaturated aliphatic carboxylic acids such as oleic acid) and alkylated malonic and succinic acids, such as octadecylsuccinic acid, and the like.
Illustrative of suitable cycloaliphatic dicarboxylic acids are those having from about 6 to about 15 carbon atoms. Such useful cycloaliphatic dicarboxylic acids include 1,3-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxymethylcyclohexane and 4,4'-dicyclohexdicarboxylic acid, and the like. Illustrative of useful aromatic carboxylic acids are terephthalic acid, isophthalic acid, o-phthalic acid, 1,3-, 1,4-, 2,6 or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylsulphone-dicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl)-idane, diphenyl ether 4,4'-dicarboxylic acid bis-p(carboxyphenyl)methane and the like.
Polyester compounds prepared from the condensation of an aliphatic or cycloaliphatic diol, such as ethylene glycol, 1,4-butane diol, and 1,4-dihydroxy cyclohexane and an aromatic dicarboxylic acid such as benzene dicarboxylic acid and naphthalene dicarboxylic acid are preferred for use in this invention. In the most preferred embodiments of this invention poly(ethylene terephthalate), poly(butylene terephthalate), and poly(1,4-cyclohexane dimethylene terephthalate), are the polyesters of choice. Among these polyesters of choice, poly(ethylene terephthalate) and poly(butylene terephthalate) are most preferred. For the composition of this invention, recycled poly(ethylene terephthalate) is useful and preferred.
The number average and the weight average molecular weight of the polyester may vary widely. Usually, the polyester is of a number average or weight average molecular weight that is sufficiently high to form a molded part and sufficiently low to allow melt processing of the polyester/polycarbonate/elastomer blend into a molded product. Such number average or weight average molecular weights are well-known to those of skill in the molding art and are usually at least about 5,000 as determined by gel permeatiom chromotography, osmometry, light scaterring methods and end-group analysis. The number average molecular weight is preferably from about 10,000 to about 100,000, more preferably from about 15,000 to about 75,0000 and most preferably from 20,000 to about 50,0000.
The intrinsic viscosity of the polyester is not critical and may vary widely depending on the processing requirements. The polyester should preferably have an intrinsic viscosity of at least about 0.3 dl/g; more preferably the from about 0.4 to about 1.2 dl/g; and most preferably from about 0.5 to about 0.95 dl/g. These viscosity values are determined with the use of a standard Ubbehlohde viscometer in a phenol-tetrachloroethane (60/40 v/v) solution in a concentration of 0.5% at room temperature.
The polyesters should preferably have active chain end groups viz., carboxylic acid end groups or an electrophilic derivative thereof. While we do not wish to be bound by any theory, it is believed that the carboxylic acid end groups are reactive with the amine groups of the elastomer. Thus, when contacted with an appropriate graft coupling agent under appropriate conditions reaction of such amine and carboxylic acid groups form amide linking groups which link the polyester and elastomer. The concentration of such groups may vary widely, but is preferably at least about 0.01 meq/g, more preferably at least about 0.02 meq/g and most preferably from about 0.03 to about 0.05 meq/g. The end groups can be determined by standard titrametric methods for carboxyl or hydroxyl determination.
The amount of polyester included in the composition may vary widely and amounts used in conventional polycarbonate/polyester blends can be used. In the preferred embodiments of the invention, the amount of polyester employed is equal to or greater than about 10 weight percent based on the total weight of elastomer, polyester and polycarbonate in the blend, and in the particularly preferred embodiments of this invention is from about 20 to about 80 weight percent on the aforementioned basis. Amongst these particularly preferred embodiments, most preferred are those embodiments where the amount of polyester employed is from about 40 to about 60 weight percent based on the total weight of polycarbonate, elastomer and polyester in the blend.
As a second primary ingredient, the composition of this invention includes a polycarbonate. Essentially any conventional polycarbonate can be used in the practice of this invention, as for example those described in U.S. Pat. Nos. 4,018,750 and 3,153,008 and references cited therein.
Illustrative of useful polycarbonates are those having one or more recurring monomeric units of the formula: ##STR1## where --R-- is a divalent aromatic group. Permissible aromatic --R-- groups include substituted or unsubstituted phenyl, tolyl, xylyl, ethylphenyl, isopropylphenyl and the like two or more of which may be linked together by divalent linking functions such as divalent alkylene or halogenated alkylene (i.e. --CH 2 --, --C 2 H 4 --, --C 3 H 6 --, and --C 4 H 8 --), --SO 2 --, --S--, --C(O)O)--, --C(O)--, --NH--, --O-- and the like. Examples include:
2,2-bis(3-chlorophenyl)propane; 2,2-bis(3-nitro phenyl)hexafluoropropane; 2,2-bis (5-methyl diphenyl) pentane; 2,4'-(5-methyl diphenyl)methane; bis-(5-ethyl phenyl)methane; bis(phenyl)methane; bis-(2-methoxy-5-nitrophenyl)methane; 1,1-bis(2-methoxy phenyl)ethane; 3,3-bis(phenyl)pentane; 2,2-dimethyl diphenyl; 2,6-dimethyl naphthalene; bis-(2-methyl diphenyl)sulfone; bis-(3,5-diethyl-2-methyl phenyl)sulfone;
2,4'-dimethyl diphenyl sulfone;
5'-chloro-3,3'-dimethoxy-diphenyl sulfone; bis-(dichloro phenyl)diphenyl sulfone; bis-(dichloro phenyl)diphenyl sulfone; 4,4'-3,3'-dimethoxy diphenyl ether; 4,4-3,3'-dimethoxy-3,3'-dichlorodiphenyl ether; 3,3-dicyano-2,5'-dihydroxydiphenyl ether; and the like. Also, useful as the polycarbonate component are modified polycarbonates or polycarbonate copolymers such as those containing copolymerized aromatic ester segments as for example polyestercarbonates.
The preferred aromatic polycarbonates are those selected from the group consisting of poly(2,2-'bis-(4-hydroxyphenyl)alkane)carbonates and poly(2,2'-bis-(4-hydroxy-3,5-dimethylphenyl)alkane)carbonates. The most preferred of these polycarbonates is a poly(2,2'-bis-(4-hydroxyphenyl)propane) carbonate.
Useful aromatic polyester can be manufactured by known processes or obtained from commercial sources. For example, useful polyester can be prepared by reacting a dihydric phenol as for example, those disclosed in U.S. Pat. Nos. 4,126,602, 2,999,835, 3,028,365, 3,334,154, and 4,131.575 with a carbonate precursor, such as phosgene, haloformate or carbonate ester as disclosed in U.S. Pat. No. 4,018,750, or by transesterification processes as disclosed in U.S. Pat. No. 3,153,008, as well as other processes well known to the art.
The amount of polycarbonate included in the composition may vary widely and amounts used in conventional polycarbonate/polyester blends can be used. In the preferred embodiments of the invention, the amount of polycarbonate employed is equal to or greater than about 10 weight percent based on the total weight of elastomer, polyester, and polycarbonate in the blend, and in the particularly preferred embodiments of this invention is from about 20 to about 80 weight percent on the aforementioned basis. Amongst these particularly preferred embodiments, most preferred are those embodiments where the amount of polycarbonate employed is from about 40 to about 60 weight percent based on the total weight of polycarbonate, elastomer and polyester in the blend.
The number average molecular weight of the polycarbonate may vary widely. Polycarbonates useful in the practice of this invention preferably have a number-average molecular weight of from about 5,000 to about 80,000. More preferably, the number-average molecular weight is from about 10,000 to about 40,000.
The intrinsic viscosity of the polycarbonate may vary widely provided that the viscosity is not so high as to prevent melt processing of the blend. The polycarbonates preferably have an intrinsic or inherent viscosity of at least about 0.2 dl/g, (deciliters/gram) as determined in dichloromethane by standard ubbehlohde viscometry at room temperature e.g. 25° C. The instrinsic viscosity is more preferably from about 0.2 to about 1.2 dl/g, is more preferably of about 0.2 to 0.9 dl/g and is most preferably from about 0.3 to about 0,6 dl/g.
Although not essential, the polycarbonates should preferably contain hydroxyl end groups.
As a third primary ingredient, the composition of this invention includes an amine functionalized elastomer. As used herein, an "amine functionalized elastomer" is a polymer having a polymeric backbone derived from polymerization of one or more α, β-unsaturated monomers, diene monomers or a combination thereof, having pendant amine functions, terminal amine functions or a combination thereof. Useful rubbers may homopolymers, or block or random copolymers. Blends of two or more rubbers may also be used in the practice of this invention.
Illustrative of useful dienes are butadiene, 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 1,4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbonene, 5-isopropylidene norbornene, 5-methylene narbonene, and the like. Illustrative of useful olefins are aliphatic and aromatic lefins such as ethylene, propylene, isobutylene, styrene, trichlorofluoroethylene, tetrafluoroethylene, acrylic acid, methyacrylic acid, vinyl toluene, alkyl acrylates such as methyl mathacrylate and methyl acrylate and the like.
The elastomer useful in the practice of this invention have an ASTM D-638 tensile modulus equal to or less than about 40,000, preferably equal to or less than about 20,000, more preferably equal to or less than about 10,000, and most preferably equal to or less than about 5,000. The elastomers have a Mooney viscosity of from about 10 to about 100 ML 1+8@127° C. units, preferably of from about 15 to about 80 units and more preferably of from about 25 to about 70 units.
Useful amine functionalized elastomers may be prepared by procedures known to those of ordinary skill in the art or may be obtained from commercial sources. For example, useful may useful elastomers may be prepared by the methods described in U.S. Pat. No. 4.987,200. Moreover, useful amine functionalized butadiene/acrylonitrile copolymers (NBRs) are commercially available for Copolymer Rubber Chemical Corporation under the tradename Nysin DN 508-14A.
Preferred elastomers are those in which the polymeric backbone are formed predominantly from alkyl acrylates, butadiene, ethylene, styrene, isobutylene, propylene, acrylonitrile, and may be homopolymers, copolymers, terpolymers and the like. More preferred polymeric backbones are polybutadiene, polyisoprene, butadiene/styrene copolymers, acrylonitrile/butadiene copolymers, isobutylene/butadiene copolymers, ethylene/propylene copolymers, ethylene/ propylene/diene terpolymers, ethylene/alkylacrylate copolymers, styrene/butadiene copolymers; and most preferred polymeric backbones are butadiene/acrylonitrile copolymers, ethylene/propylene copolymers, ethylene/alkyl acrylate copolymers, and styrene/butadiene copolymers. The polymeric backbone of choice is a copolymer having two or more divalent alkylene recurring monomeric units. Useful examples are amine functionalized ethylene/propylene copolymers and terpolymers and amine functionalized butadiene/acrylonitrile copolymers (NBR) and their hydrogenated derivatives.
The polymeric backbone is modified by copolymerization or by post reaction to form pendant amine functionalities randomly distributed along the polymeric block, terminal amine functionalities at one or both ends of the polymeric block or a combination thereof. Illustrative of such amino groups are amine (--NH 2 ) and alkyl amino groups, having an active hydrogen such as e.g. methylamine (--NHCH 3 ), ethylamine (--NHC 2 H 5 ), propylamine (--NHC 3 H 7 ), and butylamine (--NHC 4 H 9 ) and isonomers thereof. The amino group of choice is amine (--NH 2 ).
Useful grafting and copolymerization techniques used in the preparation of the same functionalized elastomer are disclosed in U.S. Pat. No. 4,987,200. In the preferred embodiments of the invention, amine functionalities are randomly distributed along the polymeric backbone and are formed by copolymerization of the monomer precursors of the recurring monomeric units in the polymeric backbone with an ethylenically unsaturated monomer containing the desired amine functionality such as p-aminostyrene, 2-aminopropylacrylamide, norbornene unsaturation types including norbornene and its higher homologs e.g. norbornenyl-methyl amines.
The mole percent of pendant and terminal mine functionalities may vary widely. The only requirement is that the amount is sufficient to allow some grafting of the elastomer and the polyester.
The amount of elastomer included in the composition may vary widely. Usually, the amount of elastomer is at least about 1% by weight of the polyester, polycarbonate and elastomer in the composition. The amount of elastomer is preferably from about 5 to about 30% by weight, more preferably from about 5 to about 20% by weight and most preferably from about 10 to about 20% by weight based on the total weight of polyester, elastomer and polycarbonate in the composition.
In the preferred embodiments of this invention, the composition includes an effective amount of an suitable "graft-coupling agent". As used herein a "graft-coupling agent" is a reagent which is believed to promote the coupling reaction between the amine functionalized elastomer and the polyester and/or chain extension crosslinking the polyester and the amine functionalized elastomer, respectively. Any graft-coupling agent which provides this function can be used in the practice of this invention. Illustrative of such graft coupling agents are phosphites such as triscaprolactam phosphorous; and phosphites having alkyl, aryl, alkylaryl and aralkyl substituents such as trinonylphenyl phosphite and triphenyl phosphite; and the like. Such graft coupling agents are described in greater detail in U.S. Pat. Nos. 5,037,897; 5,124,411; and the like.
Other useful graft coupling agents are polycarbodiimides. Illustrative of useful polycarbodiimides comprise repeat units of the formula: ##STR2## wherein --R 2 -- is a divalent hydrocarbon radical such as aliphatic radicals having from 1 to about 20 carbon atoms such as methylene, butylene, isobutylene, nonylene, dodecylene, neopentylene and the like; cycloaliphatic radicals having from 5 to about 12 carbon atoms such as cyclo-octylene, 1,4-dimethylene cyclohexylene, cyclohexylene and the like; aromatic radicals having from 6 to about 16 carbon atoms such as phenylene, naphthalene, 1,4-dimethylene phenylene, bisphenylene, diphenylmethane, 2,2-diphenylene propane and the like; or aliphatic, aromatic or cycloaliphatic radicals containing one or more divalent radicals of the formula: --O--, --SO 2 --, --C(O)--, --C(O)O)--, --NH--, --S-- and the like, such as diphenylene sulfone, diphenylene ether, diphenylene ketone, diphenylene amine, diphenylene sulfide, and the like.
Particularly useful polycarbodiimides include poly (2,4,6-triisopropyl-1,3-phenylene carbodiimide); poly(2,6 diisopropyl-1,3-phenylene carbodiimide), poly(tolyl carbodiimide); poly(4,4'-diphenylmethane carbodiimide); poly(3,3'-dimethyl-4,4'-biphenylene carbodiimide); poly(pphenylene carbodiimide); poly(m-phenylene carbodiimide); poly(3,3'-dimethyl-4,4'-diphenylmethane carbodiimide); poly(naphthylene carbodiimide); poly(isophorone carbodiimide); poly(cumene carbodiimide); poly(mesitylene carbodiimide); and mixtures thereof. Preferred polycarbodiimide are poly(2,6-diisopropyl-1,3-phenylene carbodiimide) (Stabaxol®P), poly (2,4,6-triisopropyl-1,3-phenylene carbodiimide) (Stabaxol®P-100) and poly(2,2', 6,6'-tetraisopropyldiphenylene carbodiimide) (Stabaxol® D). These preferred materials are commercially available as Stabaxol® grades from Rhein-Chemie.
Useful polycarbodiimides may be formed by processes known to those of skill in the art or from commercial sources. For example, useful polycarbodiimides can be prepared by heating the corresponding isocyanates in the presence or absence of a solvent and a catalyst such as phosphorus containing catalysts. These procedures are described in greater detail in U.S. Pat. No. 2,853,473 and Monogle, J. J. "Carbodiimides., II. Conversion of Isocyanates to Carbodiimides. Catalyst Studies", J. Org. Chem., 27, 3851 (1962).
Another class of graft-coupling agents are blocked isocyanates and diisocyanates. Examples are caprolactam blocked methylene bis(4,4'-diisocyanatobenzene) (blocked MDI), blocked toluene 2,4-diisocyanate and the like. Useful blocked isocyanates and blocked diisocyanates can be prepared by known techniques or obtained from commercial sources as for example from Miles under the tradename Desmodur isocyanates.
Yet another class graft coupling agents are di or multifunctional epoxides such as diglycidyl ether of bisphenol-A, triglycidyl ether of p-aminophenol, and epoxynovolacs (EPN-1138, ECN-1299). Certain of these materials can be prepared by procedures known to those of ordinary skill in the art or can be obtained from commercial sources as for example Ciba Geigy.
Other class of graft-coupling agents include multifunctional oxazolines (e.g. m-phenylene bisoxazolines) commercially available from Takeda, Japan.
The composition includes an "effective amount of graft-coupling agent". As used herein, an "effective amount of graft coupling agent" is an amount which when melt blended with a composition of the thermoplastic polyester, polycarbonate and amine functionalized elastomer is sufficient to enhance the extent to which a composition retain its impact strength (notch izod, at low and/or high temperature) after annealing. Usually, the amount of graft promoter is at least about 0.1% by weight of the polyester, polycarbonate and elastomer in the composition. The amount of graft promoter is preferably from about 0.3 to about 5% by weight, more preferably from about 0.5 to about 2% by weight and most preferably from about 1 to about 2% by weight on the aforementioned basis.
In addition to the above-described essential components, the blend of this invention can include various optional components which are additives commonly employed with polyester and polycarbonate resins. Such optional components include fillers such as talc, fiberglass, clay and the like; plasticizers, such as lactams, polyesters and sulfonamides such as caprolactam, aluryllactam, ortho and paratoluene ethyl sulfonamides polyester glutamate, polyester glycol, polyester adipate and the like, impact modifiers, chain extenders; colorants and pigments such as iron oxide, calcium red, rhodamine, chrome yellow, chrome green, phthalo-cyanine blue and the like; mold release agents; antioxidants; ultra violet light stabilizers; nucleators; lubricants; antistatic agents; fire retardants; and the like. These optional components are well known to those of skill in the art, accordingly, will be described herein in detail. These optional materials may be incorporated process. Typically, such optional materials are included in the mixing seeped for formation of the blend or in subsequent melt forming processes such as injection molding.
The composition of this invention exhibits relatively high impact strength both at room temperature (i.e. about 24° C.) and at low temperature (down to about -40° C.) as measured by ASTMD-256 notched Izod at 23° C., 0.1875 inch (0.476 cm) thick samples and ASTM D-638 tensile strength modulus and elongation. The blend preferably retains all or substantially all the room and low temperature strength after heating at 70° C. to 160° C. for up to 72 hours. In the preferred embodiment of this invention the composition maintains a "useful level of room and low temperature impact strength" after annealing from about 16 to about 72 hrs. at 150° C. As used herein, a "useful level of room and low temperature impact strength" is equal to or greater than 50 ft. lbs of drop weight impact strength and an initial Notched Izod before annealing at low and room temperature of equal to or greater than 5 ft lbs/in, preferably equal to or greater than about 8 ft lbs/in, more preferably equal to or greater than about 10 ft lb/in and most preferably equal to or greater than 12 ft lb/in. Amongst these preferred embodiments of the invention, preferred are the compositions which retain at least about 25% of their room temperature (23° C.) impact strength (notched izod) and at least about 20% of their low temperature (-40° C.) impact strength (notched izod) after annealing; more preferred are the compositions which retain at least about 40% of their room temperature impact strength and at least about 30of their low temperature impact strength after annealing; and most preferred are the compositions which retain at least about 60% of their room temperature impact strength and at least about 40% of their low temperature impact strength after annealing.
The composition of this invention can be prepared by blending or mixing the essential ingredients, and other optional components, as uniformly as possible employing any conventional blending means. Appropriate blending means, such as melt extrusion, batch melting and the like, are well known in the art and will not be described here in greater detail. See for example, "Extrusion" in the Encyclopedia of Polymer Science of Technology, Vo. 6, p. 571-631; John Wiley & Sons, 1986, incorporated herein by reference. Usefully, the blending procedure can be carried out at elevated temperatures above the melting point of the polymers added either alone or as a combination in a suitable form as for example, granules, pellets and powders are added to the melt with vigorous stirring. For example, the polyester can be masterbatched or preblended with the polycarbonate and elastomer in the melt and this premixed or masterbatch added to the polycarbonate and elastomer in the melt in amounts sufficient to provide the desired amount of polymers, polycarbonate and elastomer in the blend product. Similarly the blending procedure can be carried out at elevated temperatures, where one or the polymer components is melted and the other polymer component is admixed therewith by vigorously stirring the melt. Similarly, the various solid components can be granulated, and the granulated components mixed dry in a suitable blender, as for example, a Banbury mixer, as uniformly as possible, then melted in an extruder and extruded with cooling.
Alternatively, the composition of this invention can be formulated by dissolving the components in an appropriate inert solvent, after which the solvent is removed by evaporation, or other conventional solvent removing means are employed to provide the composition. The solvent is not critical, the only requirement being that it is inert to the components of the composition, and it is capable of solubilizing the various components, or at least forming dispersion thereof.
The blend according to the invention can be used for those applications for which polyesters, polycarbonates and blends thereof can be used. They are thermoplastic materials from which molded articles of manufacture having valuable properties can be produced by conventional polymer shaping processes, such as injection molding and extruding. Examples of such moldings are components for technical equipment, lawn and garden equipment, power snow shovel and snow-mobile equipment, household equipment, sports equipment, powertool equipment for the electrical and electronics industries and electrical insulations, automobile components, and semi-finished products which can be shaped by machining. The composition of this invention is especially suited for use in the fabrication of automotive parts, especially, those for use under the hood which may be exposed to high temperatures during the operation of the automobile. Similarly, the blend of this invention can be used to fabricate components of powertools, snowmobiles and similar equipment operated outdoors.
The following examples are presented to better illustrate the invention and should not be construed as limiting the invention.
COMPARATIVE EXAMPLE 1
Blend of Poly(Ethylene Terephthalate) (PET)
Polycarbonate (PC) and Ethylene/Propylene Rubber (EPR)
A pellet/pellet mixture of 6 lbs of poly(ethylene terphthalate) (PET) (IV=0.7 dl/g in phenol/TCE, 0.035 meq/g COOH) and 3 lbs of an EPR (Exxon PE 901, ummodified, Mooney viscosity of 25) was fed into the throat of a 34 mm Leistritz corotating fully intermeshing twin screw extruder. The extruder contained 10 heated barrel sections with downstream feed capability at the 4th and 6th barrel sections. A typical temperature profile has the first three barrel sections heated to 250° C. and the rest heated to 270° C. Mixing elements are located in sections 5& 7. Materials are typically starve fed at 30-35 lb/hr, at a screw speed of 200-250 revolutions per minute RPM.
Concurrently, 6 lbs of PC (GE Lexan 101) was added downstream in barrel section 4. The extrudate was water cooled, pelletized, and vacuum dried for injection molding.
COMPARATIVE EXAMPLE 2
Blend of Poly(Ethylene Terephthalate) (PET)
Polycarbonate (PC) and Maleated Ethylene Propylene Rubber (MA-EPR)
Using the procedure of Comparative Example 1, a pellet/pellet mixture of 1.2 kg of PET (IV=0.7 dl/g in phenol/TCE, 0.035 meq/g COOH), 1.2 kg of PC (GE Lexan 101), and 0.6 kg of MA-EPR (Exxon Excelor 1803, 0.7% maleation, a Mooney Viscosity of 25) was extruded on a Haake TW-100 conical twin screw extruder at 75 RPM. The extruder was heated to 230° C. 265° C., 280° C., 280° C. (zones 1-4). The extrudate was water cooled, pelletized and vacuum dried for use in injection molding experiments.
EXAMPLE 1
Blend of Poly(Ethylene Terephthalate) (PET),
Polycarbonate (PC) and Aminated Ethylene Propylene Rubber (A-EPR)
Using the procedure of Comparative Example 1, a pellet/pellet mixture of 6 lbs of PET (IV=0.7 dl/g in phenol/TCE, 0.035 meq/g COOH) and 3 lbs of an A-EPR was fed into the throat of the Leistritz extruder. Concurrently, 6 lbs of PC (GE Lexan 101) was added downstream in barrel section 4. The extrudate was water cooled and was pelletized and vacuum dried for use in injection molding experiments.
EXAMPLE 2
Blend of Poly(Ethylene Terephthalate) (PET),
Polycarbonate (PC), Amine Functional Ethylene
Propylene Rubber (A-EPR) and Graft Coupling Agent
A pellet/pellet mixture of 4.65 lbs of PET (IV=0.7 dl/g in phenol/TCE, 0.035 meq/g COOH) and 3 lbs of an A-EPR was fed into the throat of the Leistritz extruder. Concurrently, 5.85 lbs of PC (GE Lexan 101) was added downstream in barrel section 4, and a powder/powder mixture of 1.2 lbs of powdered PET (IV=0.7 dl/g in phenol/TCE, 0.035 meq/g COOH) and 0.3 lbs of a graft-coupling agent, poly(2,4,6-triisopropyl-1,3-phenylene carbodiimide) (Rhein Chemie Stabaxol P-100 powder) was added downstream in barrel section 6. The resulting blend was pelletized for use in injection molding experiments.
COMPARATIVE EXAMPLE 3
Blend of Poly(Ethylene Terephthalate)(PET),Polycarbonate(PC),
Maleated Ethylene/Propylene Rubber(MA-EPR) and Graft Coupling Agent
A pellet/pellet mixture of 4.65 lbs of PET (IV=0.7 dl/g in phenol/TCE, 0.035 meq/g COOH) and 3 lbs of MA-EPR (Exxon Excelor 1803, 0.7% maleation, Mooney Viscosity of 25) was fed into the throat of the Leistritz extruder. Concurrently, 5.85 lbs. of PC (GE Lexan 101) was added downstream in barrel section 4, and a powder/powder mixture of 1.2 lbs of powdered PET (IV=0.7 dl/g in phenol/TCE, 0.035 meq/g COOH) and 0.3 lbs of a graft-coupling agent,poly(2,4,6-triisopropyl-1,3-phenylene carbodiimide) (Rhein Chemie Stabaxol P-100 powder) was added downstream in barrel section 6. The resulting blend was pelletized for use in injection molding experiments.
COMPARATIVE EXAMPLE 4
A series of experiments were carried out to show the effect of the amine functionalized ethylene/propylene elastomer on certain properties of blends of polyester and polycarbonates. The properties selected for evaluation were initial high and low temperature Notched Izod, high and low temperature Notched Izod after annealing, initial elongation-to-break and the elongation-to-break after annealing. The blends selected for comparison were those of Comparative Examples 1 and 2, and Example 1. In these experiments, pellets of the polymer blend are injection molded into ASTM test specimens on an Arburg 25 ton Allrounder molding machine. The molded specimens are tested for notched izod impact strength (ASTM D256), tensile strength and elongation (ASTM D638), and flexural strength and modulus (ASTM D790). Some specimens are also tested for drop wt impact strength (ASTM D3029).
The results of the experiments are set forth in the following Table 1. In the Table, the abbreviations have the following meanings:
(a) "NI-23" means initial Notched Izod of a sample after molding measured at 25° C.
(b) "NI-40" means initial Notched Izod of a sample after molding measured at -40° C.
(c) "ANI-23" means Notched Izod of a sample after annealing for from 16 to 72 hrs. at 150° C., measured at 25° C.
(d) "ANI-40" means Notched Izod of a sample after annealing for from 16 to 72 hrs. at 150° C., measured at 40° C.
(e) "EB" means the initial elongation to break of a sample after molding.
(f) "AEB" means the elongation to break of a sample after annealing for from 16 to 72 hrs. at 150° C.
TABLE I__________________________________________________________________________Exp. NI-23 NI-40 ANI-23 ANI-40 EB AEBNo. Sample ft-lbs/in ft-lbs/in ft-lbs/in ft-lbs/in % %__________________________________________________________________________1 Ex. 1 14.6 16.9 6.9 4.0 196 192 Comp. 13.6 1.5 1.9 1.6 4.2 8 Ex. 13 Comp. 14.2 2.7 3.1 1.1 9 11 Ex. 2__________________________________________________________________________
COMPARATIVE EXAMPLE 5
Using the procedures of Comparative Example 4, a series of experiments were carried out to show the effect of the combination of amine functionalized ethylene/propylene elastomer and graft coupling agent on certain properties of blends of polyester and polycarbonate. The properties selected for comparison were the same as in Comparative Example 4. The blends selected for comparison are those of Comparative Examples 1, 2 and 3, and Examples 1 and 2. The results of the experiments are set forth in the following Table II and FIGS. 1 to 4.
TABLE II__________________________________________________________________________Exp. NI-23 NI-40 ANI-23 ANI-40 EB AEBNo. Sample ft-lbs/in ft-lbs/in ft-lbs/in ft-lbs/in % %__________________________________________________________________________1 Ex. 2 16 17.5 12.4 8.5 189 222 Ex. 1 14.6 16.9 6.9 4 196 193 Comp. 13.6 1.5 1.9 1.6 42 8 Ex. 14 Comp. 14.2 2.7 3.1 1.1 9 11 Ex. 25 Comp. 14.9 2.6 12.1 3.2 16 13 Ex. 3__________________________________________________________________________
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This invention relates to a blend comprising a polyester, polycarbonate and an amine functinalized elastomer and optionally an effective amount of an effective graft coupling agent.
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BACKGROUND OF THE INVENTION
The present invention relates to a collector arrangement for a solar energy heating system in which a plurality of cell elements cooperate with pipes for the passage of a heat exchange medium.
There is no doubt that there is only a limited supply of industrially extractable fossil energy sources, such as coal, oil, oil sand, oil shale, and natural gas. This applies more particularly to the present main energy source, oil. Even when taking account of new oil fields, it is excepted that oil supplies will be exhausted in about 50 years. Certain internationally recognized research institutes have in fact made even less favorable forecasts. However, even these pessimistic forecasts must not hide the fact that on the basis of the law of supply and demand the oil shortages which will occur much earlier will lead to considerable price rises. The effects of such oil rises for our economy became very apparent after the last oil crisis.
Attempts are therefore being made to find new independent energy sources. The main object of these efforts is to develop a maximum number of substitute energy sources, using these whenever possible in place of oil. World-wide statistics show that a large proportion of existing oil supplies is being used for heating purposes.
However, for this purpose solar energy constitutes an ideal substitute energy source. Quite apart from the fact that this energy is available free and in unlimited quantities, it is characterized by having no harmful effects on the environment. A further important advantage is that it can be used on a completely decentralized basis. However, it must be remembered that this energy can only be obtained by day and, in part, only with direct solar radiation. Account must also be taken of the fact that solar energy only has a relatively low intensity, particularly with clouded skies, when only the much less diffuse rays can be used.
A number of commercially usable systems for using solar energy for heating purposes are already known. In particular, a so-called solar cell system has been adopted, a distinction being necessary between flat cells and focussing cells.
In the case of flat cells, the basic construction is always essentially the same. A generally metallic flat body is provided with a radiation-absorbing surface which generally consists of black lacquer or some similar material. Pipes or ducts are placed in or on the body. Through the pipes or ducts circulates a heating exchange medium which conveys away the heat trapped by the absorbing surface. This heat can be used either directly or indirectly for heating purposes.
Since, according to the Stefan-Boltzmann law, each black body also emits thermal radiation whose intensity rises to the fourth power of its temperature, the cells are covered with one or more layers of glass or plastic. These glass or plastic layers are not transparent for the wavelength range of the rays emitted by the cell, so that the partly reflected rays are largely absorbed by the glass or plastic layers, where they are converted into heat, leading to the so-called hothouse effect.
The back of the cell is provided with a sufficiently thick insulating layer, so that only very small losses occur here.
To make the ratio between absorption and emission more favorable, in more sophisticated flat cells the black surface is replaced by a so-called selective surface. Selective surfaces have the advantage that the solar radiation is absorbed very well and emission is very small.
Flat cells have a number of advantages. Thus, they are able to convert even diffuse radiation into thermal energy. In addition, there is a good efficiency up to a heating medium temperature of 60° C. (Celsius). Furthermore, the flat cells are relatively inexpensive and simple to install.
However, reference must also be made to certain of the disadvantages of flat cells. A particular disadvantage is the poor efficiency in the high temperature range, temperatures above 100° C. (Celsius) being very difficult to obtain. Even in the case of optimum alignment of the cells relative to the sun, i.e. its position at midday, there is a particularly strong reflection from the flat covering plates in the morning and evening, due to the very acute angle of incidence, so that efficiency drops. This is very disadvantageous because, other than at night, it is particularly in the morning and evening that thermal energy is required. It is also very difficult to obtain an air-tight seal for the space between cell and covering layer. Moist air frequently enters this space and leads to fogging of the panes of glass, so that efficiency drops. The ideal solution would be a high vacuum in this space. However, due to the relatively large areas, even a low vacuum would cause the panes of glass to break. To obtain good efficiency, the cell surface must be aligned as precisely as possible with the mean solar position. However, in the case of house roofs which do not have this optimum position and inclination, installation is difficult or efficiency is low. For numerous reasons it is unlikely that a sail-like installation of the cells would be permitted. In addition, as the cells are generally only made in certain sizes, it is difficult to adapt them to particular roof shapes.
In the case of focussing solar cells, the incident solar radiation is focussed onto a point, line, or surface my means of an optical system, e.g. a mirror or lens system. In the case of solar cells for heating purposes, generally cylindrical-parabolic mirrors are used in which the incident rays are concentrated on a line. Rotationally symmetrical parabolic mirrors are less frequently encountered.
Cylindrical parabolic mirrors generally are made from glass, to the back of which is applied a thin silver coating. This coating reflects the incident rays onto the focal line of the parabolic mirror.
According to a further variant, the parabolic mirror is made from highly polished metal.
The absorber is also located in the focal line of the parabolic mirror. The absorber is generally constituted by black metal tubes or glass-covered black metal tubes, glass tubes with a black licquid which is simultaneously used as a heat carrier medium, or special metal profiles surrounded by a glass tube. A number of telescoped glass tubes could also be used, one being provided with a selective absorber coating and the underlying glass tube serving as a supply and discharge tube for the heat carrier medium.
An important feature of focussing cells is the concentration factor. This factor C forms the ratio of the admission surface of the cell to the absorber surface. The higher the factor C, the higher the temperature to which the carrier medium can be heated.
Advantages of focussing cells are, inter alia, that very high temperatures can be obtained as a function of the concentration factor. In the case of indirect further use, the temperature level is a measure for good efficiency. It is also advantageous that the emission and convection losses are much lower than with flat cells, due to the small absorber surface compared with the admission surface.
It is disadvantageous that focussing cells only operate with direct solar radiation, and must therefore follow the sun, which requires an additional mechanism. In addition, they are expensive to maintain and can only be installed on suitable roofs, preferably flat roofs. It is very difficult to install them on inclined house roofs. Their wind pressure sensitivity is a further disadvantage. They are also relatively costly, sizes cannot be varied as desired, due to their standard, and cannot be individually adapted readily to special requirements.
SUMMARY OF THE INVENTION
The problem to which the present invention is directed is to provide a system of cells combining at least the most important advantages of flat cells and focussing cells, while avoiding their disadvantages and which are particularly easy to manufacture and inexpensive, while permitting the widest possible range of applications.
According to the present invention the cell elements are bottle-shaped hollow bodies of glass or plastic, which can be placed in any desired number in juxtaposed manner on a tube and whose faces can be braced relative to one another, whereby the wall of the hollow body is spaced from and surrounds the tube.
Thus, such a cell element only has a neck and a base with an opening, the latter being able to receive the neck of a further hollow body in plug-in form. To provide adequate stability, the opening in the base can be bounded by an inwardly extending annular flange.
Such cell elements can be manufactured in an inexpensive manner in a glassworks by a bottle manufacturing process.
Preferably, the cell system is then constructed in such a way that a plurality of tubes, in each case carrying a plurality of cell elements, are arranged parallel to one another with a spacing corresponding approximately to the largest width of one cell element. Adjacent tube ends are elastically interconnected by tube bends or hoses. According to an advantageous further development the tubes carrying the cell elements are interconnected in articulated manner to form a Venetian blink-like arrangement.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a solar heating system, including, as shown in block form, a solar collector assembly, which is in accordance with a preferred embodiment of the present invention.
FIG. 2 shows both a longitudinal, sectional view of a linear fragment of a row of collector cell elements of the collector assembly of FIG. 1 and a cross-sectional view of one such cell element.
FIG. 3 shows both a partially schematic plan view, and also a partially schematic end view, of the collector assembly of FIG. 1.
FIG. 4 is a schematic end view of the collector assembly of FIG. 1 showing the rows of cell elements all oriented in the same direction.
FIG. 5 is as schematic end view of the collector of FIG. 1 showing the rows of cell elements oriented in different directions to direct the collector assembly toward the mean direction of the sun.
FIG. 6 is a schematic end view of a collector in accordance with a preferred embodiment of the present invention mounted on a vertical surface.
FIG. 7 is a schematic end view of an articulated collector in accordance with another embodiment of the present invention, the collector being arranged for covering a portion of, or all of, a swimming pool.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the solar energy heating system diagrammatically illustrated in FIG. 1, water as the heat exchange medium, is heated under the action of the sun in a cell system 10, preferably installed on the roof of a house, the water then being fed to a heat consuming means 11 in the form of a heating system, via a flow line 13. The water flow is driven by a circulating pump 12 into the return flow line 14 of the circuit system.
It is pointed out that in this way it is possible to connect a large number of further consuming means into the system. The consuming means can be of very varied types, e.g. hot water boilers and, in particular, swimming pools.
A cell system 10 which is particularly suitable for such a solar energy heating system is shown in FIGS. 2 to 7 and will be described in greater detail hereinafter.
The essential feature for such a cell system are cell elements, formed in this case by bottle-shaped hollow bodies 15 made from glass or plastic, as is shown more particularly in FIG. 2, and which can be placed in any desired number and in juxtaposed manner on a tube 16. Each hollow body 15 has a neck 17, with an internal diameter corresponding to tube 16. The external diameter of neck 17 corresponds to the internal diameter of an opening in base 18 of hollow body 15 in such a way that neck 17 can be inserted with an adequate clearance into the opening in the base 18 of another hollow body 15. To provide adequate stability, the base opening is bounded by an inwardly extending annular flange 19. Annular slots 20, 21, which serve to receive a sealing compound or a ring gasket, are provided both in base 18 and on the wall of neck 17.
The hollow bodies 15 can be placed in any desired number on a correspondingly long tube 16 and can be reciprocally braced thereon by means, for example, of flanging means 22 (FIG. 3) which can be screwed onto the tube ends, so that a closed system is formed in such a way that hollow body 15 surrounds tube 16 as a continuous glass wall, the latter being spaced from and surrounding the tube.
As can be gathered from the cross-sectional drawing of FIG. 2, the wall of the bottle-shaped cell element 15 is subdivided into two halves forming a rear 115 and a front 215, the rear 115 being coated with a reflection coating 23, preferably a silver coating. As a result of this coating, the back 115 acts as a mirror. Efficiency can be further improved by metallizing the two faces.
In the cross-section according to FIG. 2, the wall of the bottle-shaped cell element 15 can have very varied configurations. For example, in cross-section the two wall faces can have a semi-circular configuration so that together they form a right circular cylinder. However, preferably front 215 is cross-sectionally semi-circular and back 115 is cross-sectionally substantially or at least partly parabolic.
To prevent the metallized coatings from being damaged by the weather, they are additionally covered or sealed by a top coating, e.g. of long life and weather-resistant plastic. This plastic coating also serves as an insulating coating.
Depending on the size of hollow body 15 and the diameter of tube 16, a particular desired concentration factor can be obtained. It is apparent that the tube 16 must be located approximately in the focal line of the back 115 which forms the mirror. Due to the relatively large diameter of the tube as compared with the opening surface, the tube can be fitted with a relatively low level of precision. Even in the variant where back 115 only has a round surface for reasons of simplicity, the tube will still be able to collect almost all the reflected rays.
A further variant for the reflection of rays is provided by an elastic shield with a reflecting coating which, when compressed, can be inserted into the cell elements, the shield being fixed in the particular element by springing back.
As can be gathered more particularly from FIG. 3 a collector system is there formed in that a plurality of tubes 16, in each case carrying a plurality of cell elements 15, are arranged parallel to one another, preferably with a spacing which is approximately equal to the largest width of a cell element 15. Adjacent tube ends are interconnected by tube bends 24 or elastic hoses. This generally flat structure then has a continuous tube system with a connection 113 for the flow line 13 and a connection 114 for the return flow line 14 in FIG. 1. It is thus possible to assemble cell systems which can be adapted to virtually any roof shape and which has a wide range of uses, as will be described in greater detail hereinafter.
It is not only possible to obtain any desired size and adapt to any roof shape, but also possible to assemble a large number of very different cell shapes for architectural and aesthetic reasons. Thus, mosaic, star, and circular shapes can be obtained, which is certainly advantageous in view of the present attempts to obtain individuality.
A further important advantage is provided by this system for houses whose roofs do not happen to be in the optimum position relative to the sum. In this case, the cells are admittedly arranged in juxtaposed flat manner on the roof, but by simply rotating the opening plane of the individual cell elements 15 about the tube axis in the direction of the mean position of the sun, the efficiency can be significantly increased (FIG. 4). Furthermore, through the convex shape of the hollow body surface, sloping incoming rays can be trapped much better than with e.g. flat cells.
As has been stated hereinbefore, due to the flat angle of incidence with flat cells the efficiency in the morning and evening is relatively poor and this is when, other than at night, most thermal energy is required.
The present system largely obviates this disadvantage in that, according to FIG. 5, a particular number of cell elements 15 are oriented more in one or the other direction. In addition, as a result of the convex sun-side halves 215 of hollow bodies 15, sloping incoming rays are much better trapped. Thus, a more uniform temperature gradient can be obtained throughout the day.
A further important advantage of the proposed system compared with prior art systems is obtained when it is installed on flat roofs. Whereas both the flat cell and the focussing cell must project from the roof surface to be oriented at the sun, according to the novel system the individual cell elements and an additional second roof membrane can be placed flat on the roof, so that only the opening planes of the individual cell elements have to be aligned with the mean solar position by rotating about the tube axis.
A further advantage of the present system is that it can also be usefully installed on vertical house or other masonry walls which face the sun (FIG. 6). In this case, the cell elements are advantageously aligned parallel to the earth's surface and the opening planes are aligned with the mean position of the sun by rotating about the tube axis. This system also acts as an additional wall and, in addition, functions as general weather-proofing, while also acting as additional thermal insulation.
In this connection, the cell systems could even be constructed for use as garden fences or the like.
A further possible use is illustrated in FIG. 7 in which the parallel tubes 16 carrying the cell elements 15 are interconnected in articulated manner in such a way that they form a Venetian blink-like arrangement. In this embodiment, the Venetian blink arrangement serves simultaneously to cover a swimming pool 100 and can appropriately be moved into or out of a corresponding room or chamber 101. The articulated connections between the individual tubes may be articulated screw couplings or chain links.
A very important advantage of the present cell system is that it has both the main features of a flat cell and of a focussing cell. Thus, as a function of the ratio of the opening plane to the tube diameter a predetermined concentration factor can be obtained, so that the temperatures can be higher than those obtained with a flat cell. Furthermore, a larger proportion of diffuse radiant energy can be collected and converted into thermal energy.
In addition, such a cell system can be constructed so as to offer maximum resistance to aging and to the weather. The air can also be sucked out of the space between the tube and the hollow body and a vacuum produced in this space in advantageous manner. Such a cell system can also be extended or modified at any time and in simple manner. This is very important, because the requirements made on a heating system can constantly vary. Furthermore, all the components of the system can easily be produced in standard sizes and can be assembled by untrained people on a do-it-yourself basis. This is particularly significant from the cost angle for private householders. However, even if a person is undecided, his performance of a simple experiment can make a decision much easier, costs being very low. This will be a particular advantage during the initial introductory phase. Thus, the individual components can be sold by do-it-yourself chains and mail order houses, thus appealing to a much larger segment of the purchasing public.
If glass is used for the cell elements, this can be manufactured particularly inexpensively in a glassworks by a conventional bottle production process.
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Individual collector cells are fitted together in series along a heat transfer medium tube. The cells have a cylindrical housing with mating interconnecting flanges at the ends, through which the tube also passes. The flanges may have sealing gaskets. The housing has a transparent front side and a reflective back side. The cross-sectional configuration of the front is arcuate, while that of the back is parabolic. The cells are fixed with respect to the tube axis, but can rotate about it to follow the sun. Parallel cell rows can be interconnected to rotate together. Interconnected, articulated cell rows are disclosed as a removable cover for a swimming pool.
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RELATED APPLICATION
The present application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/261,678 entitled, SELF-PLANARIZING MODULE filed on Jan. 12, 2001 by Donald Curtiss et al., the contents of which are incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to optical data storage disks and, more particularly, to replicating such data storage disks.
BACKGROUND OF THE INVENTION
Data storage disks are typically produced using a disk replication process. A master disk is made having a desired surface relief pattern formed therein. The surface relief pattern is typically created using an exposure step (e.g., by laser recording) and a subsequent development step. The master disk is used to make a stamper, which in turn is used to stamp out replicas in the form of replica disk substrates as part of a disk molding or stamping process. As such, the surface relief pattern, information and precision of a single master can be transferred into many inexpensive replica disk substrates.
Conventional mold assemblies, although usually referred to as “stampers” for historical reasons, typically include a fixed side and a moving side. The stamper portion is typically attached to the moving side for replicating a desired surface relief pattern (i.e., lands, grooves and/or pits) into the replica disk substrate. A movable gate cut may be provided for cutting a central opening in the replica disk substrates. The stamper is usually secured to the moving side using an inner holder, wherein the inner holder fits over the stamper. Several more tooling parts may be located at the center of the mold assembly.
In one conventional process, during the disk molding process, a resin, typically optical grade polycarbonate, is forced in through a channel into a substrate cavity within the mold assembly to form the replica disk substrate. The surface relief pattern or formatted surface is replicated in the replica disk substrate by the stamper as the cavity is filled. After filling, the gate cut is brought forward to cut a center hole in the replica disk substrate. After the replica disk has sufficiently cooled, the mold assembly is opened and the gate cut and a product eject may be brought forward for ejecting the formatted replica disk substrate off of the stamper. The inner holder may be removable to allow changeout of the stamper.
In another conventional process, a disk is coated with a relatively thin polymer layer into which the fine details are stamped. The starting composition is not molten plastic, but can be an element comprising a very thin embossable radiation-reflective layer overlying an embossable, heat-softenable layer which can be simply thermoplastic or can also be radiation-curable. Optionally, the heat-softenable composition can be coated on a substrate. Impressing the stamper information into the heat-softenable layer can be done with a platen or roll embosser. Radiation curing helps retain the desired relief shape by crosslinking. Disks are provided with a reflective layer either before or after they are impressed with the information-carrying relief pattern.
A significant disadvantage with both of the high pressure, high temperature relief-forming methods described above is the potential for image distortion and internal stresses in the disks produced. Regardless of the particular conventional process used, one shortcoming of the techniques employed in this field is the lack of parallelism between the two platens of the stamper. The parallelism, or lack thereof, affects the pressure gradient across various regions of the blank disk as well as the precision and accuracy with which the fine details are transferred to the blank disk. Methods for replicating disks have relied on precision manufacturing and assembly of the stamping equipment to provide the tolerances needed for accurate disk replication. These methods increase the complexity and costs of the stamping equipment as well as their maintenance, calibration and operation. Therefore, a need, unmet by the prior art, exists for a less expensive and less complex stamping machine which provides the precision needed to accurately replicate optical data storage disks.
SUMMARY OF THE INVENTION
These and other shortcomings of the prior art are addressed by a stamper assembly which incorporates a self-leveling mechanism into at least one of the stamper platens which acts to dynamically bring the two platens into a parallel relationship during the stamping operation. As a result, the yield of the replication process is increased due to increased accuracy, the manufacturing cost and complexity of stamping equipment are reduced, and the repair, maintenance and operating costs of the stamping equipment is reduced.
One aspect of embodiments of the present invention for addressing the needs unmet by the prior art relates to a stamper module for optical disk replicating equipment which includes a platen which can connect with a stamper and a platen which can connect with a disk. The stamper module also includes means that dynamically orient the first and second platen into a parallel orientation during the stamping operation.
Another aspect of embodiments of the present invention relates to a stamper module for optical disk replicating equipment which includes a first and second platen in which a ball joint is connected with the first platen. The ball joint operates such that when the first and second platen are performing a stamping operation, the ball joint swivels to orient the first platen and the second platen in parallel.
Yet a further aspect of embodiments of the present invention relates to a stamper module for optical disk replicating equipment which includes a first and second platen each having a surface opposing the other. In accordance with this aspect, the module also includes a ball joint attached to the first platen and a pressure train configured to bring the opposing surfaces towards one another during a stamping operation. The position of the ball joint allows the ball joint to swivel during the stamping operation so as to orient the opposing surface parallel to one another during stamping.
The foregoing and other features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A through 1C illustrate different operating positions of disk stamping equipment according to an embodiment of the present invention.
FIG. 2 illustrates an exemplary ball joint in accordance with an embodiment of the present invention
DETAILED DESCRIPTION OF THE INVENTION
The present invention addresses needs previously unmet in the field of disk replication by providing a stamper assembly that incorporates a self-leveling mechanism into at least one of the stamper platens. The self-leveling mechanism acts to dynamically position the two platens of the assembly into a parallel relationship during the stamping operation.
FIGS. 1A through 1C illustrate portions of an optical disk replicating stamper assembly 100 during different phases of operation. Other portions of the entire stamper assembly, which are well known in the art, are not depicted in the figures so as not to obscure the merits and features of the present invention. These undepicted portions of a disk replicator include the arrangements for applying pressure 102 and 104 to the two platens 106 and 108 . Also, the stamper assembly 100 can also be enclosed in a vacuum chamber so that certain process steps, including the stamping, can be performed under vacuum.
In particular, FIG. 1A illustrates the assembly 100 in a preparatory state before the stamper 110 and disk 112 come into contact. FIG. 1B depicts the stamping operation as it is occurring while the two plates 106 and 108 are initially unparallel and FIG. 1C depicts the performing and completion of the stamping operation once the two platens 106 and 108 are positioned in a parallel arrangement.
Stamper 110 is formed according to conventional disk mastering techniques as are known in the art. According to these techniques, data to be encoded on a disk is arranged and formatted, according to the disk's eventual application, into a disk image. For example, a DVD disk might have encoded thereon MPEG-2 sequences along with surround sound audio data.
Mastering a disk typically begins with a 240 mm diameter, 5.9 mm thick glassy plate which is polished and washed. After photoresist is spin coated and baked on the glass, the mastering equipment modulates a laser according to the disk image in order to expose a pit and land pattern across the glass plate. The exposed plate is then developed and etched to create pits in the photoresist surface. The glass master is then vacuum coated with silver. The pit geometries are the fine features transferred to blank disks during replication. Pit geometry for DVD is usually less than 0.74 μm while a conventional CD-ROM's pit geometry is less than 1.6 μm, as these values represent the track pitch of these two optical disk formats.
The glass master is not robust enough for the stresses of the stamping process. Therefore, the silvered glass master is placed in a galvanized tank with a nickel electrolyte solution with the glass master connected to the cathode such that a relatively thick nickel layer is electroplated from the anode onto the glass master. The nickel layer, which forms the stamper 110 , is then separated from the glass, cleaned, punched, trimmed, and used for replication of disks.
The disk 112 to be stamped is typically a rigid disk with a thin, deformable coating on top. In certain embodiments, the deformable coating is a polymer coating, such as polymethylmethacrylate from MicroChem Corp., and typically has a thickness in the range of 100 nm to 200 nm. However, other coating materials and thicknesses are expressly contemplated depending on the feature size and intended environment of the eventual stamped disk.
The coating is usually formed by spinning on a UV curable polymer over the surface of the disk 112 and then passing the coated disk under UV light to polymerize or cure the coating. After a stamper is pressed into the polymer layer, the disk 112 is vacuum coated with Aluminum, or similar material, to provide the reflectivity necessary for playback.
While specific embodiments described herein refer to particular compact disks in order to aid in the understanding of the present invention, the present stamper assembly is not limited to these specific embodiments. In particular, substantially clear plastic disks having thicknesses other than the standard 0.6 mm and 1.2 mm sizes are contemplated. Also, compact disks having a variety of data densities, encoding formats and storage capacities such as ISO-9660, CD-DA, CD-ROM, CD-I, CD-V and DVD, for example, can benefit from the stamper assembly 100 .
Returning to FIG. 1A, the stamper assembly 100 also includes a top platen 106 and a bottom platen 108 opposedly arranged. Using any of the industry-recognized conventional methods, the stamper 110 is attached to a surface of the top platen 106 and the polymer coated disk 112 is attached to a surface of the bottom platen 108 . Alternatively, the stamper 100 and disk 112 could be attached to the opposite platens as well. The pressure train of the replicating equipment applies pressure 102 and 104 to force the platens 106 and 108 together to perform a stamping operation (see FIG. 1 B). Typical stamping pressures for most compact disks are between 5-15 Mpa and preferably at least 10 Mpa. Depending on the disk material and polymer coating characteristics, other pressure ranges can be utilized.
In one embodiment, the platens 106 and 108 are constructed from a sturdy metal, such as stainless steel, and are 15″×15″×2′. However, this platen size is dependent on, and can be adjusted for, the disk size such that the platens 106 and 108 are large enough to securely support the stamper 110 and the disk 112 .
In certain preferred embodiments, the bottom platen 108 moves vertically due to pressure 104 in order to press the disk 112 against the stamper 110 which is attached to a stationary top platen 106 . Alternatively, the top platen 106 could move while the bottom platen 108 remains stationary; also, both platens 106 and 108 can be allowed to move together simultaneously or sequentially. Any combination which causes the work pieces to contact to produce a desired pressure (e.g., 10 Mpa) is expressly contemplated.
As with conventional stamping operations and equipment, applying pressure along the center of the platen in motion (e.g., 108 ) produces a more even distribution of pressure across the work pieces; therefore, a ball joint 114 is preferably, but not necessarily, located centrally with respect to the appropriate platen. In particular, FIGS. 1A through 1C each depict the ball joint 114 attached to the top platen 106 . Alternative embodiments include attaching the ball joint to the bottom platen 108 .
The ball joint 114 , as shown in more detail in FIG. 2, includes a first section 202 having a spherical part 204 (i.e., a ball portion) that is partially surrounded by a second section 206 (i.e., a socket portion). Although the surface of the spherical part 204 and the inside surface of the second section 206 are in substantial contact with one another, the sections are not fixably connected but, instead, are free to swivel relative to one another. As recognized in the art, ball joints can include locking mechanisms which are used to adjust the amount of pressure that must be applied before the two sections will move relative to one another.
In certain embodiments, the ball joint 114 is constructed of stainless steel and includes a ball and socket with a radius of approximately 20 inches polished smooth with 1.5 micron diamond paste to a mirror finish. Other radius balls can be used but should be designed to withstand the expected pressures of the stamping operation.
Although not distinguishable in FIG. 1A, the opposing surfaces of top 106 and bottom 108 platens are not precisely parallel to one another. As previously discussed, the conventional approaches tried to manufacture the replication equipment with exact mechanical tolerances to provide rigid platens that were in precise parallel arrangement. The present stamper assembly 100 does not require such exacting tolerances regarding the parallel arrangement of the platens 106 and 108 . If the platens 106 and 108 remained out of parallel during the stamping process then the features of the stamper 110 would not be accurately transferred to the disk 112 . This is because the pressure exerted by the stamper 110 on the disk 112 will not be uniform across the entire surface of the disk 112 . The ball joint 114 , however, ensures that platens 106 and 108 are parallel during stamping.
As shown in FIG. 1B, pressure 102 and 104 is applied so that opposing platens 106 and 108 are brought together. As the stamper 110 contacts the disk 112 in an unparallel orientation, the disk 112 and the stamper 110 contact each other within region 120 but do not contact each other outside the region 120 . As more pressure is applied, the top platen surface in contact with the attached stamper 110 experiences a pressure gradient which is transmitted (due to the rigid nature of the platen) to the attached ball joint 114 . The tension of the ball joint 114 can be adjusted so that the ball and socket swivel at a pressure which is less than the pressure at which the stamper 110 significantly affects the polymer coating on the disk 112 . As a result, the ball joint 114 dynamically adjusts to the pressure gradient during a stamping operation by swiveling to compensate for the lack of parallel between the two platens 106 and 108 .
As seen in FIG. 1C, the swiveling ball joint 114 , thus, acts as a self-leveling mechanism to bring the top 106 and bottom 108 platens in parallel during the disk replication process. Once the platens 106 and 108 are in parallel, as seen in FIG. 1C, the pressure 102 and 104 is increased to where the disk 112 is accurately stamped and, furthermore, the platens 106 and 108 remain in parallel throughout the stamping operation due to the self-leveling action of the ball joint 114 . As a result, the yield of the replication process is increased due to increased accuracy, the manufacturing cost and complexity of stamping equipment are reduced, and the repair, maintenance and operating costs of the stamping equipment is reduced.
Although the present invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the scope of the present invention being limited only by the terms of the appended claims.
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In a disk replicating assembly, a blank disk is attached to one platen and a stamper is attached to the other platen. Pressure is applied so that the two platens are forced together, thereby transferring features from the stamper to the disk. A ball joint is located between a platen and the pressure train of the replicating assembly. Due to the ball joint at this location, the resulting pressure gradient when the stamper and disk are pressed together causes the one platen to swivel such that it orients itself substantially parallel to the other platen. Because the resistance of the ball joint is selected so that the one platen is able to pivot before the stamper significantly affects the disk, the fine features of the stamper are not transferred to the disk until the platens are in parallel alignment.
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BACKGROUND OF THE INVENTION
[0001] Manipulation of micrometer-scale particles is of central importance in cell biology and microfluidics. The particles can be cells or components thereof that are to be studied or small droplets containing such components. For example, individual cells can be isolated in small aquaise droplets that move in a hydrophobic medium. The cells can be moved to locations in which the cellular contents are measured. The cells can also be lysed and the cellular contents studied within the droplet that now contains the cellular contents. Ideally, thousands of such droplets can be processed in parallel by using electrical forces to move the individual droplets or particles within an apparatus.
[0002] To simplify the following discussion, the object that is being moved will be referred to as a “particle” unless the context indicates otherwise. The particle could be a small droplet containing something of interest that is to be studied. In other cases, the particle could be a cell or other object that is to be studied as opposed to a droplet containing the cell.
[0003] Optical tweezers and dielectrophoretic (DEP)-based devices have been used to actuate particle motion. In particular, optoelectronic tweezers (OETs) have emerged as useful tools in moving biological samples, as the environment of the sample can be maintained within physiological acceptable limits that do not compromise the sample being studied. In a prior art OET device, an electric field is created in the vicinity of the particle being manipulated. The particle is typically confined between two parallel surfaces. The electric field has a component that is parallel to these surfaces and a component that is perpendicular to these surfaces. Motion of a particle parallel to one of these surfaces will be referred to as lateral motion in the following discussion, and motion of a particle perpendicular to these surfaces will be referred to as vertical motion.
[0004] The dielectric nature of the particle causes the particle to move in the direction of the gradient of the electric field strength. The field typically creates a potential well as a function of lateral position. The particle moves to the minimum energy point in the well. Hence, to move a particle from its current location to the next desired location, the field is altered such that the minimum of the potential well is moved to a location that is adjacent to the current location. The particle then experiences a lateral dielectrophoretic force that causes the particle to move to the new location. The particle also experiences a vertical dielectrophoretic force that causes the particle to move toward one of the surfaces.
[0005] Prior art OET devices have a limited ability to control the shape of the electric field in the vicinity of the particle. As a result, the magnitude of the lateral component of the dielectrophoretic force that is used to move a particle varies significantly with the vertical position of the particle relative to the parallel surfaces. The control system must wait until a particle that is being moved has had time to move to the current well location before altering the location of the potential well. As a result, the maximum rate at which a particle is moved along a desired path is limited to the rate of motion at the locations corresponding to the weakest lateral dielectrophoretic force component.
SUMMARY OF THE INVENTION
[0006] The present invention includes an apparatus for controlling the motion of a particle and a method for using the same. The apparatus includes a channel containing liquid between first and second electrodes. The apparatus also includes an array of variable impedance elements, each variable impedance element connecting the first electrode to a corresponding location in the channel by a path having an average impedance that is continuously variable between first and second impedances when averaged over an update time interval. A controller sets the average impedance of each of the variable impedance elements such that a particle in the channel moves in a predetermined direction when voltage is applied between the first and second electrodes. At least one of the variable impedance elements has an average impedance that is intermediate between the first and second impedances.
[0007] In one aspect of the invention, each of the variable impedance elements includes a switchable photoconductive element having an impedance equal to the first impedance if the switchable photoconductive element is not illuminated with light and an impedance equal to the second impedance if the switchable photoconductive element is illuminated with light. The apparatus also includes an optical display that projects an image onto the array of variable impedance elements. In one embodiment, the switchable photoconductive elements include a layer of photoconductive material that connects the channel to the first electrode. In another embodiment, the switchable photoconductive elements comprise a phototransistor.
[0008] In another aspect of the invention, the controller sets the average impedance of a first one of the variable impedance elements to a first value and sets the average impedance of a second one of the variable impedance elements to a second value. The first one of the variable impedance elements is adjacent to the second one of the variable impedance elements, and the first value is different from the second value. In one embodiment, both the first and second values are intermediate between the first and second impedances.
[0009] In yet another aspect of the invention, one of the variable impedance elements has an impedance equal to the first impedance during a first part of the update time interval and an impedance equal to the second impedance during a second part of the update time interval, the first part and the second part are set to provide the average impedance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 illustrates the manner in which a prior art OET device generates an electric field that is used to manipulate a particle.
[0011] FIG. 2 illustrates the potential difference between surface 18 and the second electrode as a function of lateral position in a region around a spot that is illuminated.
[0012] FIG. 3 illustrates such a continuously varying potential.
[0013] FIG. 4 is a schematic illustration of an OET device that utilizes phototransistors in place of the photoconductive layer described above.
[0014] FIG. 5 illustrates an embodiment of a particle manipulation device according to one embodiment of the present invention.
[0015] FIGS. 6A and 6B illustrate the operation of a micro-mirror device.
[0016] FIG. 7 illustrates a particle manipulation device according to an embodiment of the present invention that utilizes an LCD display.
[0017] FIG. 8 illustrates a particle motion device according to another embodiment of the present invention in which a direct contact display arrangement is utilized.
DETAILED DESCRIPTION
[0018] The manner in which the present invention provides its advantages can be more easily understood with reference to FIG. 1 , which illustrates the manner in which a prior art OET device generates an electric field that is used to manipulate a particle. OET device 10 includes a first electrode 12 and a second electrode 14 having a potential applied therebetween by AC source 13 . Electrode 12 is a transparent electrode. In some embodiments, electrode 14 is also a transparent electrode to allow the contents of the channel between the electrodes to be viewed using a suitable optical system. The channel can be a two-dimensional channel or a one-dimensional channel.
[0019] A photoconductive layer 15 is placed adjacent to first electrode 12 and prevents the applied voltage between electrodes 12 and 14 from reaching surface 18 of photoconductive layer 15 . At locations that are illuminated such as location 21 , surface 18 is connected to electrode 12 and becomes a counter electrode to second electrode 14 . The resulting electric field lines are shown at 19 . A particle 11 that is suspended between first electrode 12 and second electrode 14 experiences a force that is directed along the gradient of the electric field strength at that location. That force has a lateral component 16 and a vertical component 17 . Lateral component 16 causes particle 11 to move until particle 11 is at field line 22 . The magnitude of the lateral component depends on the distance, Z, of the particle from surface 18 . Particles that are closer to surface 18 experience a significantly higher lateral field component than particles that are closer to second electrode 14 . Hence, a particle that is closer to second electrode 14 takes longer to reach a location on field line 22 than one that is closer to surface 18 .
[0020] The use of an AC source ensures that charged particles will not have a net movement toward one of the electrodes, since the vertical forces on the particle reverse with each cycle of the AC source 13 , and hence, the vertical location of the particle oscillates about some equilibrium location.
[0021] At any given time, there is some potential difference between the first and second electrodes and that potential difference appears across the space between the two plates at those locations at which the photoconducting layer is illuminated. Refer now to FIG. 2 , which illustrates the potential difference between surface 18 and the second electrode as a function of lateral position in a region around a spot that is illuminated. To simplify the discussion, the lateral position of the center of the spot is chosen to be at x=0. This is also the equilibrium location to which a particle that is within the field generated by this potential will move. It should be noted that while the size of the conducting spot on surface 18 can be changed, the voltage within the conducting spot remains constant as a function of position in the spot. This constraint results in the undesirable variation in the lateral dielectrophoretic force discussed above.
[0022] The present invention is based on the observation that the electric field shape could be altered to provide a relatively larger lateral dielectric force and a relatively smaller vertical dielectrophoretic force if the potential as a function of lateral position on surface 18 could be varied. Refer now to FIG. 3 , which illustrates such a continuously varying potential. In the example shown in FIG. 3 , the potential difference satisfies the relationship:
[0000] V ( x )= x 2 for x=[− 10,10] and
[0000] V ( x )=0 otherwise (1)
[0000] Here, x=0 is also the desired position of the particle after the particle moves. It can be shown that the lateral dielectrophoretic force can be made substantially larger than the vertical dielectrophoretic force for the voltage distribution of FIG. 3 , whereas the reverse is true for the voltage distribution of FIG. 2 .
[0023] The manner in which this type of voltage pattern can be generated on the surface of the channel through which the particles move can be more easily understood with reference to FIG. 4 , which is a schematic illustration of an OET device that utilizes phototransistors in place of the photoconductive layer described above. In OET device 40 , the layer of photoconductive material discussed above with respect to OET device 10 is replaced by an array of phototransistors that are surrounded by insulating regions. A typical phototransistor is labeled at 41 , and a typical surrounding insulating region is labeled at 42 . The top surface of each of the phototransistors is connected to a conducting pad such as pad 43 . When a particular phototransistor, such as phototransistor 47 , is illumined with a light beam 46 , the pad connected to that phototransistor is connected to electrode 45 . The array of phototransistors is preferred in OET devices in which the medium in channel 50 has a high conductivity. In such cases, the impedance between the channel and electrode 45 needs to be less than the impedance between electrode 44 and pad 43 when phototransistor 47 is illuminated. The phototransistors provide a larger impedance variation than the photoconductive layer such as that described with reference to FIG. 1 .
[0024] To achieve the voltage patterns shown in Eq. (1), a potential other than that achieved by switching a pad between two fixed voltages is required. That is, the particle must experience an electric field that would be created by an “analog” potential on the pads in the vicinity of the particle. Since adjacent pads need to have different potentials, the potential cannot be generated merely by changing the amplitude of the signal from voltage source 49 .
[0025] To simplify the following discussion, denote the peak potential on the pads when a phototransistor is fully conducting by V max and the potential on the pads when the phototransistor is non-conducting by V min . As noted above, the applied potentials are typically AC signals, and hence, V min and V max refer to the maximum amplitude of the AC signal. To achieve the desired potential pattern, each pad in the vicinity of a particle must exhibit an AC potential that has an amplitude between V max and V min . Such a potential will be referred to as an “intermediate” potential in the following discussion. If a DC potential is applied, the DC potential has an average potential between V max and V min . To simplify the following discussion, V max and V min will be used to denote the maximum and minimum amplitudes of the AC voltage, respectively, when an AC signal is used unless the context indicates otherwise.
[0026] A particle is moved within channel 50 by setting a potential pattern and waiting for a time that will be referred to as the “update time interval”. The update time interval is chosen to be sufficient for the particles to move to a new location at which a different potential pattern is needed to continue the motion of the particle in the desired direction. At the end of the update time interval, the potential pattern is updated to reflect the new position of the particle and the dielectrophoretic force needed to continue the particle's motion in the desired direction. Update times intervals are typically of the order of 100 msec to 1 second. In the prior art systems, the potential pattern is held constant for the entire update time interval, and each pad has an AC voltage that has a maximum amplitude equal to either V max or V min .
[0027] In one aspect of the present invention, the slow response of the particle to a change in potential on a pad is utilized to achieve the desired potential pattern. As will be explained in more detail below, the time needed to change a potential pattern is of the order of 10 microseconds. Consider a case in which the potential on a pad is turned on and off repeatedly during the update time interval. The potential on a pad can be turned on and off much faster than a particle can respond to the change. In effect, the particle averages the changes in potential. As a result, the particle experiences an intermediate effective potential whose magnitude is determined by the fraction of the update time interval the pad is at V max . The fraction of the time in which the pad is at V max will be referred to as the duty factor in the following discussion. The average potential is proportional to the duty factor. In one embodiment, the duty factor is achieved by using a sequence of high frequency pulses having the desired duty factor. In another embodiment, the duty factor is achieved by applying V max to the pad for a fixed period of time and then applying V min for the remainder of the update time interval. It should be noted that the duty factor will, in general, vary for different pads in the vicinity of the particle, so that not all pads have the same duty factor.
[0028] In the above-described embodiments, the potential on each pad is controlled by illuminating the pad with a light source. In general, there are large numbers of particles that are being manipulated in parallel. In one aspect of the invention, the OET device is controlled by projecting an “image” onto the first electrode, which is a transparent electrode. Transparent electrodes are known to one skilled in the art, and hence, will not be discussed in detail here. Refer now to FIG. 5 , which illustrates an embodiment of a particle manipulation device according to one embodiment of the present invention. Particle manipulation device 60 includes an OET device 61 that functions in the manner described above with reference to FIG. 4 or FIG. 1 . An image is projected through the transparent electrode of OET device 61 via an objective lens 62 that images a display 63 onto the photosensitive elements of OET device 61 . As will be discussed in more detail below, in this embodiment, display 63 is a micro-mirror array that is illuminated by a light source 65 . Display 63 is controlled by a controller 64 which determines which mirrors in display 63 reflect light onto OET device 61 .
[0029] Commercially available digital micro-mirror devices are available from companies such as Texas Instruments. The mirror response times are on the order of 10 microseconds. Refer now to FIGS. 6A and 6B , which illustrate the operation of such a micro-mirror device. The micro-mirror device includes an array of mirrors of which mirrors 74 - 76 are typical. Each mirror can be independently adjusted such that the mirror reflects light from light source 72 toward OET device 73 or away from OET device 73 . Each mirror corresponds to a different pad in OET device 73 . In FIG. 6A , mirrors 74 - 76 are all set to reflect light toward OET device 73 , and hence, illuminate the photoconductive elements associated with three corresponding pads in OET device 73 . In FIG. 6B , mirror 75 has been set to reflect light away from OET device 73 , and hence, the photoconductive element associated with the corresponding pad will not be illuminated.
[0030] As the mirrors switch positions, the light from a moving mirror may briefly strike photoconductive elements that are not supposed to be conducting at the time of the mirror switching. This can lead to some noise in the generated electric field in some regions of the channel. Such noise can be avoided by turning off light source 72 briefly during the time that the mirrors are being switched.
[0031] It should be noted that other image generating devices could be used to selectively illuminate the photoconductive elements in the OET devices discussed above. Refer now to FIG. 7 , which illustrates a particle manipulation device according to an embodiment of the present invention that utilizes an LCD display. In particle manipulation device 80 , the micro-mirror array discussed above has been replaced by an LCD display 81 that is illuminated by light source 82 . Alternatively, LCD display 81 could be replaced by an array of LEDs which do not require a separate light source. Organic LEDs are particularly attractive in this regard because of the relatively low cost of displays based on such LEDs.
[0032] The above-described embodiments utilize an array of photoconductive elements and an imaging system to generate the desired voltage pattern on one surface of the channel in which the particles move. However, non-optical methods for generating the voltage patterns can also be utilized. One surface of the channel can be viewed as having an array of conductive pads that can be selectively connected to a common electrode by a circuit that has a variable impedance. In the embodiments discussed above, the variable impedance has essentially two states. The first state has an impedance that is small compared to the impedance of the medium in the channel. The second state has an impedance that is large compared to the impedance of the media in the channel. In the above embodiments, the circuits are addressed optically to cause the circuits to switch impedance states.
[0033] In the embodiments shown in FIG. 7 , LCD display 81 is separated from OET device 61 and a lens is used to image LCD display 81 onto OET device 61 . However, embodiments in which a display comprising an LCD display or an LED display is in direct contact with OET device 61 can also be constructed. The pixel density of organic LED displays is sufficiently high that such direct particle manipulation devices can be used in some applications. In addition, the pixel density of organic LED displays continually improves. Refer now to FIG. 8 , which illustrates a particle motion device according to another embodiment of the present invention in which a direct contact display arrangement is utilized. Particle motion device 90 includes an OET device 91 in which the photoconductive elements are near the surface of the bottom side of the OET device. An LED display 92 is positioned such that each LED illuminates a corresponding one of the photoconductive elements in OET device 91 . To prevent cross-talk, a channel plate 93 can optionally be inserted between LED display 92 and OET device 91 to collimate the light from LED display 92 . Controller 94 can be part of LED display 92 or a separate controller that updates the controller in LED display 92 . This type of embodiment provides two advantages. First, the elimination of the optical system that imaged the display on the OET reduces the cost and complexity of the particle motion device. Second, organic LED displays are mass produced as inexpensive display components, which further reduces the system cost.
[0034] However, embodiments that utilize variable impedance elements that are addressed electrically can also be utilized. Arrays of TFT transistors are utilized in many optical displays to control a corresponding array of LEDs or LCD elements. The TFT transistors in the array can be addressed individually and can have a variable impedance that is continuously variable between two limits. Each pad in the channel can be connected to the first electrode via one of these TFT transistors. If used as a switch for switching between two impedance levels as discussed above, the transistors can be turned on and off with the appropriate duty cycle to simulate an intermediate potential across the channel. The circuit element can be viewed as having an average impedance that is the intermediate impedance of the desired value.
[0035] However, by utilizing the continuously variable impedance of the transistors, an intermediate voltage can be achieved without the need for switching the transistors back and forth with the corresponding duty factor. Such embodiments also have the advantage of only requiring that a transistor be addressed when the impedance level of that transistor is changed, since the driving circuits can include a storage element that maintains the impedance at the desired level when the transistor is not being addressed. An example of a TFT transistor array that operates an array of organic LEDs can be found in U.S. Pat. No. 6,965,361, which is hereby incorporated by reference. Arrays of variable impedance elements can also be constructed from other types of semiconductor elements including EEPROM memory cells and ferroelectric FETs.
[0036] In the above-described embodiments, the potential between the first and second electrodes is an AC potential with an average voltage of zero. As noted above, this ensures that particles that have a net charge are not moved to one or the other of the electrodes. However, in some cases, it can be advantageous to include a non-zero DC component to the potential. First, consider the case in which the particles have no net charge. These particles move in the electric field because of the dipole moment of the particles. The particles are attracted to the region of maximum electric field strength. Since the region of absolute maximum field strength will be at a pad on the edge of the channel, the particles will move in a direction that has both a horizontal and vertical component. Since the direction of the AC field does not alter the point of maximum field strength, the particles will accumulate on the pad. To move the particles horizontally, it is advantageous to move the particles off of the pad prior to applying a potential pattern to a neighboring set of pads. This can be accomplished by interrupting the electric field, i.e., turning the potential “off” on the pad at which the particles have accumulated and allowing Brownian motion to re-suspend the particles. However, this increases the time needed to move the particles of interest from one location to another.
[0037] If the particles also have a net charge, a DC component added to the AC field can be used to counteract the vertical motion of the particles that results from the dielectrophoretic attractive forces. The magnitude of the DC component needed to prevent the particles from accumulating on a pad also provides information about the particle. In particular, different types of particles can, in principle, be identified based on this DC component.
[0038] The rate at which particles move in the extended electric fields provided by the present invention can also be used to separate different particles based on their speed of motion in the extended electric field. Consider a heterogeneous population of particles having different dielectric constants that have been trapped over one of the pads. If the potential pattern is now altered so that the electric field causes particles to move laterally toward a new maximum field strength position, particles having different dielectric constants will move toward the new maximum field strength location at different velocities. If the electric field generated by the potential pattern has a sufficient lateral extent, the particles will be separated spatially by an amount sufficient to identify different classes of particles before the potential pattern must be moved to keep the particles moving or the particles all finally reach the new position of maximum absolute field strength. The present invention allows such an extended electric field to be generated. Any pattern of electrode effective voltages that yields a monotonically increasing or decreasing electric field strength in the lateral (horizontal) direction would suffice to allow particle separations, as described above, to occur. In one aspect of the invention, the lateral extent of the region of monotonically increasing or decreasing electric field strength is greater than 10 times the diameter of the particles being separated, although much longer lateral extents can be envisioned for separating particles that have very similar dielectric constants.
[0039] The above-described embodiments of the present invention have been provided to illustrate various aspects of the invention. However, it is to be understood that different aspects of the present invention that are shown in different specific embodiments can be combined to provide other embodiments of the present invention. In addition, various modifications to the present invention will become apparent from the foregoing description and accompanying drawings. Accordingly, the present invention is to be limited solely by the scope of the following claims.
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An apparatus for controlling the motion of a particle and a method for using the same are disclosed. The apparatus includes a channel containing liquid between first and second electrodes. The apparatus also includes an array of variable impedance elements, each variable impedance element connecting the first electrode to a corresponding location in the channel by a path having an average impedance that is continuously variable between first and second impedances when averaged over an update time interval. A controller sets the average impedance of each of the variable impedance elements such that a particle in the channel moves in a predetermined direction when voltage is applied between the first and second electrodes. At least one of the variable impedance elements has an average impedance that is intermediate between the first and second impedances.
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FIELD AND BACKGROUND OF THE INVENTION
This invention relates in general to welding and in particular to a new and useful process and device for a reciprocal guidance of workpieces and tools that move relative to one another particularly for effecting rolling seam welding.
German patent disclosure No. 29 28 620 discloses a process and a device for guiding a workpiece on a rolling seam welding machine, whereby the workpiece is guided and moved with respect to the rolling seam welding machine on a pre-set path by means of a joint arrangement and a slot link. Conveyance is accomplished with this device entirely by means of the two driven contact rollers frictionally engaged with the workpiece that pull the workpiece along with the joint arrangement. It keeps to the rolling seam path thanks to monitoring by an optical sensor on the link that moves along with the joint arrangement. In order to correct deviations from the path, a special rotary drive is provided on the joint arrangement that rotates a pivoting holding trough in which the workpiece is seated counter to the direction of deviation.
The prior art device has the disadvantage that it is not well suited for components of large dimensions and heavy weight. Furthermore, a costly auxiliary device is required to control and correct deviations from the path, a device which must be changed, moreover, when the type or workpiece is changed.
SUMMARY OF THE INVENTION
The present invention provides a device and method for guiding even bulky and heavy workpieces and makes the re-setting work easier.
The invention process and apparatus allows for many variants. For one thing, it does not matter whether the workpiece is guided and moved with respect to the tool or the tool with respect to the workpiece. This relative motion can be achieved, furthermore, in addition to an absolute motion of both parts.
Any deviations from the preset rolling seam path can be detected by means of a speed differential, which may be determined easily either directly or indirectly. The process involves monitoring as primary data the relative relationship of the two speeds to one another and not a possible deviation from an absolute norm. Absolute value control can, of course, be applied secondarily. The correction of any deviations from the path is accomplished simply without auxiliary rotary drives by equalizing the two speeds with short-term compensation of the incurred differential. In this process it is basically unimportant from which drive the difference originated. To make the correction, either the contact roller drive or the guide drive can be readjusted.
According to the invention, the process and corresponding devices are suitable not only for rolling seam welding machines, but also for other tools or machine tools where the driven tool effects a conveyance of the workpiece.
The synchronization of the conveyor speeds can be monitored by a different method. For one thing, it is possible to read the guide speed and the roller conveyor speed directly by means of speed sensors and compare them. A particularly easy and precise method of monitoring, which is furthermore independent of the size and shape of the moved part, can be achieved with the use of a displacement sensor. It detects a path deviation as a motion or torque of one of the two parts around its mounting. This is preferably done on the moved part, but can be applied as well to the part at rest relative thereto.
The process according to the invention and corresponding device permit the tracking of rolling weld seams that are as complicated and three-dimensional as desired. This is also true for flanges or rolling weld seams twisted around the direction of the flange extension. It is also an advantage that it can quickly correct all path deviations regardless of whether they are caused by faulty gripping, by speed differences or by other factors.
The solution according to the invention also permits secure seam tracking on curves, not allowing slippage between the contact rollers and the workpiece to affect the course of the seam. This also improves the quality of the weld seam, in that outside influences, such as partial material changes, increases in temperature and the like, are compensated for.
To guide the moving part, preferably the workpiece, it is recommended that a continuous path control manipulatng device, preferably a multi-axis industrial robot, be used.
The path control is thus accomplished merely by means of a program, which can be changed easily when there is a change of workpiece. A continuous path industrial robot can also guide the workpiece back and forth.
It is recommended that the displacement sensor be positioned on the mounting bracket of the manipulator and that the measuring signals be fed into the controls of the manipulator to readjust guide speed. This is particularly advantageous when workpieces with curved rolling seam paths are to be welded. In this situation, it is particularly recommended that the mounting bracket and the displacement sensor be so positioned with respect to the workpiece that they are roughly the same distance from all radial centers of the curbed rolling seam path. In this way, guide speeds that are different and too high at the mounting bracket are avoided.
In order to work on pieces whose shapes do not permit such an arrangement, it is recommended that the mounting bracket and the displacement sensor be connected adjustably along one or more extra axes with the workpiece or its clamping device. The displacement sensor, however, may also be firmly connected to the clamping device and be moved along with the clamping device in the adjustment with respect to the mounting bracket. Because of the opportunity for adjustment, the distances to the radial centers can be changed, preferably shortened, and limit the guide speeds conveyed via the mounting bracket of the manipulator.
Differences between the conveyor speed of the contact rollers and the guide speed of the workpiece at the clamping point between the contact rollers or a deviation induced by other factors of the contact rollers from the rolling seam path lead to faulty gripping or turning of the workpiece around the mounting bracket of the manipulator.
In consequence, the displacement sensor is designed differently. In a preferred embodiment a torque sensor is provided that has a high sensitivity and can measure the torque incurred in terms of the extent and direction. Its sensitivity can be further increased by enlarging the measurement basis by means of extension arms. In the simple embodiment shown, the rolling seam path runs in one plane so that only torque around the normal axis of the plane needs to be detected. For complicated rolling seam paths, correspondingly more expensive, multi-dimensional torque sensors are needed, capable of measuring force and torque in up to six axes.
Accordingly it is an object of the invention to provide a device for regulating the movement of a workpiece to effect the welding thereof and which comprises a movable tool which is engageable with the workpiece for moving the workpiece and for effecting the welding along a continuous welding seam and which includes a manipulator which is engageable with the workpiece for employing a motion in a similar direction to that imparted by the movable tool and which includes a sensor connected between the manipulator and the movable tool for sensing any variation of movement between them and which acts upon one of the movable tools or the manipulator for adjusting the speed correspondingly.
A further object of the invention is to provide a process of regulating movement of a workpiece to effect the welding thereof and using a manipulator to move the workpiece and using a tool that engages the workpiece to weld it and to move it which comprises sensing the relative movement of the drive of the workpiece by the tool and the drive of the workpiece by the manipulator and acting on at least one of the drives for adjusting the speed depending upon the sensing.
A further object of the invention is to provide a device for manipulating a tool for the purpose of welding it which is simple in design, rugged in construction and economical to manufacture.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which preferred embodiments of the invention are illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a side elevational view of a rolling seam welding machine and a workpiece guided by means of a manipulating device;
FIG. 2 is a bottom plan view of the workpiece with clamping means, seen in the direction indicated by the arrow II in FIG. 1;
FIGS. 3 and 4 are enlarged partial side elevational views showing the displacement sensor of FIG. 1 and a possible alternative for the torque sensor;
FIG. 5 is a basic wiring diagram for the control circuit for the guidance;
FIG. 6 is a view similar to FIG. 3 but including a mounting bracket with an extra adjustment device; and
FIG. 7 is a view of the workpiece as in FIG. 2 but with an adjustment device pursuant to FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings in particular the invention embodied therein comprises a device for an apparatus for regulating the movement of a workpiece 2 to effect the welding thereof around a continuous seam 11 to join mating flanges of workpiece parts having a continuous encircling flange 10. The movable tool comprising a pair of rotating rollers 3. Rollers 3 arranged in opposition and engage the workpiece for other sides and effect the welding of the workpiece parts as well as a movement which is continuous along a welding seam. In addition to the motion imparted through the action of movable tool 3, there is a manipulator 4 which engages the workpiece from imparting a motion in a similar direction to the imparting of a motion of the workpiece by the two operating roller members 3 of the tool. In accordance with the invention, sensor means 6 are connected between the tool 3 and the manipulator 4 acting on the workpiece 2 to sense any variation of movement imparted by either the tool 3 or the manipulator 4.
Sensor means 6 are connected in a circuit as indicated in FIG. 5 through a control 9 and a connecting circuit to act upon the manipulator 4 and/or the drive for the tool so as to adjust the movement imparted to the workpiece so as to provide a corresponding motion inputs to the workpiece 2.
FIG. 1 shows a stationary rolling seam welding machine 1 with two contact rollers 3 installable opposite one another. The rollers 3 being driven separately or jointly by a motor, (not shown). The workpiece 2 in the example shown is a tank or the like whose two halves were previously tacked on an encircling flange 10 and are now to be welded in the rolling seam welding machine 1 see FIG. 2. The workpiece 2 is fastened to a clamping device 13, which is connected through a displacement sensor 6 with the mounting bracket 5 of a manipulating device 4, in this instance a multi-axis industrial robot. The industrial robot 4 is controlled in a continuous path represented by a program in the control unit 9. It is thus possible to dispense with a sot link, limit stops or the like.
During the welding process, the encircling flange 10 is held friction tight between the two contact rollers 3, which thus advance the workpiece 2 in the direction of the arrow 30, see FIG. 2. The rolling seam welding process then proceeds concentrically along the rolling seam pathall running the length of the flange 10. The workpiece 2 is guided and driven in this process by the industrial robot 4. The direction of motion and the guide speed are determined by the path control unit, which as the course of the rolling seam path 11 programmed into it. The industrial robot 4 thus guides the workpiece 2 in a straight line through the contact rollers 3 on the long sides of the flange 10 and turns it at the corners or curved portions of the flange, so that both conveyance directions always coincide. The continuous path control is so coordinated with the rolling seam welding machine 1 that the conveyor speed with which the flange 10 is moved through the contact rollers 3 is exactly the same as the conveyor speed of the contact rollers 3.
Due to wear of the contact rollers 3, slippage, irregularities in the flange 10 or other circumstances, a difference may arise between the guide speed of the manipulator 4 and the conveyor speed of the contact rollers 3. If the frictional engagement between contact rollers 3 and flange 10 is maintained, this leads to torque around the holding bracket 5, distanced from the clamping point, manifested in faulty gripping or a deviant motion of the workpiece 2. In both cases, the result is a deviation of the contact rollers 3 from the preset rolling seam path 11. This is particularly critical in the curved areas of the flange 10. Torque also occurs even when conveyor speeds are the same if due to imprecision in the path control or other factors the contact rollers 3 deviate from the rolling seam path 11.
A similar mismatch in conveyor forces, resulting in torque as indicated above, also ensues when there is slippage in the clamping point between the contact rollers 3 and flange 10. This can also have a negative impact on weld quality and adherence to the rolling seam path -1.
As FIG. 2 shows, the workpiece 2 is held by a clamping device 13. The clamping device is connected via a displacement sensor 6 with the mounting bracket 5 of the industrial robot 4. The mounting bracket 5 in this instance is the rotary take-off end of the industrial robot 4, known as the robot's hand. As FIGS. 1 and 2 show, the longitudinal axes of the mounting bracket 5 and the displacement sensor 6 coincide, and they are so connected at a distance from the encircling flange 10 with the clamping device 13 that they are at an equal distance from all the radial centers 12 of the curved portions of the flange 10. Any torque around the axis of the mounting bracket 5 introduced via the clamping device 13 will be detected in terms of extent and direction by the displacment sensor 6.
The displacement sensor 6 sends this measurement signal over the circuit to be described below and shown in FIG. 5 to the control unit 9 of the industrial robot 4. The extent and direction of the torque constitute analog values for the extent and direction of the path deviation or the difference in conveyor speeds and conveyor forces. The control unit 9 compensates for this differential in conveyor speeds or forces by overlaying the continuous path control and increasing or decreasing the guide speed. The guide direction programmed into the continuous path control is maintained in the process. During the readjustment of the guide speed, a certain overcompensation occurs which temporarily establishes an opposing force couple or turning moment. This has the result that the path deviation is not only compensated but even retraced. The contact rollers 3 thus wander in an arc back to the preset rolling seam path 11. When they reach that position, the torque disappears and the workpiece 2 continues on with the continuous path control exercising its normal function.
In the example shown in FIG. 3, the sensor comprises a cylindrical tube in the shell of which are positioned recesses 16 leaving vertical, flexible bars 15 between them. On the bars 15 are positioned strain gauge strips 14 in a conventional fashion. Torque conveyed via the clamping device 13 twists the tube 7 of the torque sensor 8, whereupon the bars 15 are bent in accordance with the force and direction of that torsion.
FIG. 4 shows an alternative design for the torque sensor 6. The clamping device 13 and the mounting bracket 5 are mounted axially on one another, but can turn counter to one another around the longitudinal axis of the mounting bracket. In this arrangement, there are positioned on the clamping device 13 and the mounting bracket 5 two radially projecting extensions 8 maintained at a distance from one another but covering the same area and connected on their ends by flexible bars 15 with strain gauge strips 14. By increasing the distance of the bars 15 from the axis of torsion, measuring sensitivity is increased.
FIGS. 6 and 7 show an adjustment device with which the distance of the mounting bracket 5 from the radial centers 12 can be changed to produce different effects. An adjustment capability of this kind is particularly recommended for workpieces that are very long or complicated in shape. The larger the distance between centers, the higher the rotating speed that must be conveyed to the mounting bracket 5 in order to pivot the workpiece at the clamping point of the flange 10 with the requisite conveyor speed. This circumstance also causes problems with acceleration and braking. By means of the adjustment device, permitting a change of position with respect to one or more axes, those distances can be shortened.
In the embodiment shown, the clamping device 13 can move with respect to one axis in a guide frame 20 and has its position changed with respect to the mounting bracket 5 and the displacement sensor 6 by means of an adjusting drive 21. A guide frame 20 is rigidly connected on a side with the displacement sensor 6 and conveys to the sensor the torque transmitted from the clamping device 13. The adjusting drive 21 is control coupled with the continuous path control and consists preferably of an electrical servomotor with a displacement indicator and a drive spindle.
Pursuant to FIG. 7, for work on the straight segments of the flange 10 the mounting bracket 5 and the displacement indicator 6 are located in the center position of the adjustment device, where the straight lines connecting the radial centers 12 intersect. Before the curves on the flange are reached, the adjusting drive 21 moves the clamping device 13 with the workpiece 2, whereupon the mounting bracket 5 with the displacement sensor 6 ends up in the position indicated with dash-dotted lines with respect to the workpiece 2, in which position the distance to the closer radial centers 12 is markedly reduced. The adjusting motion is controlled by the continuous path control and compensated with the guide motion by the industrial robot 4, so that the guide speed occurring at the clamping point is not altered by the adjustment. For work on the long, straight segments of the flange, the clamping device 13 is moved back to the center position and subsequently into the other outer position.
Variations on the embodiment shown may be introduced, in that for purposes of multi-axis adjustment a guide frame 20 designed as a compound slide rest or the like can be installed with a corresponding adjusting drive 21. As another instance, the displacement sensor 6 may be fastened to the clamping device 13 and be movably mounted itself in the guide frame 20. It would then be moved, too, during adjustment.
FIG. 5 shows the basic wiring diagram for path readjustment. The torque sensor with strain gauge strips 14 will detect torque that occurs around the longitudinal axis of the mounting bracket 5 and measure it in terms of extent and direction. The measuring circuit used operates at a high cycle rate that allows it to detect torque even before the contact rollers 3 have actually deviated from the rolling seam path 11. The measurement signals from the strain gauge strips 14 installed different directions are conveyed to the bridge input 17, there evaluated and converted into a signal representing the torque in terms of extent and direction. This signal is transmitted to the control unit 9 of the manipulator 4 via an adapting circuit 18 and processed in a program with overlay of path control. The guide speed is increased or reduced for as long as the torque sensor 7 reports the existence of torque. Via a balancing line 19 and the adapting circuit 18, a null-balance procedure can be operated on the torque sensor 7 before a new workpiece 2 is fed into the rolling seam welding machine 1.
While specific embodiments of the invention have been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.
List of Parts
(1) Tool, rolling seam welding machine, part
(2) Workpiece, part
(3) Contact roller
(4) Manipulator, industrial robot
(5) Mounting bracket
(6) Displacement sensor
(7) Torque sensor
(8) Extension
(9) Control unit
(10) Flange
(11) Rolling seam, rolling seam path
(12) Radial center
(13) Clamping device
(14) Strain gauge strip
(15) Bar
(16) Recess
(17) Bridge input
(18) Adapting circuit
(19) Balance line
(20) Guide frame
(21) Adjusting drive
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The invention relates to a process for guiding workpieces on a rolling seam welding machine or vice versa. In the process the relatively moved part is driven via its guide means of a continuous path manipulating device in an extra conveyor motion in the same direction and with the same speed as a tool-caused conveyor motion. The two conveyor motions are monitored for synchronicity by a displacement sensor that is connected for control purposes with a control unit of the manipulating device. When a difference occurs between the two conveyor speeds, manifested by the turning of the moved part around the displacement sensor, one of the two conveyor speeds is readjusted, with short-term over-compensation of the difference.
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BACKGROUND OF THE INVENTION
The present invention relates to injection molding machines and to an improved clamp mechanism for use therein.
Injection molding machines having hydraulically actuated and clamped platens are known in the art. Typically, these machines work on the principle of two separate hydraulic circuits, one to open and close the clamp and the second to generate the clamping force between the closed platens.
Some prior art machines employ a system wherein a column attached to a moving platen is blocked against the clamp piston by shutters. U.S. Pat. Nos. 4,017,236 to Penkman and 4,230,442 to Rees illustrate such a system. A gripper bushing system for blocking the column against the clamp piston is shown in co-pending U.S. patent application Ser. No. 637,814, filed Jan. 7, 1991 to Ing. U.S. Pat. No. 4,867,938 to Schad uses a gripper bushing system to control alternative movement of platens so that the two molding stations in the injection molding system are operated sequentially. Both these systems suffer from disadvantages which affect the performance of the clamp mechanism.
The shutter type of clamp must wait for the shutters to be interposed between the column and clamp piston before the clamp can be energized. This finite period of time during both clamp up and unclamp extends the molding cycle. Typically, shutter speed is about 0.5 seconds in each direction. As a result, approximately 1 second of the molding cycle time is waiting for shutter actuation.
The gripper style of clamping mechanism requires very high oil pressures to be generated in order to actuate the gripping bushing. Typically, 7-8,000 psi oil pressure must be used, whereas all other machine hydraulic requirements are typically 2,200 psi. This higher pressure requirement adds cost to the machine.
Additionally, gripper devices suffer from premature wearing of bushing and column surfaces. Still further, close tolerances between the bushing and the column are required. This adds cost to the clamp construction and to its maintenance.
Very large clamp mechanisms, more than 1,000 tons, mean that clamp blocking shutters or gripping bushings become very large and their disadvantages become more than proportionally counterproductive.
Accordingly, it is an object of the present invention to provide an improved clamping mechanism which reduces cycle time by decreasing clamp wait time.
It is a further object of the present invention to provide a clamping mechanism as above which operates at normal hydraulic pressures and clearances.
It is yet a further object of the present invention to provide a clamping mechanism as above whose capacity can be increased simply and without incurring major cost or cycle penalties.
It is yet a further object of the present invention to provide a clamp mechanism as above which may be used on a wide variety of machines including but not limited to injection molding machines and vertical presses.
Still another object of the present invention is to eliminate the need for an independent mold shutheight adjustment means.
Other objects and advantages of the present invention will become clearer from the following description and drawings.
SUMMARY OF THE INVENTION
The foregoing objects are achieved by the clamp mechanism of the present invention which comprises at least two brake plates mounted to a component such as a moving platen and at least one brake unit for engaging the brake plates. Each brake unit has one or more pairs of brake pad linings forming passageways through which the brake plates may slide and at least one piston-cylinder unit for causing frictional engagement between the brake pad linings and sides of the brake plates. When actuated, the brake unit becomes locked to the brake plates allowing a clamping force generated by a clamping unit to be transmitted to the component via the brake plates.
The brake pad linings employed in the present invention are conventional brake pads such as those used in automobile brake systems. Preferably, they are maintained in position by carrier plates within the brake unit.
The clamp mechanism of the present invention may be employed in a wide variety of machines. For example, it may be employed in TANDEM® injection molding machines where it is desired to selectively open and close adjacent mold portions. It may also be employed in simple molding machines where it is desired to apply a clamping force to a moving platen. Still further, it may be employed in a novel injection molding machine wherein the brake plates replace tiebars.
Further details of the present invention are set out in the following description and drawings wherein like reference numerals depict like elements.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a prior art gripper system employed on a TANDEM® injection molding machine;
FIG. 2 illustrates a TANDEM® injection molding machine employing the improved clamping mechanism of the present invention;
FIG. 3 is a sectional view of a braking unit employed in the clamping mechanism of the present invention;
FIG. 4 is a side view of the braking unit shown in FIGS. 2 and 3;
FIG. 5 is another sectional view of the braking unit shown in FIGS. 2-4;
FIG. 6 is a view in partial cross section of an injection molding machine employing the clamping mechanism of the present invention;
FIG. 7 illustrates the injection molding machine of FIG. 6 in a clamp open position;
FIG. 8 illustrates an injection molding machine having an alternative embodiment of the clamping mechanism of the present invention;
FIG. 9 is a side view of an injection molding machine in partial section showing yet another embodiment of the clamping mechanism of the present invention;
FIG. 10 is a top view of the injection molding machine of FIG. 9;
FIG. 11 is a side view similar to that of FIG. 9 showing the mold in a mold open position; and
FIG. 12 is a top view similar to that of FIG. 10 showing the mold in a mold open position.
DETAILED DESCRIPTION
FIG. 1 illustrates a prior art TANDEM® injection molding machine 10 consisting of a stationary platen 12, a center platen 14 and a moving platen 16. A first mold A is formed between the stationary platen 12 and the center platen 14 by a first set of mold halfs affixed to the platens 12 and 14. A second mold B is formed between the center platen 14 and the moving platen 16 by a second set of mold halfs affixed to the platens 14 and
16. The machine 10 further consists of a clamp block 18 and a plurality of tiebars 20 extending between the clamp block 18 and the stationary platen 12. The center platen 14 and the moving platen 16 slide along the tiebars between a mold open position and a mold closed position.
A clamping unit 22 is provided which consists of a piston and cylinder. The clamping unit 22 acts on one or more columns 24 attached to the moving platen 16 to clamp the molds A and B when they are in a closed position. If desired, multiple clamp units 22 can be employed. Stroke cylinders 26 are provided to cause the moving platen 16 to move with respect to the clamp block 18.
In order to open and close the two molds A and B independently, "grippers" 30 mounted on the moving platen 16 and the stationary platen 12 alternately grip a rod 28 mounted to the center platen 14, such that when the stationary platen gripper is activated and the moving platen gripper is released, the mold B is allowed to open and close while the mold A remains closed. Similarly, when the moving platen gripper is activated and the stationary platen gripper is released, the mold A is allowed to open and close while the mold B remains closed.
FIG. 1 illustrates a prior art gripper method wherein a gripper shaft 28 is fixed to the side of the center platen 14. The gripper shaft extends beyond the length of the clamping unit 22. Gripper bushings 30 mounted on the moving and stationary platens 12 and 16, through which the shaft 28 slides, are used to grip the shaft. The gripper bushings includes bushes (not shown) which deflect inwardly to grip the outer surface of the shaft 28 by frictions. Deflection of the bushes to accomplish their gripping function is caused by the introduction of high pressure fluid. The clearance between the shaft's outer surface and the bushing's inner surface is very small to minimize the amount of deflection of the inner surface. Typically, the clearance is on the order of 0.010" to 0.020". In order to minimize misalignment between the rod and bush, the shaft does not disengage from the bushing at any stroke position of the platens. It has been learned that the re-engagement of a short shaft can cause severe damage to the bushing because of the limited available clearance. Consequently, the shaft which is employed is longer than the clamp unit in order not to disengage from the bushings.
FIG. 2 illustrates a TANDEM® injection molding machine employing the improved clamping mechanism of the present invention. As can be seen from this Figure, all the components of the TANDEM® machine are identical except for the omission of the gripper shaft 28 and the gripper bushings 30. In lieu of these elements, the machine of FIG. 2 has brake plates 32 mounted to the side of the center platen 14 and brake units 34 mounted to the sides of stationary and moving platens 12 and 16 for gripping the brake plates. While it is preferred to mount two brake plates to the side of the center platen, a single plate may be used for low tonnage machines where less surface area for a brake pad is needed.
As can be seen from FIG. 2, the brake plates 32 are spaced apart by a desired distance. Additionally, the brake plates extend in a direction substantially parallel to the axial direction of movement of the moving platen 16 and the center platen 14 as they move between the mold open and closed positions.
FIGS. 3-5 illustrate the construction of the brake units 34. As can be seen from these figures, the brake plates 32 pass through two passageways in each brake unit defined by brake pad linings or wear pads 36. The brake pad linings 36 employed in the unit 34 may be conventional brake pad linings used in conventional braking systems.
Each brake unit 34 include a housing formed by a top frame member 38, a bottom frame member 40, an end plate 42 and a fixed carrier plate 44. The frame members 38 and 40, the end plate 42 and the fixed carrier plate 44 are held together by bolts 50.
Each brake unit further includes movable carrier plates 46 and 48. The fixed carrier plate and the movable carrier plates hold the replaceable brake pad linings 36. The movable carrier plates have extended portions 52 that engage grooves 54 cut in the top and bottom frame members. It should be noted that other fixing means beside those shown herein can be used.
As can be seen from these figures, the carrier plates 44, 46 and 48 define two passageways or slots 56 through which the brake plates 32 can move. In order to facilitate such movement, the carrier plates are constantly urged apart by springs 58 at their corners.
Referring now to FIG. 5, stop blocks 303 and part of frames 38 and 40 control the relaxed position of carrier plate 46 such that it is centered to equalize the clearances between the brake plates 32 and the wear pads 36.
The entire brake unit 34 may be affixed to the sides of the moving platen 16 and the stationary platen 12 using any suitable means known in the art. Preferably, they are keyed 60 and screwed to the platens 12 and 16.
Each brake unit further includes at least one piston-cylinder unit 62 in the end plate 42. High pressure fluid is supplied to the cylinder 64 portion of each unit by a fluid passageway 66. When fluid is introduced into the cylinder, the piston 68 moves in a direction transverse to the axial direction along which the platens 14 and 16 and the attached brake plates 32 move. When activated by high pressure fluid, the piston 68 moves against the movable carrier plate 48 and the movable carrier plate 46. This causes the movable carriers and the brake pad linings to frictionally engage and grip the sides 70 of the brake plates 32. This in turn clamps the movable carriers and the brake plates to the side of the platen 12 or 16, thus locking the platen's position relative to the brake plate. When a moving force is transmitted to the moving platen 16, by stroke cylinders 26, it can be effectively transferred to the molds via the brake plates 32 and the brake units 34.
When one of the molds must remain closed and clamped to retain residual packing pressure therein during the cooling phase of the cycle, the appropriate brake unit is activated to grip the brake plate and keep the mold closed and clamped before the main clamp unit 22 is released. The brake unit thus continues to maintain the clamping force on the mold imparted to it by the main unit 22.
There are numerous advantages to the clamping mechanism of the present invention. For example, the brake plates 32 can completely disengage from the brake units 34 by virtue of the relatively large clearances between the brake plates and the brake pad linings. As a result, much shorter brake plates can be used when compared to the earlier gripper shafts. Furthermore, the gripping force can be greatly increased by using multiple plates and braking pistons. While the disclosed clamping mechanism uses two brake plates and two pistons per brake unit, this could be increased for larger machines to generate higher gripping forces or reduced for smaller machines. The earlier gripper bushing method was severely limited to the amount of gripping force that could be generated. Still further, the replaceable brake pad liner feature of the present invention makes the brake units much more serviceable than the earlier gripper bushings.
Another advantage of the present invention is the elimination of the need to provide means for mold shutheight adjustment.
Referring now to FIGS. 6 and 7, the present invention is shown as it can be applied to the clamp mechanism of a conventional two platen injection molding machine The molding machine 110 has a stationary platen 112 and a moving platen 116. A mold A is formed between the platens 112 and 116 by mold halfs affixed to the platens.
Two or more brake plates 132 are mounted to a rear surface of the moving platen 116. The brake plates 132 pass through slots 115 cut in the main clamp block 118 and slots 117 in the brake housing 119. The brake housing 119 slides along tiebars 120 extending between the clamp block 118 and the stationary platen 112.
The mechanism for clamping the mold in a closed position includes a clamp piston 121 which slides in a clamp cylinder 123. The brake housing 119 is mounted on the end of the clamp piston 121.
As shown in FIG. 6, the brake housing 119 has a plurality of brake pad linings 136 which define the slots 117. Brake pistons 162 are mounted within a cylinder chamber 164 within the brake housing. As before, the pistons 162 move in a direction transverse to the direction of movement of the brake plates 132 and the moving platen 116. When activated, the brake pistons act on the brake linings 136 to grip the sides of the brake plates 132.
Fluid admitted to the space 165 in the brake housing causes all brake pistons to be simultaneously actuated and to grip the brake plates. Fluid is admitted to space 165 through flexible hose(s) 300 from a valve and pump arrangement (not shown). Due to this construction, the piston stroke is very short and the action is very fast. Stroke cylinders 301 mounted on clamp block 118 cause the platen 116 to move. Prior art clamps provided a shutheight adjustment means in order to accommodate different mold heights. This was done by moving the entire clamp block with respect to the base by using powered nuts acting on tiebar threads, or by providing additional travel in the main clamp cylinder. Both methods added cost and complication to the machine.
The instant invention can accommodate various mold shutheights without the need to adjust the clamp block position or provide additional travel to the clamp piston. Since the brake plates 132, can be gripped at any position and the clamp force transmitted through them to the mold, independent shutheight adjusting means are not required.
FIG. 7 shows the clamp in the open position with the brake pistons released and the brake plates free to move past the main clamp cylinder 123. Conventional stroke cylinders for moving the platen 116 between a mold open position and a mold closed position are not shown.
To apply a clamping force to the moving platen 116, the brake pistons are actuated to move against the brake pad linings causing the brake pad linings to grip the side surfaces of the brake plates. Then the clamping piston and cylinder are actuated to transmit the clamping force to the brake housing which in turn transmit it to the moving platen via the gripped brake plates. In this arrangement, the clamping force is directed to the moving platen.
FIG. 8 shows a molding machine 210 similar to that shown in FIGS. 6 and 7. The machine 210 includes a stationary platen 212 and a moving platen 216 which is movable between a mold open position and a mold closed position by a conventional stroke cylinders 302. The machine 210 also includes a clamp block 218, tiebars 220 extending between the clamp block 218 and the stationary platen 212 and a brake housing 219 slidable on said tiebars The clamp block 218 may have a single central passageway through which the brake plates 232 may move.
As shown in FIG. 8, the brake plates 232 are positioned close to the center line C--C of the machine 210. Brake pad linings 236 are positioned within the brake housing 219 and define a number of passageways through which the brake plates can move.
The brake housing 219 further includes fluid actuated brake pistons 262 positioned within cylinders 264. Once again, the brake pistons 262 move in a direction transverse to the direction of movement of the brake plates and the moving platen.
The clamp block 218 is different in that it includes internal clamping cylinders 223 and clamping pistons 221. The clamping pistons each have one end affixed to the brake housing 219. When the main clamping pistons 221 and the clamping cylinders and the brake pistons are each actuated, the clamping pistons and the clamping cylinders act on the housing 219 to transmit the clamping force to the moving platen via the gripped brake plates.
This embodiment is advantageous in that it concentrates the clamping force applied to the moving platen at the center of the platen.
FIGS. 9 through 12 show yet another injection molding machine 310 utilizing the brake clamping mechanism of the present invention. The molding machine includes a stationary platen 312 and a moving platen 314. Both platens are mounted to a machine base 316. A mold A is formed between the platens 312 and 314 by mold halfs 322 and 324. A conventional injection unit 326 is provided for introducing molten plastic material into the mold when the mold is in a closed position. The machine further includes stroke cylinders 330 mounted between the two platens for causing movement of the moving platen 314.
The stationary platen 312 may be fixed to the base 316 using any suitable conventional means known in the art. The moving platen 314 slides on the machine base 316 on hardened ways 340. The hardened ways 340 may be firmed from conventional hardened steel, with bronze wear pads 342 on platen 314. The adjustable wear pads or plates 342 are provided to adjust the parallelism and alignment of the moving platen 314 with respect to the stationary platen 312.
This molding machine differs from those previously disclosed in that it does not have tiebars and a main clamp block. Instead of tiebars, the machine 310 has four brake plates 318 which are fixed to the moving platen 314 and slide through passageways 320 in the stationary platen 312. The passageways 320 have flat ground wear plates 360 mounted therein which facilitates maintenance and make alignment of the platens convenient.
Two brake housings 328 are provided to engage the brake plates 318. The brake housings are positioned on opposite sides of the injection unit. Each brake housing includes at least two pairs of brake pad linings 332 for defining passageways 334 through which the brake plates slide and for gripping the sides of the brake plates. Each brake housing further includes at least two piston-cylinder units 336 for causing said brake pad linings to move into engagement with the brake plates. As before, fluid introduced into the cylinder via a conduit not shown causes the piston to move against the brake pad linings.
Clamping piston-cylinder units 344 are provided in the brake housings 328. Each piston-cylinder unit comprises a cylinder 346 into which fluid can be introduced by conduits not shown and a movable piston 348 having one end attached to the stationary platen 312.
In operation, the brake pistons 338 are actuated so that the brake pad linings grip the sides of the brake plates and thereby lock the housings 328 to the brake plates 318. Thereafter, the clamping piston-cylinder units are actuated. When actuated they act on the stationary platen 312 so as to cause each brake housing to move away from the stationary platen and to cause the mold between the platens to become clamped. In this design, the brake plates 318 are put into tension by this clamping action and accordingly act like tiebars. Unlike the other designs disclosed herein, there is no risk of the brake plates buckling in compression. As a result they do not need to be made as stiff.
It should be noted that the brake plates completely disengage from the brake units and the brake pad linings when the mold is in an open position. This results in the use of shorter brake plates than otherwise would be required if tiebars and gripper bushings were used. This machine is particularly advantageous in that it is shorter than other machines due to the elimination of the main clamp block.
While the present invention has been discussed in the context of injection molding machines, the brake clamp mechanism of the present invention may be used in conjunction with vertical presses and the like which employ clamp mechanisms. It may also be useful to use the present invention in robots and fast moving product handling equipment.
It is apparent that there has been provided in accordance with this invention a brake clamp mechanism which fully satisfies the objects, means and advantages set forth hereinbefore. While the invention has been described in combination with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims.
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The present invention relates to an improved clamping mechanism for use in injection molding machines and similar pieces of equipment where it is desired to apply a clamping force to particular components. The clamping mechanism of the present invention employs at least one spaced apart brake plate mounted to one component and a braking unit for engaging the brake plates. The braking unit has at least one pair of brake pad linings surrounding the brake plates and at least one piston-cylinder unit for causing frictional engagement between the respective brake pad linings and the brake plate(s). When the brake pad linings grip the brake plate(s), the braking unit becomes locked to the components to which the brake plate(s) are attached. The clamping mechanism of the present invention may be employed on simple injection molding machines as well as TANDEM® injection molding machines.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of prior copending application Ser. No. 089,944, filed Oct. 31, 1979, for VERTICALLY COLLAPSING CLOSURE SYSTEM, now U.S. Pat. No. 4,303,117.
BACKGROUND OF THE INVENTION
The referenced patent application discloses a vertically collapsing overhead storable closure consisting of plural rectangular hingedly connecting panel sections and guide means for the collapsing closure between full open or stored and fully closed positions. The closure guide means in the application includes panel mounted roller assemblies, vertical guide rails at each side of the closure, and cam means to cooperate with the guide roller assemblies in the operation of the closure. A counterweight system for the movable closure has its counterweighting effectiveness varied with the position of the components which make up the counterweight to adapt the counterweight to varying forces exerted by the closure during the movement thereof.
The present invention seeks to improve on the collapsing closure in the referenced application in a number of respects. First, the invention provides a means of further reducing the overall height of the installed system through an improvement in guide roller mounting. Second, a more simplified upper guide roller track arrangement of lesser manufacturing cost is provided, along with a similarly improved lower guide track arrangement. The invention includes an embodiment suitable for a commercial or residential movable interior partition, to be used in lieu of current rotational and laterally movable interior partitions which occupy valuable floor space. The invention also provides an embodiment usable as a removable roof for shopping malls, swimming pool enclosures and the like. A very important feature of the invention resides in more energy efficient guide roller assemblies especially for large closures or partitions. More particularly, in the improved guide roller assemblies, the guide roller axis is capable of displacement laterally relative to the roller mounting bracket. This arrangement enables the closure panel sections to remain in a common vertical plane promoting appearance and weather-tightness.
The invention can provide a door that offers a rail and stile exterior facade, while incorporating section insulation and an interior flush surface more compatible architecturally with surrounding interior finishing. Currently, only flush closure sections are insulated while the more popular rail and stile variety possesses no adequate insulation with thicknesses limited to approximately one-quarter inch.
Another major feature of the present invention resides in a more simplified embodiment of a variable counterweight system. Finally, the invention provides as one of its features a unique means for latching the closure in its down or closed position.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing the interior of a collapsing closure system according to the invention.
FIG. 2 is a composite schematic side elevation showing the operational stages of the collapsing closure system.
FIG. 3 is a fragmentary schematic interior elevational view of the closure showing panel section guide roller assemblies.
FIG. 4 is an enlarged elevational view of the collapsing closure corresponding to the position of the closure shown in FIG. 2 (g).
FIG. 5a is a side elevation of an upper guide rail unit.
FIG. 5b is a further side elevation of the upper guide rail, with parts broken away.
FIG. 5c is an end elevation of the upper guide rail.
FIG. 5d is an edge elevation thereof.
FIG. 6a is an elevational view showing the collapsing closure embodied in an interior partition for a residence.
FIG. 6b is a plan view of the same.
FIG. 7 is an enlarged vertical section through the interior partition in the full down position.
FIG. 7a is a similar view showing the partition in an intermediate position.
FIG. 8 is a fragmentary side elevation of a closure panel guide roller mounting assembly common to all but the two lowermost panel sections of the closure and also showing a lifting cable guide sheave.
FIG. 8a is an end elevational view, partly in section, of the elements in FIG. 8.
FIG. 9 is an end elevation of a guide roller mounting assembly for the next-to-lowest panel section.
FIG. 9a is a side elevation thereof.
FIG. 10 is a fragmentary side elevation of a guide roller and lifting cable attachment assembly for the lowermost closure panel.
FIG. 10a is an end elevation thereof.
FIG. 11 is an exterior side elevation of a collapsing closure having a rail and stile exterior facade.
FIG. 11a is a vertical section taken on line 11a--11a of FIG. 11.
FIG. 12 is a fragmentary cross sectional view of a closure counterweight system.
FIG. 13 is a similar view of the counterweight system when the closure is in the full up or opened condition.
FIG. 14 is a similar view of the counterweight system arranged for closure opening.
FIG. 15 is a similar view of the counterweight system in another operational mode.
FIG. 16 is a fragmentary elevational view of a latching and unlatching device for the counterweights' platform.
FIG. 16A is a side elevation of parts shown in FIG. 16.
FIG. 16B is a plan view of parts shown in FIG. 16.
FIG. 17 is an elevational view, partly broken away and partly in section, of the closure, counterweight system and interconnecting cable means.
FIG. 18 is a perspective view showing an embodiment of the collapsing closure suitable for a swimming cool cover, roof or the like.
FIG. 19 is a composite schematic view showing the operational stages of the closure in FIG. 18.
FIG. 20 is a fragmentary cross sectional view showing the lower roller guide rail and associated parts.
FIG. 20a is a similar view of the lower roller guide rail as it accommodates the end rollers of a pair of closure panels.
FIG. 20b is a fragmentary side elevation showing the juncture of components in FIG. 20a with the perimeter wall box beam.
FIG. 21 is a side elevation of a modified form of upper roller guide rail having an interceptor plate to effect roller diversion.
FIG. 21a is a horizontal section taken on line 21a--21a of FIG. 21.
FIG. 21b is a similar section taken on line 21b--21b of FIG. 21.
FIG. 21c is a similar section taken on line 21c--21c of FIG. 21.
FIG. 22 is a fragmentary side elevation of a closure mounted cam follower and associated parts.
FIG. 22a is a fragmentary vertical section taken on line 22a--22a of FIG. 22.
FIG. 22b is a similar section taken on line 22b--22b of FIG. 22.
FIG. 23 is a side elevation of a further modified upper roller guide rail system.
FIG. 23a is a horizontal section taken on line 23a--23a of FIG. 23.
FIG. 24 is a fragmentary vertical section taken through one panel of a rail and stile insulated collapsing closure depicting a feature of the invention.
DETAILED DESCRIPTION
Referring to the drawings in detail and initially referring to diagrams (a) through (g) of FIG. 2, a first major improvements feature of the invention is schematically shown, namely, a substantial decrease in the collapsed height of the closure compared to the closure in the referenced application. Diagram (g) shows the collapsed height of the prior application closure, while diagram (f) shows the substantially reduced collapsed height of the closure herein. In these FIG. 2 diagrams, a vertical wall 40 and overhead interior storage cabinet 41 for the collapsed closure 42 are shown. The numeral 43 designates a vertical closure guide track extending at 43' in the cabinet 41. The numeral 44 designates a diversionary branch guide track extending into the storage cabinet 41.
In diagram (b), it is shown that the collapsing closure 42 comprises a plurality of equal width closure panel sections 45, 46, 47, 48, 49 and 50. These panel sections are equipped at opposite ends with guide rollers 50' which follow the tracks 43, 43' and 44. Except in two instances, the guide rollers 50' have their axes coinciding with the hinge or articulation axes 51 between the panel sections. The next-to-lowermost guide rollers 50' are substantially above the hinge 51 between the two lowermost panel sections 49 and 50 and are preferably on the panel section 49 near its vertical center. The next uppermost guide rollers 50' are on the panel section 47 slightly above the axis of hinge 51 between panel sections 47 and 48. This simple relocation of two pairs of guide rollers compared to the prior application makes possible the substantially reduced collapsed height of the closure 42 shown in diagram (f) of FIG. 2.
Diagram (c) shows the articulated closure 42 beginning to ascend into the storage cabinet 41 with the uppermost rollers 50' following the track section 43'. Diagram (d) shows the next lowermost rollers 50' being diverted onto the branch track 44. Diagram (e) shows the continued collapse of the two uppermost panel sections 45 and 46 and the vertical movement of the next lowermost panel section 47 along track section 43'. In diagram (e), the two sets of guide rollers 50' on panel sections 47 and 49, displaced upwardly from the adjacent hinges 51, have not yet reached the elevation of the cabinet 41.
In diagram (f) showing the fully collapsed state of the improved closure 42, these two displaced sets of rollers 50' have both been diverted to the branch track 44 as shown, resulting in the significantly reduced collapsed height of the closure compared to the prior referenced application. As stated, this is one of the major features of the present invention.
Schematic FIG. 3 showing the interior side of the fully down closure 42 depicts the panel sections 45 through 50, vertical guide tracks 43 and the sets of guide rollers 50' with the next-to-lowermost guide rollers 50' between panel sections 50 and 49 relocated upwardly on panel section 49 and the like guide rollers above panel section 48 relocated slightly upwardly on panel section 47 as described relative to diagram (b) of FIG. 2.
FIG. 4 corresponds to diagram (f) of FIG. 2 and shows in greater detail the geometry involved in the reduced height collapse of closure 42 due to relocation of two pairs of the rollers 50' relative to the adjacent hinge axes 51.
FIGS. 5(a) through 5(d) show another improvement feature, namely, an improved upper roller guide track system. Basically, each upper guide track unit of the system is stamped from sheet metal to form a variable width shallow pan 52 and a curved face roller guide rail section 53. The latter element can be spot welded to the pan 52 just inwardly of a vertical edge flange 54 thereof. Another edge flange 55 rises from the flat shear panel 56 of the pan 52 perpendicular thereto and this latter flange 55 follows the curved diversionary edge portion of the pan-like sheet metal track unit.
The straight edge flange 54 forms a mounting flange for connecting each upper guide track unit to the wall 40. It also serves to support the concave roller guide strip 53. The flange 55 serves to constrain the diverted panel guide rollers in the operation of the closure.
Each upper guide track unit is completed by the attachment thereto of an upper mounting bracket 57, closure lifting cable sheave assembly 58 and a small latch cable sheave, not shown.
FIGS. 6a through 7a show a further embodiment of the invention in the form of a vertical overhead collapsing and storing partition for residential or commercial facilities. As shown in FIG. 6a, ceiling joists 59, roof trusses 60 and ridge beam 61 form the facilities' overhead structure, the floor 62 and floor joists also being shown. Lifting cable means 63 for a collapsing vertical partition 64 are directed over to a variable counterweight system 65 which is concealed in a fixed wall space. An electric motor, not shown, and associated controls may be added in the usual manner. The partition 64 may collapse upwardly into the overhead space above the ceiling joists 59 or may collapse into a supported cabinet 66 similar to the previously-described cabinet 41.
The partition 64 may be constructed identically to the previously-described collapsing closure 42, and possesses a plurality of equal width hingedly connected panel sections 67, 68, 69, 70, 71 and 72 which are guided in their movement by the guide track means described in the prior embodiment of the invention including a vertical track portion 73 and overhead pan-type roller guide tracks 74. The guide rollers of the panel sections 67 through 72 are also positioned as described previously in FIGS. 2, 3 and 4 of the prior embodiment.
As shown in FIG. 6b, a plan view, trim strips 75 are added to conceal each vertical track 73 for the sake of appearance and safety.
FIGS. 7 and 7a show the vertically collapsing partition 64 with the supported storage cabinet option 66. FIG. 7 shows the partition 64 in the full down position while FIG. 7a shows the overhead collapsing and storage mode which may correspond exactly to that described in the prior embodiment of FIG. 2, etc.
FIGS. 8 and 8a are side and end views, respectively, of a roller guide assembly for all panel roller locations except those of the two lowermost panels 49 and 50 or 71 and 72. A bored cylindrical bar 76 has an internal diameter such that the inserted guide roller axle 77 can freely slide but does not allow sufficient vertical displacement of the roller 50'. Unless closure weights are heavy, such relative motion can occur without significant friction if a suitable machinery lubricant is used. Under heavier loads, low friction bearings or bushings may have to be employed. The length and wall thickness of the bar 76 are determined through usual structural considerations. In the case of wood closure panels, the bar 76 is deeply recessed into the panel, FIGS. 8 and 9a, and this doweling effect greatly increases strength. When necessary, a small sheave 78 is applied to accommodate the zigzag arrangement of the usual lifting cable means for the closure inducing panel joint moments. A retainer 79 for the lifting cable on the sheave 78 is preferably provided, as shown. The sheave and retainer are attached to an assembly mounting plate 80 using a headed axle pin 81 welded to the mounting plate 80.
FIGS. 9 and 9a show a similar mounting and guide assembly for the mid-level closure panels. The lifting cable sheaves 78 are absent and the geometry of mounting plate 82 is somewhat changed compared to the mounting plate 80.
FIGS. 10 and 10a show similar guide roller mounting arrangement for the lowermost closure panel 50 or 72 to which the lifting cable means 63 is attached. An angle mounting plate 83 is employed on the lowermost panel section for increased strength. A stranded cable attachment plate 84 and pivot pin 85 for the same are used for the attachment of lifting cable means 63. A lower edge weather seal 86 for the closure is also shown. The position of guide roller axle sleeve 76 or bar relative to mounting plate 83 is a function of the geometry of seal 86 and the desired position of lowermost guide roller 50' relative to the floor.
FIGS. 11 and 11a show another important feature of the invention in which a six panel vertically collapsing closure 87 is embodied in a garage door whose exterior surface, FIG. 11, is of popular rail and stile design.
As shown in FIG. 11a, the interior face 88 of the closure 87 is flush or continuous to match internal surroundings and each articulated closure panel 89, 90, 91, 92, 93 and 94 contains an insulating core 95 of substantial thickness. By virtue of this arrangement, the garage door forms a good thermal barrier while achieving the most popular appearance and other attributes of the invention already described. Customarily, rail and stile doors have panels which are only about one-quarter inch thick without thermal insulation.
FIGS. 12 through 17 show a simplified variable counterweight system for the vertically collapsing closure or partition forming another important aspect of the invention. FIG. 12 shows the counterweight system ready for ascent, necessary to produce closure lowering. The counterweight raceway consists of side tracks 96 and 97 fixed to adjacent studs 98 or the like. A header plate 99 attaches to top members 100 and a lower plate 101 is fixed on a base plate 102.
Weight segments 103 and 104 are of one-piece form and equipped with guide rollers 105 at their opposite sides engaging tracks 96 and 97. The weight segments 103 and 104 are intercepted by projections 106 and 107 at fixed elevations, respectively.
Another weight segment consists of two weight parts 108 and 109. The upper part 108 has guide rollers 110 engaging guide tracks 96 and 97. The weight part 108 is arrested by projections 111. Weight part 109 is arrested by suspension rods 112 that are fixed to the upper weight part 108. The rods 112 and lower weight part 109 are such that the rods extend fully into the latter during all motion phases except the arrested configuration shown in FIG. 12. In this configuration, flanges on the lower ends of rods 112 have been intercepted by the upper surface of lower weight part 109. These flanges are omitted for simplicity. As arrested, the weight part 109 is supported by the rods 112 which in turn are supported by the upper weight part 108, supported by the side projections 111.
A weight segment 113 also serves as the counterweight support platform. FIG. 16 provides further detail of this element. The platform element 113 is connected to each lower corner of the closure by lifting cables 114 and 115, FIG. 16. It is connected to the underlying weight segment 116 by mechanical latches. Weight segment 116 consists of a single piece mass with two sets of guide rollers 117 and 118.
As will be further discussed, the counterweight system commences its ascent and hence the lowering of the closure 42 commences once the weight segment 116 is mechanically unlatched from the support platform 113. It is this action that effectively reduces all upper counterweight mass stages by the mass of the disconnected weight part 116. Hence, this action instantly reconfigures from the door opening geometry to door or closure closing geometry.
Mechanical devices 119 are operated by cable extending to the main external closure latch to cause the disconnect of weight segment 116 from platform element 113. Accordingly, weight segment 116 effectively serves as the latch component holding the closure in the open position. Weight segment 120 serves as a weight part. However, its primary role is as a platform for weight segment 116 and a return means for a cable 121 extending from it to a cable winding drum attached to a small electric motor, not shown. Cables 114 and 115 extend from the closure down through an opening centered in each weight segment 103, 104 and 108 to their points of attachment to the main weight support platform 113. Cable 121 extends from an electric motor, not shown, down through the same weight openings. However, it similarly passes through the platform 113 and the underlying weight component 116 to a center point of attachment with the secondary platform element or weight 120. Rubber bumpers 122 mounted on the lower raceway plate 101 act to terminate counterweight descent. An upper cable sheave assembly 123 is provided to guide the three cables 114, 115 and 121 from the counterweight raceway to their respective termination points.
In FIG. 13, the mechanical devices 19 have been activated, unlatching platform element 113 from weight segment 116. The closure 42 has commenced its descent and hence the counterweight its ascent. Weight segment 116 and secondary support platform 120 remain fixed at the bottom of the raceway. As shown in FIG. 13, the weight segment 104 is next to be added added to the effective traveling counterweight mass.
FIG. 14 shows the counterweight system fully ascended in the raceway and corresponding to the full down position of the closure 42, 87 or the partition 64. The closure has now been mechanically locked down by latches at the bottoms of guide rails 40. The counterweight system is ready for subsequent closure opening by the raising of weight segment 116 and connection thereof to main support platform element 113. Mechanical latches mounted on the latter achieve such connection by engagement with the axles of the upper guide roller set 118. Upon reaching the full down position, the closure contacts a limit switch, not shown, which activates an electric motor. Cable 121 is then wound on a cable drum driven by the motor causing secondary support platform 120 to elevate weight segment 116 the required distance, at which point the connection of segment 116 with platform element 113 occurs. Simultaneously with this connection, weight segment 116 contacts another limit switch, not shown, causing the electric motor to reverse or stop and gear release in order that cable 121 can be retracted. Secondary weight support platform 120 now functions in its other role of insuring full retraction of cable 121.
FIG. 15 illustrates the resulting counterweight configuration now ready to effect closure raising once the lower mechanical closure latches are opened. As the cable retraction plate 120 approaches the full down position, a third limit switch is operated to stop the electric motor preparing it for the subsequent withdrawal of cable 121. In the system shown in FIGS. 12 through 15, the vertical closure can be raised and lowered without application of external energy. Only mechanical unlatching of the closure is necessary to initiate the movement cycle.
In FIGS. 16 through 16b, closure lifting cables 114 and 115 are fixed to platform element 113. Counterweight lift cable 121 freely passes through the provided opening 124, FIG. 16b. Guide roller equipped side brackets 125 are mounted on opposite sides of platform 113 to assure proper platform alignment. The platform guide rollers 126 are supported on brackets 125. Also, pivoting around these axles, are the mechanical latches 127 used to connect the platform assembly to the lower weight segment 116. Springs 128 are mounted on the latches 127 to assure the latter will deviate from the vertical only in response to engagement with the guide roller axles 118 of lower weight segment 116.
FIG. 17 shows the relationship of the described counterweight system to the closure support and guide system. The electric motor equipped with a cable winding drum 129 to retract cable 121 rests on a platform 130 attached to the adjacent upper closure guide track or pan 52. Lifting cable 115 is directed for attachment to the lower left hand corner of the closure via a sheave 131 at the top of the left hand upper guide track 52. Lifting cable 114 passes over an adjoining sheave at the same location and leads to another directional sheave similarly positioned on the right hand upper guide track or pan 52. As shown at 132 in FIG. 17, the overhead collapsing storage cabinet is extended to enclose the electric motor and its drum 129 and counterweight raceway cable directional sheave 123 at the top of the raceway.
Thus far, the present invention has been shown and described as a collapsing vertical closure or partition. FIGS. 18 and 19 show an application of the invention as an inclined roof, swimming pool cover or the like. More particularly, FIG. 18 illustrates a structure for enclosing a residential swimming pool. Vertically collapsing wall panels 133, 134, 135, 136, 137 and 138 according to the previously-described embodiments are shown. An extended cabinet 139 encloses the described upper guide tracks or pans 52 and allows overhead storage of the panels 133 through 138.
A roof structure consists of plural inclined collapsing closures or panels 140, 141 and 142. The intermediate collapsing panel 142 is shown in the partly collapsed state. The previously-described upper guide roller pans 52 are utilized in the inclined roof together with inclined longitudinal guide tracks 143, 144, 145 and 146 constructed like the vertical tracks 40. Springs 147, 148, 149 have been added connecting each pan 52 to an intermediate point along the edge of each uppermost panel section 150 of the plural section roof panels or closures.
The diagrams of FIG. 19 show the operation of the collapsing inclined roof panels. The added springs 147 on the pans 52 accommodate independent collapse of roof panels 140, 141 and 142.
Cross sectional views of guide tracks 143 and 144 are shown in FIGS. 20 and 20a. All roof panels 140, 141 and 142 can be operated by a single counterweight system, or separately by individual counterweight systems. The panels may be opaque or translucent and may be formed of plastics or glass.
Referring to FIG. 19, the intermediate roof panel 142 has been illustrated schematically and employs six equal width collapsing panel sections for simplicity in lieu of eight sections as shown in FIG. 18. Lower diagram (a), FIG. 19, shows roof closure panel 142 fully extended and lying in one inclined plane above support roof joist 151. The tension spring 147 of diagram (a) extends between the transitional portion of pan 52 at the mid-point of the edge of upper panel section 153. In some cases, the weight of the roof panel and its slope may be such that panel collapse and extension can occur in response to gravity and the tensioned lifting cable only. In the case of lesser roof slopes, the spring is necessary to supplemental gravity forces in insuring that the upper panel section 153 is constrained relative to the lower panel sections 154, 155, 156, 157 and 158 so that proper panel collapsing occurs. The spring will also assist in the extension of the roof panel.
Diagram (b) in FIG. 19 shows the initial opening or collapsing of roof panel 142. A lifting force has been applied to lowermost panel section 158 and all articulated sections have commenced movement up the incline. Also, the panel collapse sequence has begun at the articulation axis of panel sections 153 and 154. The spring 147 has assisted the cable means, not shown, in this collapsing action.
Diagram (c) shows the continued collapsing of the roof panel 142 and the force of spring 147 is steadily increasing as panel sections 153 and 154 have completed their rotational phase.
Diagram (d) shows the full open or collapsed panel configuration which is basically the same as in the prior embodiments regarding latches and other mechanical details.
FIG. 20b is a side elevation of the structure in FIG. 20a and of the perimeter cable 139. A weather seal 159 will be thrust against the underside of panel 142 as the latter contacts a weatherstrip projection 160 forcing in turn the insert bar 161 to thrust outwardly from weatherstrip case 162. A facia strip 163 is shown equipped with an opening to permit drainage.
FIG. 21 and FIGS. 21a through 21c show a modified upper roller guide rail in lieu of the guide rail or pan 52, previously described. An alternate means of achieving closure panel section guide roller diversion is made available. More particularly, a curved interceptor plate 164 is added to the lower curved terminal of the roller constraint flange 165. As shown in FIG. 21c, the two elements 164 and 165 are perpendicular and the element 164 is spaced from and parallel to the body portion 166 of the roller guide unit. In other respects, the unit corresponds to the previously-described unit 52.
In FIGS. 22 through 22b, a cam follower 167 is attached to the diversion guide roller mounting plate 168 in a manner which allows the cam follower to coact with the curved interceptor plate 164 to achieve interception and controlled diversion of the closure panel section guide roller 169 to cause proper collapse of the closure hinge joint. The interceptor plate 164 need extend only a limited distance along the roller constraint flange 165, as lateral components of hinge joint forces are sufficient to complete the collapsing or folding action. The interceptor plate 164 is positioned so that its outer projecting flange extends between the guide roller axle 170 and the cam follower 167 without contacting either, FIG. 22b, during their entry into the restricting region of the interceptor plate 164. While the cam follower 167 is within the latter, the projecting flange of interceptor plate 164 is positioned outwardly from the guide roller constraint surface such that the guide roller must slightly rise from the latter in order that the cam follower 167 engage and, hence, be constrained by the projecting flange of the interceptor plate. Additionally, such outward positioning is limited to preclude interference with the guide roller axle 170. The improved guide roller constraint and diversion structure is simple, positive, reliable and economical to manufacture.
In FIGS. 23 and 23a, the upper guide roller tracking units are modified to enable the solid web or plate elements 171 to also serve as the end walls of the overhead storage cabinet 172 for the vertically collapsing closure. To facilitate this, the element 171 is formed rectangular to match the cabinet geometry and straight and curved constraint rails or flanges 173 and 174 are provided to afford the necessary panel section roller guidance and diversion. The flange 174 can be welded to the flat plate or wall 171. A vertical flange 175 is formed integral with the wall 171 to facilitate attachment of the front cabinet panel 172.
In FIG. 24, a feature is shown to prevent twisting of the frame 176 of an insulated rail and stile closure panel due to thermal expansion and contraction of the inner and outer panels 177 and 178. To alleviate this problem, the outer panel 178 has a snug slip fit within mounting grooves 179, with small voids provided by the grooves to allow the necessary relative movement due to thermal contraction or expansion. The inner panel 177 is glued fixedly to the frame 176.
It is to be understood that the forms of the invention herewith shown and described are to be taken as preferred examples of the same, and that various changes in the shape, size and arrangement of parts may be resorted to, without departing from the spirit of the invention or scope of the subjoined claims.
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Vertical and non-vertical collapsing panel closures for various applications are disclosed. The closure has reduced stacking height when collapsed and possesses a more energy efficient panel section guide roller system operating with a more economical and versatile upper and lower guide roller track arrangement. An insulated closure having an interior flush surface and an exterior rail and stile facade is achieved. A more simplified variable dynamic closure counterweighting system is provided.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This is a national of PCT/EP10/005064 filed Aug. 17, 2010 and published in German, which claims the priority of German number 10 2009 037 845.6 filed Aug. 18, 2009, hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to a disposable element comprising at least one first part, in which channel structures are recessed in the surface, and a second part sealingly covering said first part, with the larger part of the first part and/or of the second part being made rigid and/or being applied to a rigid carrier structure, and with these first and/or second parts, however, having at least one flexibly made region. The invention furthermore relates to a system for pumping and a method for pumping a liquid.
2. Description of the Prior Act
Disposable cassettes are already known from the prior art which are preferably used in the area of analytical technology. These cassettes have, for example, a plurality of layers which have rigid and flexible regions and which are made in one piece using two-component injection molding technology. The flexible regions can be made, for example, as pump chambers which can be pushed in by a corresponding actuator so that a fluid displacement takes place. A pump movement and/or also corresponding valve functions in the flexible regions is/are thus generated by mechanically driven plungers. Such mechanical interfaces, however, cause problems in the coupling of the disposable cassette to a corresponding machine. On the one hand, the so-called disposable cannot be placed completely smoothly on the machine part since there are always projections or recesses of the mechanical interfaces. On the other hand, a mechanical activation of the membranes can cause damage, for instance by the mechanical flexing movements of the flexible regions, which can result in the failure of the component. Such a corresponding disposable cassette is known, for example, from DE 102 39 597 A1.
U.S. Pat. No. 6,261,065 B1 furthermore describes a blood treatment system which is connected to a blood separation unit. This system has a cassette which has at least one pneumatically actuated pump.
U.S. 2007/0278155 A1 describes a mechanical fluid system having disposable cassettes which have flexible layers. Balance chamber systems for very precise liquid balancing are described which have first and second pump chambers and are separated by a flexible membrane. The inflow of a first fluid quantity into a first chamber of the balance chamber causes the displacement of the corresponding quantity of fluid from the second chamber. For this balance pump movement, a permanent magnet can be worked onto the flexible membrane which separates the two chambers and which can be moved by external electromagnets.
An electromagnetically operated membrane pump is furthermore known from DE 58 93 98 which is in particular provided for the aeration of aquariums. A magnetic armature is brought to oscillation by means of an electromagnet so that an air blast can be generated which can be introduced into the aquarium by means of a pressure pipe.
A drive for blood pumps is known from DE 199 63 306 A1 which is made in the form of a loudspeaker drive. In this connection, the drive has a magnet system and a mechanically sliding piston which is controlled by an absolute-position encoder and has windings which can be switched over and/or off, in which magnet system the piston can be fixed mechanically.
U.S. Pat. No. 4,459,977 relates to an apparatus for dialostic blood retroperfusion which can have an electromagnetically operated membrane pump.
U.S. Pat. No. 4,498,850 describes a pump having a pump chamber recess which is divided into two chambers by a magnetically actuable membrane and which is let into a pump chamber housing. A plurality of means are provided around the recess by means of which a magnetic field is applied so that the magnetically actuable membrane can be moved to trigger a pump movement.
WO 2006/123329 A2 describes a dispensing apparatus for a therapeutic fluid, in particular a dispensing apparatus for insulin, which is easy to handle and is preferably made in credit-card format. A membrane pump is described in connection with this apparatus which cooperates with two membrane valves which are each disposed upstream and are likewise activated electromagnetically.
SUMMARY OF THE INVENTION
It is therefore the object of the present invention to further develop a disposable element of the initially named kind in an advantageous manner, in particular such that it can be actuated in a contactless manner, can be operated simply and safely and is able to pump liquids, in particular medical liquids, highly precisely.
This object is solved in accordance with the invention by a disposable element having the features described herein. Provision is accordingly made that a disposable element is made of at least one first part, in which channel structures are recessed in the surface, and a second part sealingly covering said first part, with the larger part of the first part and/or of the second part being made rigid and/or being applied to a rigid carrier structure, and with these first and/or second parts, however, having at least one flexibly made region. Provision is further made that the at least one flexible region has at least one permanent magnet and/or at least one permanent magnetic region so that liquid can be displaced by means of the flexible region by application of a magnetic field.
The advantage thereby results that now no mechanical interface with a machine part which drives the flexible region is necessary for the generation of the movement of the flexible region by the permanent magnet. It is rather now possible to act on the flexible region in a contactless manner to be able to displace liquid hereby. Due to the omission of the plungers which had previously acted on corresponding flexible regions of known disposable elements, such as disposable cassettes, the coupling of the disposable element in accordance with the invention to a corresponding machine is simplified. Because now a substantially smooth application to the corresponding machine part is possible since a correspondingly smoothed, matched surface can be provided due to the omission of the mechanical, movable interface components. Furthermore, mechanical damage can no longer occur due to the contactless activation, which minimizes the failure probability of the component. The advantage furthermore results that the energy consumption for the activation of a pump, which can be formed by the flexible region, for example, can be reduced. The advantage further results that the corresponding apparatus into which the disposable element can be inserted can now be made more simply and compact.
It is conceivable that conventional thermoplastic elastomers are used for the flexible region. Polymer blends of SEBS (i.e., Styrene Ethylene Butylene Styrene) and PP (i.e., Polypropylene) can preferably be used. These blends have the advantage that they can be steam sterilized. It is alternatively conceivable that other blends can also be used provided they are compatible with the common sterilization methods in medical engineering. It is conceivable that the first and second parts are made in layer form. The carrier structure can also be made in layer form and can, for example, carry the part which is formed as a completely flexible layer and in which channel structures are formed. It is advantageously conceivable in this connection that the first part forms a middle layer which is enclosed in sandwich form by the carrier structure on the one side and by the sealingly covering second layer, which is formed by the second part, on the other side.
Provision can furthermore be made that the disposable element is manufactured by a process in which rigid and flexible regions of the first and/or second part are manufactured in one piece by means of two-component injection molding.
It is furthermore advantageously conceivable that the carrier structure and/or the first and/or second part are manufactured in one piece by means of two-component injection molding. The advantage thereby results of being able to make the advantageous structure of the disposable element with rigid and flexible regions cost-effectively and simply in only one single injection molding procedure.
Provision can furthermore be made that the at least one flexible region with the permanent magnet and/or the permanent magnetic region is made in chamber-like or dome-like form. It is, for example, conceivable in this connection that the chamber base is formed by the second part which sealingly covers the first part. The advantage thereby results that a fluid-dynamically favorable and simultaneously simply realizable pump chamber can be formed.
It is of advantage if the flexible region made in chamber-like form is a pump chamber of a membrane pump.
Provision can furthermore be made that the flexible region has at least one inflow and at least one outflow, with the inflow and the outflow each being formed by a channel structure and/or being connected to a channel structure. It is conceivable in this connection that a respective valve element is present in the region or in functional relationship with the inflow and outflow so that the flexible region can be used as a membrane pump. Provision can thus be made for the suction phase of the pump chamber of the membrane pump that the valve element is closed in the outflow and the valve element is open in the inflow. The valve element is then closed in the inflow and open in the outflow for the ejection phase.
It is furthermore conceivable that the permanent magnet and/or that the permanent magnetic part is an insertion part which is completely encased by the flexible region. The advantage thereby results that such an insertion part can be inserted into the injection molding tool before the plastic injection molding, in particular before the start of the two-component injection molding, and is then completely encased by the flexible portion of the disposable element during production. It thereby becomes possible to work the permanent magnet and/or the permanent magnetic region simply into the pump segment and furthermore to achieve the advantage that the permanent magnet and/or the permanent magnetic region has no fluid contact due to its casing.
Provision can furthermore be made that the permanent magnet and/or the permanent magnetic region is arranged in a part of the flexible region which is disposed opposite a wall so that the flexible region is movable in the direction of the wall by application of a magnetic field with a first orientation and/or so that the flexible region is movable away from the wall by application of a magnetic field with a second orientation. The wall can advantageously be a region of the second part. It is conceivable in this respect that a reduction of the pump chamber volume takes place on application of a magnetic field in the first orientation and a restoration of the chamber walls takes place on the application of the magnetic field with the second orientation and the pump chamber is again also already in the suction phase in this step.
It is furthermore possible that the flexible region has a side wall which is made peripherally concave and which has a diameter reducing toward the region with the permanent magnet and/or the permanent magnetic region. This can advantageously be realized in that the flexible region is a dome-like pump chamber of a membrane pump made substantially round. In this case, the region with the permanent magnet and/or the permanent magnetic region is arranged in the upper region of the chamber when the wall, which is made by the second part of the disposable element, for example, is considered as a chamber base.
Provision can advantageously be made that the side wall is resilient and opposes a pressing in of the flexible region with a resilient force which effects a self-restoration of the flexible region on load removal. The flexible region or the membrane of the membrane pump can therefore be made such that a material tension is built up on the activation from its rest position in the membrane or in the side walls of the membrane so that a restoration force is simultaneously adopted. Due to the application of the magnetic field, the membrane only has to be pressed in to generate a pump function so that a magnetic field only has to be applied in one single deflection direction. The correspondingly opposing movement for the restoration then takes place solely from the restoration force of the flexible region or of the membrane. A pole reversal of the magnetic field is thus not necessary.
The restoration movement of the membrane can, however, as already described above, likewise be supported by a reversed magnetic field. This is, however, preferably only possible when a permanent magnet is used as the magnetic element in the membrane. The membrane can thus only be operated continuously with a homogeneous force profile from one side.
The present invention furthermore relates to a system for pumping having the features described herein. Provision is accordingly made that a system for pumping has a disposable element as described herein as well as a reception apparatus into which the disposable element can be inserted. In this respect, the system has at least one means for the generation of a magnetic field by means of which the flexible region of the disposable element is movable with the at least one permanent magnet and/or at least one permanent magnetic region.
Provision can furthermore be made that the reception apparatus engages in a shaped-matched manner around the disposable element and/or that the means for the generation of a magnetic field is an electromagnetic coil, preferably an electromagnetic coil provided with an iron core, with the electromagnetic coil being arranged in a housing with a receiver for the flexible region.
A sinusoidal voltage characteristic is of advantage for the control of the electromagnet in alternating field operation. Voltage peaks can thus be avoided which could cause damage to the electronics of the system. Other voltage characteristics are likewise conceivable if an improved pump performance should be achieved.
The pumping movement of the membrane is advantageously correlated with further functional parts of the machine side or of the disposable element. The membrane position can in particular be regulated to the disposable element with valve units. In accordance with a corresponding arrangement, liquids can thus be pumped or sucked.
The advantage furthermore results from an electromagnetic control that the system is able to control the pump rate. The pump rate can also be varied by an electric regulation and can react to instructions of a corresponding control unit. It is conceivable in this connection that the system has corresponding regulation and/or control means. It is furthermore conceivable that conclusions can be drawn on the pump power via a calibration or on the basis of already known volume ratios and with reference to the electric control. It thereby becomes possible to achieve a very exact balancing of the conveyed liquid volume.
It is particularly advantageous if the system is a blood treatment apparatus, in particular a dialysis machine. Provision can equally be made that it is an analysis unit.
The present invention furthermore relates to a method for pumping a liquid as described herein. Provision is accordingly made that, in a method for the pumping of a liquid by application of a magnetic field, a flexible region with at least one permanent magnet and/or with at least one permanent magnetic region of a disposable element displaces the liquid. In this respect, the disposable element comprises at least one first part in which channel structures are recessed in the surface and a second part sealingly covering it, with the larger part of the first part and/or of the second part being made rigid and/or being applied to a rigid carrier structure and with these first and/or second parts, however, having at least one flexibly made region.
It is particularly advantageous if the method is carried out using a disposable element having the features described herein and/or using a system having the features described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
Further details and advantages of the invention will now be explained in more detail with reference to an embodiment shown in the drawing. There is shown:
The drawing figure provides a schematic sectional representation through a system for the pumping of liquids.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
The drawing figure shows, in section, a system in accordance with the invention for the pumping of liquids, wherein a disposable element 10 is received into the reception apparatus of the system otherwise only shown by the housing 110 with a receiver 114 and the electromagnetic coil 120 .
The disposable element 10 has a flexible first part 12 , which is made as a flexible layer. Channel structures 13 are recessed in the flexible first part 12 which are sealed by the second part 14 , which is made as a rigid cassette base. The flexible first part 12 is carried by a rigid carrier structure 16 so that the flexible first part 12 is enclosed between the rigid carrier structure 16 and the second part 14 . The disposable element 10 is in this respect partly made in the two-component injection molding process, with the flexible first part 12 and the rigid carrier structure 16 being made in the two-component injection molding process. The second part 14 is adhered subsequently. It is also conceivable that the second part 14 is formed by a sheet.
The disposable element 10 is in this respect made as a disposable cassette 10 .
The pump chamber 20 of an electromagnetically actuated membrane pump is located in the middle region of the disposable cassette 10 . The pump membrane 21 is a flexible region 21 which is a part of the flexible part 12 ; i.e., of the flexible layer. The flexible region 21 in this respect rises in dome-like form from the flexible first part 12 and passes through the rigid carrier structure 16 . The pump membrane 21 has side walls 22 which are made from flexible elastomer and which can preferably be made as side walls 22 in a peripherally circularly continuous manner. The pump chamber 20 is made round, preferably circular, in such a case. If it is assumed that the chamber base is formed by the layer 14 , i.e., the second part 14 of the disposable element 10 ,the pump chamber roof is formed by the wall region 24 of the flexible region 21 .
The disposable cassette 10 can generally be oriented as desired with the pump chamber 20 , that is can be inserted and operated, for instance, in a perpendicular, horizontal or slanted alignment in a corresponding receiver. The functionality of the membrane pump is not impaired by this.
The permanent magnet 30 , which is completely encased by the flexible region 21 , is located in this wall region 24 . Due to the flexible structure and the dome-like geometry of the pump membrane 21 , it is self-restoring, that is, the pump membrane 21 always returns to the zero position shown in the drawing figure by resilience in the unloaded state.
The pump chamber 20 has an inlet 26 and an outlet 28 which are each arranged at the end of a supplying or discharging channel structure 13 . The supplying channel structure 13 comes from the cassette inlet 60 which can be connected to a fluid supply 40 by means of a sealing element 62 . The sealing element 62 is in this connection shaped by an extension, preferably a ring-shaped extension, of the flexible first part 12 which passes through the rigid carrier structure 16 . The fluid inflow 40 furthermore has a valve element 42 by means of which the inflow can be blocked.The direction of the inflowing fluid F is indicated by arrows.
The cassette oufflow 70 is substantially made in the same construction as the inlet 60 and likewise has a sealing element 72 which is made in ring shape by the flexible first part 12 . The fluid outflow 70 is in this connection connectable to the outflow channel 50 , with the outflow channel 50 having a valve element 52 by means of which the outflow channel 50 can be blocked.
At the machine side, a support surface 100 is provided on which the carrier structure 16 can be placed. The support surface 100 is penetrated by the housing 110 of the means for the generation of a magnetic field. The means for the generation of a magnetic field is a coil 120 which is fully engaged around by the housing. The housing 110 furthermore has a receiver 114 which is adapted to the geometry of the pump membrane 21 . The housing 110 furthermore has a hollow space 112 into which an iron core can optionally be inserted for the reinforcement of the magnetic field.
The operation of the system for pumping shown in the drawing figure can be made as follows in this respect: A magnetic field is applied by means of the electromagnet 120 so that the permanent magnet 30 is repulsed and is driven in the direction of the wall 14 . At the same time, the valve element 42 must be closed to prevent a backflow movement and the valve element 52 must be open to enable an outflow of the fluid F. The pump membrane 21 restores itself automatically by switching off the magnetic field or the electromagnet 120 . The valve element 52 is advantageously already closed at the moment of restoration and the valve element 42 is open so that the fluid F can again flow into the pump chamber 20 . The valve 42 is then closed again and the valve 52 is opened and the magnetic field is applied by the electromagnet 120 so that a displacement of fluid from the pump chamber 20 again takes place by the repulsion of the permanent magnet 30 .
The invention being thus described, it will be apparent that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be recognized by one skilled in the art are intended to be included within the scope of the following claims.
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A disposable pump element has at least one first part, in which channel structures are recessed in the surface, and a second part sealingly covering the first part. A larger portion of the first part is applied to a rigid carrier structure. The first part has at least one flexible region, and at the flexible region thereof, the first part is not applied to the rigid carrier structure. A system for pumping, and a method for pumping a liquid, both employ the disposable pump element.
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RELATED APPLICATION INFORMATION
[0001] The present application claims priority to and the benefit of German patent application no. 10 2013 206 641.4, which was filed in Germany on Apr. 15, 2013, the disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a method for carrying out at least one learning function in a motor vehicle and a system or arrangement which are provided for implementing such a method.
BACKGROUND INFORMATION
[0003] During the manufacturing of motor vehicles, certain tolerances of the components used, in particular the components of internal combustion engines or the internal combustion engines themselves, are unavoidable. Such tolerances may be, for example, differences in the compression values of the cylinders of an internal combustion engine and differences in the compression mean values between multiple internal combustion engines of the same type or series. Corresponding tolerances also occur in the installed injectors and in all exhaust-relevant components of internal combustion engines (turbocharger, air mass sensor, exhaust gas recirculation valve, etc.).
[0004] Those skilled in the art frequently refer in this context to so-called min and max components. A max injector will inject more fuel during the same activation duration than a nominal injector. A nominal injector is an injector here which corresponds to its particular specification without any deviation (i.e., has a tolerance of zero). One also refers in this case to a “golden injector” or a corresponding “golden” component. During the development of motor vehicles, a “golden system” is used in the so-called application phase. This applies in particular for the application phase of the exhaust gas optimization. A “golden system” or a “golden engine” only has nominal components.
[0005] In order to compensate for nominal value deviations in the actually constructed motor vehicles, an array of learning functions is known, to each of which specific input variables are applied. Learning functions which may be used within the scope of the present invention are, for example, provided in the case of IQA (injector quantity adjustment; compensation of the manufacturing tolerance during the injector manufacture), MCC (model-based charge control; model-supported charge regulation), PWC (pressure wave compensation; compensation of hydraulic oscillations), MBC (model-based boost pressure control; model-supported boost pressure regulation), ZFC (zero fuel calibration; correction of the pilot injection, zero-fuel quantity calibration), FBC (fuel balance control; balancing of the cylinder scattering of the injection quantity), FMA (fuel mean value adaptation; lambda-based air mass and air quantity correction), and FMO (fuel mass observer; lambda-based correction of the quantity at full load), which predominantly relate to diesel engines. Learning functions exist in the case of gasoline engines for the mixture adaptation or the torque loss adaptation, for example.
[0006] Learning functions correct engine activation parameters with the aid of corresponding correction values, for example, so that the internal combustion engine behaves like a “golden engine” after application of the correction values. Ideally, after a corresponding correction, an internal combustion engine having exclusively min or max components also has an identical power and identical exhaust gas results as an engine having nominal components. Corresponding learning functions also correct deviations or drifts which may occur during the service life of the motor vehicle. The nominal value deviations are therefore also referred to here as “manufacturing-related” and as “age-related” nominal value deviations. For example, if an injector drifts in the course of operation of a vehicle within a certain scope away from the originally provided value, this is corrected by the learning functions.
[0007] The explained learning functions have the disadvantage that they require several thousand kilometers (typically approximately 5000 km), until they may effectively act or may be activated. This is to be attributed to the fact that the learning functions must each ascertain corresponding characteristics for a variety of operating states of the motor vehicle, which are each defined differently, and are only then capable of providing the correction values. Furthermore, corresponding learning functions must be continuously recalibrated over the entire service life of the motor vehicle, which also includes the ascertainment of corresponding characteristics in multiple defined operating states.
[0008] Therefore, the need still exists for improvements in the performance of corresponding learning functions, in particular for the reduction of the time which is required for corresponding learning functions.
SUMMARY OF THE INVENTION
[0009] Against this background, the present invention provides a method for carrying out at least one learning function in a motor vehicle and also arrangement for implementing such a method having the features of the independent patent claims.
[0010] Exemplary embodiments are the subject matter of the dependent patent claims and the following description.
[0011] The present invention is directed to a method for carrying out a corresponding learning function, which is used to provide a correction value to compensate for at least one nominal value deviation of at least one component of a motor vehicle. In this case, with the aid of the learning function, characteristics are ascertained in at least one defined operating state of the motor vehicle and used to determine the correction values.
[0012] In conventional motor vehicles, corresponding learning functions run in the background. The driver is not aware that a learning function is carried out. A connection between the learning functions and the traveled driving route also does not conventionally exist.
[0013] It is provided according to the present invention, to accelerate and simplify carrying out a corresponding learning function, that a driver of the motor vehicle is prompted, in particular during at least one learning operation period of time, to operate the motor vehicle in the at least one defined operating state and advantageously to incorporate a driving route which has been traveled and/or is to be traveled, during the carrying out of the learning function.
[0014] In particular, the time which corresponding learning functions require to be able to provide correction values to compensate for the nominal value deviations (i.e., to be “trained”) is reduced by the measures according to the present invention. For example, the above-mentioned zero fuel calibration (ZFC), which will be explained hereafter, is “learned” in overrun phases at a specific speed and a specific rail pressure.
[0015] In the case of the zero fuel calibration, as is disclosed, for example, in DE 101 59 016 A1, for example, an activation duration for a first partial injection, for example, a pilot injection, is increased proceeding from a zero value, at which injection reliably does not occur, until the characteristic, for example, an ion current, which characterizes an ignition lag, is detected. The activation duration is then increased further until the characteristic which characterizes the ignition lag no longer substantially changes. The method is based on the fact that the ignition lag, i.e., the time interval between an activation of a valve and the beginning of combustion, initially decreases with increasing activation duration. From a specific activation duration, the ignition lag no longer changes. The activation duration at which the ignition lag transitions into the saturation is considered to be the optimal activation duration for a pilot injection and is used as a standard value for the activation. The ascertained value represents the learned value of the zero fuel calibration function and is used to provide corresponding correction values.
[0016] An “overrun phase” refers to a phase, during which, in the case of a gasoline engine, the throttle valve is closed, the gas pedal is not actuated, and the engine is not at idle speed. In general, the term “overrun phase” may also refer to a phase, during which an internal combustion engine is not fired and the clutch is engaged. The internal combustion engine is thus entrained via the wheels during overrun phases. For example, during the zero fuel calibration, each cylinder must be trained individually in corresponding overrun phases. In the case of a twelve-cylinder engine having automatic transmission, in which overrun phases occur relatively rarely, a relatively long time is necessary for training all cylinders. The motor vehicle is thus in a state which is not optimal with respect to its performance capability and its emission values for a long time. The optimal state is only provided when all learning functions are trained and the motor vehicle corresponds to a nominal (“golden”) system.
[0017] The present invention overcomes these restrictions in that the driver is incorporated in corresponding learning functions and is prompted to operate the motor vehicle in the at least one defined operating state.
[0018] A corresponding motor vehicle may therefore be put more rapidly into an optimal state, in which the exhaust and consumption values are nearly optimal. Since the training time of a corresponding learning function is shortened, the vehicle will potentially emit less pollutants and carbon dioxide.
[0019] Furthermore, the present invention allows the emission limits to be maintained during production and field tests, as are prescribed, for example, in the regulations about the documentation of the so-called COP (conformity of production) and “in-use compliance” (CAP 2000 or Euro 3/Euro 4). These are to ensure that motor vehicles maintain the emission regulations in the field over a specific time or route. In the case of Euro 4, for example, these are five years or 100,000 km.
[0020] The learning state of the learning functions is advantageously registered by the engine control unit, for example, which already has all required items of information. The “learning state” specifies, for example, which fraction of the provided learning functions is already trained or which areas or fractions of the learning functions are not yet trained. For example, the learning state—optionally in prepared form—may subsequently be transmitted to the driver. Simultaneously, instructions may be transmitted to the driver, which specify how the not yet trained learning functions (or corresponding fractions) may be trained. For example, it may be communicated to the driver which gear choice/speed combination has not yet been able to be taken into consideration within the scope of a corresponding learning function.
[0021] For example, a known user information system of a motor vehicle, as is implemented in the onboard computer, may be used to transmit corresponding items of information to a driver. The items of information may be transmitted, for example, by a visual display via digital instruments and/or optionally audio-visually via an entertainment system.
[0022] The scope and the richness of detail of the items of information to be transmitted to the driver may be made dependent on various factors. For example, the degree of abstraction of the items of information may be preselected within the scope of various professionalism levels. For example, it may be communicated to an experienced driver having wide-ranging knowledge about the engine control unit that an overrun phase is necessary, so that he knows independently which measures are to be taken for this purpose.
[0023] For example, simple scenarios may be displayed to a less experienced driver, which allow him to set specific operating states of the motor vehicle or to operate the vehicle in such operating states. The driver may be prompted in this way, for example, to initiate an overrun phase having a minimum engine speed and a defined gear. Furthermore, the driver may be admonished to drive in specific speed ranges, for example. In the case of a manual transmission, this may include shifting later or earlier than usual, for example, in the case of automatic or semiautomatic transmissions, the driver may be prompted to change into a corresponding manual operation. For example, the driver may also be requested to turn off the start-stop system when idle phases are necessary for the training. Alternatively thereto, this may also be performed independently by the vehicle, as is also the case in the event of a request of the battery management, for example, if the onboard electrical system voltage is excessively weak or there is a demand of an air-conditioning system. This may be communicated to the driver, so that he does not erroneously presume a malfunction of the vehicle.
[0024] A corresponding user information system may also include a so-called dashboard, for example, which gives the driver the instruction, for example: “If possible, start up overrun phases in the third gear more frequently. Please obey the traffic regulations and observe road safety.” If the training of the function is successful, feedback may be given to the driver that the attempt was successful. The driver is hereby incorporated in the learning function.
[0025] If a so-called gear change display is provided, this may advantageously also be used. The gear change display indicates the optimal shift points on the speedometer or gives the driver the instruction in which gear he should drive. Via a corresponding gear change display, alternatively to the conventional predefined shift points, during a training phase of a learning function, the shift points which are optimal for training the learning function may be predefined. This permits different operating points than usual to be approached and thereby causes a more rapid training. In the case of an automatic transmission, the shift points may be changed by the engine control unit, so that the ranges required for the learning function may be approached in a targeted manner.
[0026] An incorporation of the traveled route or the route to be traveled may also be advantageous within the scope of the present invention. For this purpose, for example, a communication may occur between the engine control unit and a navigation system (for example, via a CAN bus). The navigation system provides items of information about the traveled route and about the upcoming driving demands (for example, downhill grade or uphill grade or traffic jams communicated via a traffic information system). An engine control unit may therefore reasonably prioritize and plan the training of specific functions depending on the driving route. If a downhill grade is coming up, many overrun phases are presumably possible. If an uphill grade is coming up, in contrast, the instruction to the driver to set an overrun phase is less reasonable. The method may thus include a determination of a corresponding probability.
[0027] If a driver specifies a specific destination in a navigation system, the engine control unit may estimate, as a function of the profile of the driving route and the traffic conditions, which learning functions and in what regard these learning functions may be trained. If many different overrun phases are to be expected at different speeds (city, highway, freeway), the system may first wait before it gives an instruction to the driver. In this case, the functions could possibly also be learned without incorporation of the driver, which will possibly be perceived to be annoying.
[0028] An incorporation of so-called onboard diagnostic functions is also possible in the sense of more rapid training of the learning functions. An array of such onboard diagnostic functions also requires a specific mode of driving and/or specific conditions (operating points, engine temperature) to be activated and to be able to carry out a diagnosis.
[0029] A computing unit according to the present invention, for example, a control unit of a motor vehicle, is configured as a system or arrangement for implementing the method according to the present invention, in particular by programming, for the purpose of carrying out a method according to the present invention.
[0030] The implementation of the method in the form of software is also advantageous, since this causes particularly low costs, in particular if an executing control unit is also used for further tasks and is therefore present in any case. Suitable data media for providing the computer program are in particular diskettes, hard drives, flash memories, EEPROMs, CD-ROMs, DVDs, etc. A download of a program via computer networks (Internet, intranet, etc.) is also possible.
[0031] Further advantages and embodiments of the present invention result from the description and the appended drawings.
[0032] It is understood that the above-mentioned features and the features still to be explained hereafter are usable not only in the particular specified combination, but rather also in other combinations or alone, without departing from the scope of the present invention.
[0033] The present invention is schematically shown on the basis of an exemplary embodiment in the drawing and will be described in greater detail hereafter with reference to the drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 shows components of a motor vehicle, which may be operated according to the present invention, in a schematic view.
[0035] FIG. 2 shows a method according to one specific embodiment of the present invention in the form of a schematic flow chart.
DETAILED DESCRIPTION
[0036] In FIG. 1 , components of a motor vehicle, which may be operated according to the present invention, are schematically shown and are identified as a whole with reference numeral 1 . A piston 2 of an internal combustion engine (not shown in greater detail) is movable up and down in a cylinder 3 . A crankshaft 14 , via which ultimately at least one wheel of motor vehicle 1 is driven using a drive torque, is set into a rotational movement by the piston. The crankshaft is connected for this purpose to a drivetrain, which typically has a transmission, a clutch, brakes, and an electric machine, etc.
[0037] Cylinder 3 is provided with a combustion chamber 4 , to which an intake manifold 6 and an exhaust pipe 7 are connected via valves 5 . Intake manifold 6 is connected to exhaust pipe 7 via an exhaust gas recirculation valve 13 having a valve flap as an actuator for external exhaust gas recirculation. Exhaust gas recirculation valve 13 is controllable using a signal EGR from a control unit (ECU) 16 . Furthermore, an injector 8 , which is controllable using a signal TI, and a spark plug 9 , which is controllable using a signal ZW, are connected to combustion chamber 4 . The internal combustion engine of motor vehicle 1 according to FIG. 1 is based on the spark ignition principle. However, it is to be clarified that the present invention is not dependent on the ignition method of the internal combustion engine and is also well suitable for internal combustion engines using compression ignition. The present invention may also be used in internal combustion engines without exhaust gas recirculation.
[0038] A boost pressure sensor 18 , which outputs a signal LD, which indicates the boost pressure in the intake manifold, and a throttle valve 12 , the rotational position of which is settable with the aid of a signal DK, are housed in intake manifold 6 . Intake manifold 6 is furthermore provided with an air flow sensor 10 and exhaust pipe 7 is provided with a lambda sensor 11 . Air flow sensor 10 measures the air flow of the fresh air supplied to intake manifold 6 and generates a signal LM as a function thereof. Lambda sensor 11 measures the oxygen content of the exhaust gas in exhaust pipe 7 and generates a signal lambda (λ) as a function thereof. An exhaust system (not shown), including a catalytic converter, for example, a three-way catalytic converter, is connected downstream from lambda sensor 11 .
[0039] In this example, in the case of internal combustion engines having turbocharging, compressor 19 of a turbocharger is situated between air flow sensor 10 and throttle valve 12 . Compressor 19 , in particular a regulating valve of compressor 19 , is controllable with the aid of a signal KP. In the case of internal combustion engines having turbocharging, turbine 20 of the turbocharger is installed downstream from lambda sensor 11 . Turbine 20 , in particular a speed of turbine 20 , is controllable with the aid of a signal TR.
[0040] Furthermore, control unit 16 is connected to a gas pedal sensor, which generates a signal FP, which specifies the position of a gas pedal 17 , which is actuatable by a driver, and therefore the engine torque requested by the driver.
[0041] A speed sensor 21 is provided. It is configured to provide a signal DZ, which is also transmitted to control unit 16 . This is correspondingly true for a velocity signal SP of a speedometer 26 .
[0042] Furthermore, a shift unit 15 is provided. Shift unit 15 may be configured in this example as a shift unit 15 of a manual shift transmission (not shown) of the motor vehicle. A gear may be engaged with the aid of shift unit 15 . Simultaneously, control unit 16 may be made aware of the gear selection via a corresponding signal GW.
[0043] Signal LD of boost pressure sensor 18 , signal LM of the air flow sensor, signal lambda (λ) of lambda sensor 11 , and signal DZ of speed sensor 21 are, for example, characteristics which result in the case of a defined operating state of the internal combustion engine, for example, a defined position of the regulating valve of compressor 19 , which is controlled with the aid of signal KP, a defined speed of turbine 20 , which is controlled with the aid of signal TR, and/or a defined injection quantity, which results from the control of injector 8 using signal TI. The precise values which these characteristics have is dependent on various manufacturing-related and/or age-related nominal value deviations. Such nominal value deviations are compensated for with the aid of correction values, which are ascertained with the aid of a learning method. Control unit 16 is also configured for this purpose.
[0044] A user information unit 22 , with the aid of which a driver of motor vehicle 1 may be prompted to set at least one defined operating state of motor vehicle 1 , is connected to control unit 16 . For this purpose, the user may receive corresponding instructions with the aid of visual arrangement 23 or acoustic arrangement 24 , for example, with the aid of a display screen of a navigation system, with the aid of a shift point display, and/or with the aid of a loudspeaker. For example, route and/or traffic data may be provided to user information unit 22 and/or control unit 16 via a navigation system 25 .
[0045] In FIG. 2 , a method according to one specific embodiment of the present invention is shown in the form of a flow chart and identified as a whole with reference numeral 100 .
[0046] The method according to the present invention begins in a step 110 , which may be carried out cyclically, for example, as illustrated with a sequence arrow 111 . In step 110 , the method or a corresponding control unit 16 transitions into a status in which a learning function is to be ascertained.
[0047] In a step 120 , the above-explained prioritization and the selection of the particular approach for more rapid training of a corresponding learning function take place. For example, items of information 121 , which are provided with the aid of a navigation system 130 with respect to a travel route and/or traffic conditions, for example, may be taken into consideration in this case.
[0048] Depending on the selection made in step 120 , steps 140 through 170 and/or further steps (not shown) are carried out. For example, in a step 140 , other shift points may be displayed with the aid of a shift point display or set in an automatic transmission. The driver may be informed about this. In a step 150 , for example, a start-stop system may be turned off and the driver may optionally be informed of this. Alternatively, the driver may also be prompted to turn off the start-stop system. In a step 160 , for example, the driver may be prompted to travel in a specific driving mode, i.e., using a specific gear and a specific velocity. If carrying out a learning function is not required or reasonable, the method may be continued in a step 170 with or without informing the driver.
[0049] In a step 180 , it is checked whether or not a corresponding function was successfully trained. If not, the method progresses via sequence arrow 111 with step 110 , i.e., a learning function is again carried out. If all learning functions have been successfully trained, the driver may optionally be informed of this in a step 190 .
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A method for carrying out a learning function is described, which is used to provide at least one correction value to compensate for at least one nominal value deviation of at least one component of a motor vehicle. At least one characteristic is ascertained in the case of at least one defined operating state of the motor vehicle with the aid of the learning function and used to determine the at least one correction value. The method includes prompting a driver of the motor vehicle to operate the motor vehicle in the at least one defined operating state. A system for implementing a corresponding method is also described.
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BACKGROUND
[0001] This invention relates generally to memory devices and particularly to memory devices with a multilevel cell architecture.
[0002] A multilevel cell memory is comprised of multilevel cells, each of which is able to store multiple charge states or levels. Each of the charge states is associated with a memory element bit pattern.
[0003] A flash EEPROM memory cell, as well as other types of memory cells, is configurable to store multiple threshold levels (V t ). In a memory cell capable of storing two bits per cell, for example, four threshold levels (V t ) are used. Consequently, two bits are designated for each threshold level.
[0004] In one embodiment, the multilevel cell may store four charge states. Level 3 maintains a higher charge than level 2, level 2 maintains a higher charge than level 1, and level 1 maintains a higher charge than level 0. A reference voltage may separate the various charge states. For example, a first voltage reference may separate level 3 and level 2, a second voltage reference may separate level 2 from level 1, and a third reference voltage may separate level 1 from level 0.
[0005] A multilevel cell memory is able to store more than one bit of data based upon the number of charge states. For example, a multilevel cell memory that can store four charge states can store two bits of data, a multilevel cell memory that can store eight charge states can store three bits of data, and a multilevel cell that can store sixteen charge states can store four bits of data. For each of the n-bit multilevel cell memories, various memory element bit patterns can be associated with each of the different charge states.
[0006] The number of charge states storable in a multilevel cell, however, is not limited to powers of two. For example, a multilevel cell with three charge states stores 1.5 bits of data. When this multilevel cell is combined with additional decoding logic and coupled to a second similar multilevel cell, three bits of data are provided as the output of the two-cell combination. Various other multi-cell combinations are also possible.
[0007] The retrieval of information from multilevel cell memories is currently slower than the retrieval from single-bit cell memories because the sensing time of multilevel cell memories is greater. This is primarily because sensing more than one bit takes more time than sensing one bit.
[0008] Generally, with conventional multilevel cell designs, a word may consist of a plurality of bits. A first set of two bits of the word may be stored in the same cell(in a 2 bit multilevel cell example) and then the next set of two bits may be stored in the same cell and so on to store the entire word. Then, to access to word, after decoding, both the first and second bits of the cell are sensed. Only when both bits have been sensed is the output accessible. In effect, then, the output must wait for both the first and the second bits to be sensed.
[0009] Thus, there is a need for a way to decrease access times for multilevel cell memories.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] [0010]FIG. 1 is a block depiction of one embodiment of the present invention;
[0011] [0011]FIG. 2 is a schematic depiction of the memory architecture in accordance with one embodiment of the present invention;
[0012] [0012]FIG. 3 is a schematic depiction of the memory architecture in accordance with the prior art;
[0013] [0013]FIG. 4 is a flow chart in accordance with one embodiment of the present invention; and
[0014] [0014]FIG. 5 is a flow chart in accordance with the prior art.
DETAILED DESCRIPTION
[0015] Referring to FIG. 1, a processor 100 may be coupled through a bus 102 to a multilevel cell memory 104 . The memory 104 contains an interface controller 105 , a write state machine 106 and a multilevel cell memory array 150 . The processor 100 is coupled by the bus 102 to both the interface controller 105 and the memory array 150 in one embodiment of the present invention.
[0016] The interface controller 105 provides control over the multilevel cell memory array 150 . The write state machine 106 communicates with the interface controller 105 and the memory array 150 . The interface controller 105 passes data to be written into the array 150 to the state machine 106 and the state machine 106 executes the sequence of events to write data into the array 150 . In one embodiment, the interface controller 105 , the write state machine 106 and the multilevel cell memory array 150 are located on a single integrated circuit die.
[0017] Although embodiments are described in conjunction with a memory array 150 storing two bits per cell, any number of bits may be stored in a single cell, for example by increasing the number of threshold levels, without deviating from the spirit and scope of the present invention. Although embodiments of the present invention are described in conjunction with a memory array 150 of flash cells, other cells, such as read only memory (ROM), erasable programmable read only memory (EPROM), conventional electrically erasable programmable read only memory (EEPROM), or dynamic random access memory (DRAM), to mention a few examples, may be substituted without deviating from the spirit and the scope of the present invention.
[0018] Referring to FIG. 2, two words 10 and 12 stored in the memory array 150 include a plurality of bits 14 and 16 , respectively. In the architecture depicted in FIG. 2, instead of placing adjacent bits within the same word in the same memory cell 18 , adjacent bits 14 in the same word 10 or 12 are placed in different multilevel memory cells 18 . For example, the bit 14 a for the word 10 is stored with the bit 16 a from the word 12 to form a cell 18 a . Likewise, the other bits 14 of each word 10 or 12 are stored such that each memory cell 18 in the array 150 includes bits 14 from different words 10 or 12 .
[0019] While in one embodiment to the present invention, one bit from each of two words is paired with one bit from the other of two words, a variety of other arrangements may be used. By placing bits from the same word in different cells, the access times of the memory array 150 may be improved relative to sensing both words before outputting either word.
[0020] Advantages of some embodiments of the present invention may be better understood by comparing the embodiment of FIG. 2 to a prior art architecture shown in FIG. 3. In FIG. 3, the words 20 and 22 have bits 14 and 16 as before. However, in accordance with the conventional approach, adjacent bits 14 or 16 in the same word 10 or 12 (such as the bits 14 a and 14 b ) are stored in the same multilevel memory cell (e.g., the cell 20 a ).
[0021] As a result, in order to access information from the prior art memory array, it is necessary to first decode and then to successfully sense the first bit, such as the bit 14 a . Next, it is necessary to successfully sense the second bit, such as the bit 14 b , and finally to output the information. The access time for the cell 20 is the combination of the times to decode, to sense both the first and second bits and finally to output the sensed information.
[0022] In contrast with the embodiment shown in FIG. 2, the access time for the first word is a function of the decode time together with the time to sense the first bit plus the output time. In other words, the access time may be comparable to that of conventional single bit memories. The access time for the second word is a combination of the time to sense the second bit and the output time since no decoding is necessary the second time around.
[0023] Thus, the writing of the information into the array 150 may be controlled by hardware, for example, in the write state machine 106 and microcode stored therein, in one embodiment of the present invention. However, wholly software or wholly hardware based approaches may also be used.
[0024] In one embodiment, the sensing code 122 may initially cause the decoding to occur as indicated in block 24 . Next, the first word is sensed as indicated in block 26 . The first word is then outputted as indicated in block 28 .
[0025] Next, the second word is sensed as indicated in block 30 and the second word is outputted as indicated in block 32 . This sequence continues consistently with the architecture shown in FIG. 2.
[0026] Referring to FIG. 5, the access code 122 a in accordance with the prior art initially decodes as indicated in block 24 and then senses the first word as indicated in block 26 . Then the prior art approach senses the second word as indicated in block 30 and finally outputs the first and second words as indicated in block 34 after sensing both the first and second words. Clearly the access time to the first word is significantly slower than with the technique illustrated for example in FIG. 4.
[0027] While the present invention has been described with respect to a limited number of embodiments, those skilled in the art will appreciate numerous modifications and variations therefrom. It is intended that the appended claims cover all such modifications and variations as fall within the true spirit and scope of this present invention.
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A multilevel cell memory may use an architecture in which bits from different words are stored in the same multilevel memory cell. This may improve access time because it is not necessary to sense both cells before the word can be outputted. Therefore, the access time may be improved by removing a serial element from the access chain.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to the use of thin film deposition technology to create high density interconnects on a printed wiring board substrate. More specifically, the present invention pertains to an improved method for controlling the impedance of signal lines formed on a high-density interconnect substrate. The present invention increases the surface area available for routing wiring having improved impedance characteristics. The method of the present invention can be used with or without an initial build-up layer on a printed wiring substrate provided by a substrate vendor, and is useful for high density integrated circuit packaging of single chip or multi-chip hybrid circuits including components such as resistors and capacitors. The method of the present invention is also useful for creating interconnections on high-density “daughter” boards that carry packaged devices.
[0002] The semiconductor industry continues to produce integrated circuits of increasing complexity and increasing density. The increased complexity of some of these integrated circuits has in turn resulted in an increased number of input/output pads on the circuit chips. At the same time, the increased density of the chips has driven the input/output pad pitch, i.e. the spacing between pads, downward. The combination of these two trends has been both a significant increase in the connector pin wiring density and closer spacing of the pins. Concurrent with this increased pin density and lower pitch has been an increase in the frequency of signals that are sent through the wiring substrate. A simple, uncharacterized wire is no longer optimum for these high frequency signals, and a signal line having a selected characteristic is desired. In other words, it is desirable that the signal lines are transmission lines with a known and controlled characteristic impedance.
[0003] A number of different technologies have been developed to interconnect multiple integrated circuits and related components. One such technology, based on traditional printed wiring board (“PWB”) technology is often referred to as MCM-L or laminate MCM technology. This technology found wide use during the period in which integrated circuits were packaged in dual-in-line packages (“DIPs”). MCM-L technology typically uses sub-laminate boards of copper foil and dielectric material layers to create a laminated interconnect structures. Conductive patterns on the sub-laminate in MCM-L process are typically formed using a dry film of photo resist over the copper layer, patterning and developing the photo resist to from an appropriate mask, and selectively etching away the unwanted copper, thereby leaving the desired patterned conductive layer.
[0004] Substrates used in MCM-L technology can be manufactured in large-area panels that are efficient and relatively low-cost. Interconnect solutions using this technology generally have relatively good performance characteristics when used with the generally wide-pitch, low pin density DIP components. The printed wiring board industry, however, has not kept pace with the advances in semiconductor manufacturing in terms of pad density.
[0005] In some applications, two or more sub-laminates are stacked together to form a final, stacked structure, or multi-layer laminated printed wiring substrate. Interconnection between stacked layers can be provided by a plated through hole (“PTH”). One way to make a PTH is to drill a hole through the board, and then plate the interior surface of the hole. The drilling process is relatively slow and expensive and can require a large amount of board space, thus reducing the area available for signal routing. As the number of interconnect pads increases, an increased number of signal layers is often used to form the interconnect structure. Because of these limitations, the conventional printed wiring board technology needs to use a large number of metal layers (e.g. greater than eight layers for some of the applications) in high density integrated circuit packaging and daughter board fabrication. Utilizing a large number of metal layers in this context generally increases cost and decreases electrical performance. Also, the pad size limits the wiring density on any given layer with this technology. Thus, MCM-L technology, while useful for some applications, is not capable of providing the connection density required in other applications.
[0006] To improve the interconnect density of MCM-L technology, an advanced printed wiring board technology approach called build-up multi-layer has been developed. In this technology a traditional laminated printed wiring board core is the starting point. Standard drilling and plating techniques are used to form plated through holes in the core. From the basic core this build-up approach has many variations. Typically, a dielectric layer approximately 50 micrometers thick is formed on the top, bottom, or both major surfaces of the laminated wiring board substrate, although in some instances the layer may be only about 30 microns thick. Vias are formed in the build-up layer by laser ablation, photo mask/plasma etch, photo exposure and development, or other methods. An electroless seeding step is then done prior to a panel plating step to metallize the surface(s) of the dielectric layer(s). The metal layer is typically 10-15 microns thick, but could be as thin as 4-5 microns. Typically, subsequent masking and wet etching steps then define a desired conductive pattern in the metal layer on the build-up dielectric layer.
[0007] Another approach used to package high density input/output uses thick film (i.e. screen printing) over co-fired ceramic substrates. This technology is sometimes referred to as “MCM-C”, for co-fired ceramic MCM and thick film MCM technology. Basically, MCM-C technology involves rolling a ceramic mixture into sheets, drying the sheets, punching vias through the green ceramic sheets, screening the rolled sheets with a metal paste to form an electrical trace pattern on the surface of the ceramic sheet(s), stacking and laminating all the sheets together, then co-firing at a high temperature (e.g. typically at a temperature greater than 850° C.) to form a substrate assembly with the desired interconnections.
[0008] MCM-C construction has found extensive use in high density and high reliability products where the robustness of the high density interconnect package outweighs the cost considerations. The ability to create a hermetic seal in the ceramic improves the ability to withstand environments not tolerable to conventional printed wiring board technology. While this technology is capable of high-density packaging applications (e.g. greater than 1000 pads), it is also very costly. Additionally, performance characteristics, such as signal propagation time, are affected by the relatively high dielectric constant (e.g. typically between 5.0 and 9.0) of the ceramic material. MCM-C technology provides higher connection density than MCM-L technology, but is not capable of providing the connection density required for some of today's high density interconnect applications, and is difficult to use to produce large panels.
[0009] A third approach which the high density interconnect and packaging industry has moved toward to address these high density interconnect applications uses thin film MCM technology and is sometimes referred to as “MCM-D” for MCM deposition technology. In some applications, such MCM-D technology includes forming and patterning thin film conductive traces over large substrates such as the laminated printed wiring boards discussed above. Such large substrates may have a surface area of 40 centimeters by 40 centimeters or more, thereby providing efficiencies that lower the costs of production. This type of technology is also sometimes referred to as “DONL” for deposited-on-laminate.
[0010] MCM-D technology utilizes a combination of low cost printed wiring board structures, with or without the use of the build-up multi-layers (i.e. a build-up layer and a first metal layer supplied by the substrate vendor) on the laminated printed wiring board, as a starting point to meet higher density and lower cost interconnect requirements. One feature of MCM-D technology is that it can produce a high-density interconnect substrate using thin film processes on only one side of the printed wiring board. The total thickness of several of these deposited layers can be less than the thickness of a single traditional build-up layer. This can eliminate the need for balancing the build-up layers on both top and bottom to prevent the substrate from warping.
[0011] Despite the definite advantages of MCM-D technology, there are potential problems that may result in failure modes and performance limitations if the thin film formation is not properly implemented. One such limitation resulting from improperly deposited thin film build-up layers is sub-optimized inter-layer impedance. The thin-film techniques used in MCM-D technology can provide for narrow, closely spaced signal lines in the patterned conductor layer, and for a conductor layer that is separated from another conductor layer by a relatively very thin dielectric layer. These and other factors can result in a signal line of high and/or varying impedance.
[0012] Accordingly, improved methods and structures are desirable to control the impedance of signal lines in the build-up portion of MCM-D substrates.
SUMMARY OF THE INVENTION
[0013] The present invention provides a solution to the problem of controlling the impedance of signal lines in the build-up layers of printed circuit wiring substrates. The invention enables a higher portion of the total number of signal lines to achieve a desired impedance, and to reduce the uncontrolled impedance effects on the electrical performance of the high density interconnect device. Alternatively or additionally, the invention enables greater freedom in choosing a routing pattern for signal lines while retaining a desired impedance. The present invention provides a significant increase in ground reference plane area, providing increased routing of signal lines over a reference plane to achieve a controlled characteristic impedance. In one embodiment, increased pad density and a transition between a coarse pad pitch, e.g. 1 mm, and a fine pad pitch, e.g. less than or equal to about 0.1 mm, is also achieved.
[0014] According to one embodiment of the present invention, a planarized layer is formed on a laminated printed wiring substrate to improve the electrical performance of the layer and allow for finer geometry processes to define a subsequent metal layer. In one embodiment this metal layer is a thin-film layer formed by sputtering, also known as physical vapor deposition (“PVD”), or pattern plating. The fine-geometry achieved by the combination of the planarized layer and subsequent thin-film metal layer results in a smaller pad footprint, allowing more of the metal layer to serve as a “ground” (reference) plane. Alternatively, the fine-geometry methods allow definition of narrower signal lines, allowing more signal lines to be routed in a selected area, and/or allowing greater flexibility in the placement of signal lines. The use of thin layers also preserves the planarity of the surface of the thin film stack as it is built on the substrate, especially in conjunction with liquid dielectric layer precursors.
[0015] In a further embodiment, a thin dielectric layer is formed over the first thin-film metal layer and a second thin-film metal layer is formed over the thin dielectric layer. Thus, a layer stack having a planarized layer and two thin-film metal layers separated by a thin dielectric layer have been formed on a surface of a laminated printed wiring board. Portions of the first thin-film metal layer serve as a reference plane to signal lines patterned in the second thin-film metal layer. Furthermore, in one embodiment, the reference plane portions shield, at least partially, the signal lines from electrical fields in the metal layer of the laminated printed wiring substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1A is a simplified cross section of a laminated board as is used to form a multi-layer laminated wiring substrate;
[0017] [0017]FIG. 1B is a simplified cross section of a multi-layer laminated wiring substrate;
[0018] [0018]FIG. 1C is a simplified cross section of a multi-layer laminated wiring substrate with a dielectric build-up layer on a surface of the substrate;
[0019] [0019]FIG. 1D is a simplified cross section of a multi-layer laminated wiring substrate with a planarized layer according to an embodiment of the present invention;
[0020] [0020]FIG. 2 is a simplified flow chart of a process for making a planarized layer on a laminated printed wiring substrate and subsequent patterned thin-film metal layer, according to another embodiment of the present invention;
[0021] [0021]FIG. 3A is a simplified top view of a pad, insulating ring, and remaining area in a surface metal layer of a laminated wiring board;
[0022] [0022]FIG. 3B is a simplified top view of a pad, insulating ring, and remaining area in a thin-film metal layer formed on a planarized layer;
[0023] [0023]FIG. 4 is a simplified cross section of a wiring substrate having a multi-layer thin-film stack and a planarized layer formed on a laminated printed wiring substrate; and
[0024] [0024]FIG. 5 is a simplified graph illustrating the improvement in line impedance gained by various embodiments of the present invention in relation to conventional printed wiring substrates.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0025] The present invention provides a printed wiring substrate with improved impedance characteristics and a method for making such substrates. In one embodiment, the beneficial characteristics are obtained by applying methods from semiconductor device manufacturing technology adapted by and in combination with additional techniques for application to laminated printed wiring substrates. Methods and devices are shown with improved planarity and line resolution compared to conventional laminated substrates. These and other attributes, in combination with an improved ground plane, allow a greater portion of signal lines to pass over or under the ground plane. Such signal lines exhibit more predictable and consistent impedance, and in some instances reduced noise or cross-talk.
[0026] In order to properly provide details of the present invention, it is desirable to understand the printed wiring substrate upon which it is implemented. The printed wiring substrate serves two main functions. First, it is the platform upon which a high-density thin-film interconnection is built. Second, it can provide a transition between the very small pitch (e.g. 50-250 microns) of the solder bump, ball grid, or flip chip devices mounted on the substrate and the relatively coarse pitch (e.g. 0.8-1.27 mm) of the electrical contacts needed to mate to the outside world, such as through an edge connector or cable connector.
[0027] [0027]FIG. 1A is a simplified cross-sectional view of a single laminate printed wiring board substrate 10 that can be used as a sub-laminate sheet in a multi-layer laminated substrate. The substrate is formed from a layer of insulating material 12 such as “NEMA FR5” epoxy resin with copper sheets 14 and 16 laminated to its upper and lower surfaces, respectively. “Upper and lower” are used herein simply as relative terms for ease of description, and do not limit the actual orientation of any layer or structure. The copper sheets are half-ounce copper foil, for example. A desired conductor pattern 18 is transferred to the copper using photolithography and a wet chemical etch to remove the unwanted copper, leaving the desired circuit pattern. Several of these sub-laminates with various circuit patterns can be laminated together to form a four layer printed wiring substrate as shown in FIG. 1B.
[0028] [0028]FIG. 1B is a simplified cross-sectional view of a four layer-printed wiring board substrate 20 which can make use of the present invention. The substrate includes two sub-laminate structures similar to that shown in FIG. 1A. “Four-layer” refers to the four metal layers- two on each sub-laminate sheet. An additional insulative epoxy layer 22 separates and joins the sub-laminate sheets. Internal conductive layers 24 , 26 are typically used for power and ground planes and to provide stiffness to the printed wiring board substrate, although signal lines may be incorporated into these layers. A plated through hole (“PTH”) 28 forms an electrical connection between one conductive layer and another. These plated through holes are filled with a plug material 30 , for example, a conductive epoxy. The plug material provides a planar surface with the collar or flange of the PTH to form a pad 32 , however, the surface step topology of this laminated substrate is typically about 20-35 microns. Alternatively, the PTH can be capped (not shown), with or without filling.
[0029] [0029]FIG. 1C is a simplified cross section of a portion of a printed wiring substrate 40 with a laminated substrate base 42 . The laminated substrate base includes a dielectric layer 44 , as discussed above in relation to FIG. 1B, as well as a patterned metal layer 46 . A conventional build-up layer 48 has been applied to the laminated substrate. This build-up layer has at least two attributes that affect its use in subsequently forming signal lines having a selected characteristic impedance. First, the thickness of the build-up layer varies, such as at the corners 50 of the metal features 52 . Second, the layer is not planar, but dips 54 between the metal features, having a typical surface step topology of between about 3-5 microns. Another aspect of the build-up layer is that it is often thick enough to cause some laminated substrates to warp unless a compensating build-up layer is also formed on the opposite surface of the substrate.
[0030] [0030]FIG. 1D is a simplified cross section of a portion of a printed wiring substrate with a planarized layer 56 according to an embodiment of the present invention. The planarizing layer 56 has been formed by applying a second layer 58 of dielectric material over a first layer 57 of dielectric material. The planarizing layer material could be applied as a liquid, by spinning, spraying, or curtain dipping, for example. In a preferred embodiment, both layers are the same material, resulting in consistent dielectric properties throughout the layer, as well as convenient photo-developing. It is believed that the resultant planarized surface is achieved through a combination of the surface tension and viscosity of the applied liquid dielectric layer precursor, in addition to the reduced step height and “softening” (rounding) of the step edges produced by the first dielectric layer.
[0031] [0031]FIG. 2 is a simplified flow chart of a process 200 of fabricating a high-density, improved impedance wiring substrate according to an embodiment of the present invention. A first layer of a liquid dielectric precursor material is applied to a laminated wiring substrate (step 202 ). In a preferred embodiment, the planarizing dielectric material is spun-on V-259PA™, available from NIPPON STEEL of Tokyo, Japan, or AVATREL™, available from the BF GOODRICH COMPANY, for example. In another embodiment, a planarizing dielectric layer may be applied on a build-up surface a substrate supplied by the substrate vendor. In general, it is desirable that the planarized dielectric layer have a surface step topology of about 2 microns or less. After forming the planarized dielectric layer, vias are formed through the dielectric layer (step 206 ), by photo exposing, developing, and curing to access underlying metal features.
[0032] In a particular embodiment, an initial 35 micron step height of the surface metal layer was reduced to about 20 microns with a first application of a 10 micron thick spun-on layer of V-259PA™. The assembly was pre-baked at 90° C. for 30 minutes and a second coat of V-259PA™ was spun-on. The second coat was also applied to a thickness of about 10 microns, for a total dielectric layer thickness of about 25 microns, and pre-baked. The thicknesses of the dielectric layers are those thicknesses that would be expected to result if a single layer were applied. However, applying one layer over another, without intermediate developing or complete polymerization, results in some swelling of the first layer, and hence a total thickness slightly greater than might be expected from a simple sum of the thicknesses of the two layers. Vias were formed in this dielectric layer by photo exposing and developing, as is known in the art, followed by a curing bake at 160° C. for 1.5 hours.
[0033] A thin metal base was formed by sputtering a metal base or “seed” coat of chromium-copper about 2 microns thick (step 208 ) onto the planarized dielectric layer and then copper plating (step 210 ). Alternatively, the entire layer may be sputtered or alternative plating methods can be used. The metal layer can then be patterned using well known techniques such as a photo-lithography and etch process.
[0034] [0034]FIG. 3A is a simplified representation of a top view of PTH pads 32 on the surface of a multi-layer laminated substrate 20 . The pads, which serve as an electrical contact area for the PTHs (not shown in this view) that are filled with a plug material 30 , have an electrically insulating circumferential ring or gap 60 between the pad 32 and the metal field 62 to electrically isolate the two structures. By way of example only, if the pitch of the PTHs is 1 mm (typically laid out in a grid pattern) and the diameter of a metal flange and its associated circumferential gap is 0.8 mm, then the distance, represented by the arrow 64 , between two adjoining PTHs is only 0.2 mm. These dimensions are consistent with current laminated board technology. For ease of discussion, the combined area of the pad and its associated circumferential gap will be referred to as the “pad footprint”.
[0035] [0035]FIG. 3B is a simplified representation of a top view of a pad 66 formed on a planarized layer using a thin-film process according to the present invention. For purposes of illustration, the PTH pitch is 1 mm and a PTH (not shown) underlies and is electrically connected to the pad; however, because of the improved process control provided by forming the pad on the planarized layer, the reduced footprint of the pads provides a separation, represented by the arrow 68 , of approximately 0.75 mm. Thus, by stepping the contact pad from the laminate to the planarized layer, the metal plane 70 that remains is greatly increased.
[0036] [0036]FIG. 4 is a simplified cross section of a planarized layer 56 on a laminated wiring substrate 20 with a thin film stack 72 having three thin-film metal layers 74 , 76 , 78 , according to an embodiment of the present invention. “Thin-film” generally means that the metal layers are less than about 10 microns thick. Processes for forming such layers include sputtering and pattern plating. In pattern plating, a very thin “seed” layer is typically sputtered before a plating step provides the rest of the metal to the layer. Alternatively, the entire layer could be sputtered; however, pattern plating is preferred to retain the desired pattern geometry. The dielectric layers in the thin-film stack are similarly as thin, in general; however, in some applications the dielectric layer may be thicker than 10 microns. Additionally, in some structures, multiple thin dielectric layers may combine to form a portion of a dielectric layer that is thicker than 10 microns. The intervening dielectric layer(s) are typically formed by applying a viscous liquid polymer precursor that generally results in a dielectric material with a relative dielectric constant less than 5, and in some instance as low as about 2, or less.
[0037] A planarized dielectric layer 56 has been formed on the laminated wiring substrate 20 , and a first patterned thin-film metal layer 74 has been formed on the build-up layer, which is about 15-30 microns thick. In relative terms, the surface of the planarized layer is 90% fully planarized with a step topology of about 2 microns. The first thin-film metal layer is about 4-10 microns thick, and is copper plated over a chrome-copper seed layer. Portions of this first thin-film metal layer serve as a reference, or “ground”, plane 80 , as discussed in further detail below. It is understood that “ground” is a relative term, and that the actual reference potential may not be at earth ground potential. A conductive via 82 , such as described above in conjunction with FIG. 3B, makes electrical contact to the underlying PTH 28 . The top of the conductive via is shown as flat, and the thicknesses of the layers are exaggerated, for purposes of illustration. It is understood that a small dimple or depression may occur over the via opening; however, because of the thinness of the layers in the thin-film stack, in addition to the use of viscous liquid polymer precursors for subsequent dielectric layers, acceptable planarity is maintained. The pads 84 associated with these vias have a substantially smaller footprint, typically teardrop shaped, with a width (essentially perpendicular to the signal line routing direction typically between about 50-68 microns, but often less than 40 microns, than the underlying PTH pads, due at least in part to the superior planarity of the surface in combination with the line resolution of the thin-film processes. For comparison, a similar pad formed on a conventional build-up layer over a laminated surface metal layer would have a width of typically between about 75-100 microns, but possibly as low as 45 microns, using similar process technology.
[0038] A second dielectric layer 86 has been formed over the first thin-film metal layer 74 . This second dielectric layer is spun-on V-259PA™, for example, and is about 10 microns thick, but could be other material and/or another thickness. A second thin-film metal layer 76 has been formed over the second dielectric layer 86 and patterned. The second thin-film metal layer is formed by pattern plating or sputtering, for example. A second conductive via 88 has been formed using a photo-exposure and development process. The pad 90 of the second conductive via is only about 38 microns across in one embodiment, but smaller dimensions are possible.
[0039] In this embodiment, signal lines 92 patterned in the second thin-film metal layer operate in conjunction with the second dielectric layer 86 , and a reference plane portion 80 of the first thin-film metal layer to form a signal transmission line of a desired characteristic impedance, Z 0 . In a particular embodiment, the signal lines are about 16 microns wide and are separated from each other by a spacing of about 16 microns to result in a nominal line impedance of about 50 ohms. In another embodiment, the signal lines are wider to achieve lower impedance. Alternatively, the intervening dielectric layer can be made thinner to retain high-density routing of the signal lines. This desired impedance depends on, among other factors, the width of the signal lines, the distance of the signal line from the reference plane, and the dielectric constant of the dielectric material separating the signal line 92 from the reference plane 80 . Therefore, the thickness of the dielectric material is chosen according, at least in part, to the dielectric constant of the material to achieve a selected coupling between the signal lines and the reference plane, in light of the desired characteristic impedance.
[0040] In one embodiment, it is desired that most of the signal lines have a characteristic impedance of about 50 ohms. In another embodiment it is desirable that most of the signal lines have a characteristic impedance of about 28 ohms. In general, a signal line with an impedance higher than 50 ohms is more susceptible to noise. A signal line with a very low impedance may take additional charge and/or time to reach a desired signal potential. It is desirable, but not essential, that the reference plane be situated between the signal lines and the laminated wiring substrate. It is also desirable that the signal lines do not pass over a pad.
[0041] First, the pad (which may not be at ground potential) and the gap around the pad disrupt the characteristic impedance of the line. Second, a pad may be “hot”, having either a DC or AC voltage that affects signals carried on the signal line. Additionally, even if a pad is not hot, it may act as a noise source, coupling noise energy onto the signal line. It is understood that a signal line does not have to pass over the reference plane for its entire length to achieve the desired impedance, and that some portions, such as the ends, of the signal lines will not pass over the reference plane. However, if a signal line passes over the reference plane for a substantial portion of its length, the desired impedance can be obtained. Referring again to FIGS. 3A, 3B, and 4 , the stepped pad structure in combination with the thin-film metal layer provides an improved reference plane structure that allows most of the signal lines to be routed substantially over the reference plane and thus to achieve the desired impedance.
[0042] A third dielectric layer 94 about 10 microns thick has been formed over the second metal layer 76 . The third dielectric layer can be V-259PA™, for example, with a thickness of about 10 microns. This dielectric layer, and others, can also serve to passivate the underlying metal, and if used as the top layer in a stack, can also serve as a solder mask. If only the first thin film metal layer 74 is present, than the second (next) dielectric layer 86 could serve as a solder mask and passivating layer, etc. In other words, greater or fewer numbers of layers could be used, and this thin film stack is merely exemplary.
[0043] In this embodiment, an optional third thin-film metal layer 78 about 3.5 microns thick has been formed over the third dielectric layer 94 . Additional vias between the metal layers are present, but have not been shown for purposes of illustration. Signal lines 96 have been patterned in the third thin-film metal layer. These signal lines are further away from the reference plane 80 than the signal lines 92 in the second thin-film metal layer. In order to achieve the same desired characteristic impedance, the signal lines in the third thin-film metal layer are wider than the signal lines in the second thin-film metal layer. However, it is not essential that all signal lines in the thin-film stack are designed to have the same characteristic impedance.
[0044] A passivation layer 98 about 10 microns thick has been formed over the third thin-film metal layer. Contact openings 99 in the top of the passivation layer provide the high-density connection pads for an integrated circuit device that can be electrically connected to the thin-film stack of the printed wiring substrate by, for example, wire bonding or flip chip techniques as understood by a person of ordinary skill in the art. Additional vias (not shown) connect various conductive features in different layers of the thin-film stack to the laminated substrate. Plated through holes 28 , provide the low-density connection pads on the opposite side (not shown) of the laminated printed wiring substrate 20 that interface to the outside world. Optionally, a second build-up layer (not shown) can be applied to the opposite side of the laminated substrate 20 to balance the stress placed on the printed wiring substrate by the build-up layers on the surface with the thin-film stack. This balancing layer can also serve as a solder mask to connect the high density interconnect structure to the outside world, for example, to a mother board, cable, or connector.
[0045] Table 1, below, shows the area of ground plane available for signal trace wiring, stated as a percentage, for different metal layers in a printed wiring substrate. A pad pitch of 1 mm is used as an example. The first column is the nominal pad footprint diameter (pad plus insulating gap). The second column is the distance the ground plane runs between pads, and the third column is the percentage of the ground plane potentially available for signal trace wiring where the entire length of the trace would be over the ground reference plane. It is understood that signal trace orientation, interconnect pad location, and chip components reduce the available ground plane area and that these numbers are given as comparative examples. Furthermore, if very few traces are involved, all of the traces could be over the reference plane. The effect that available ground plane and deposition/lithography technologies have on line impedance is further discussed below in conjunction with FIG. 5.
TAB;E1 % Groundplane Technology Pad Footprint Ground Plane Run Available Laminated 0.8 mm 0.2 mm 20 PWB Build-Up 0.45 mm 0.55 mm 55 Layer Thin-film 0.16 mm 0.84 mm 84 Layer
[0046] The pad pitch is determined by the desired mounting pitch of the host board. For purposes of this example, the pitch will remain constant while the pad opening diameters can change as the pads are stepped up through the layers. For example, a typical ball grid array has a pad pitch of 1.0 mm. Since the pad opening diameter of the conventional (laminated) printed wiring board is about 0.8 mm, it can be seen that only about 0.2 mm of ground plane exists between pads. This allows only about five signal lines, each about 16 microns wide with 16 micron gaps separating the lines, to be routed between pads and over the ground plane.
[0047] As the data in Table 1 show, on a conventional build-up layer, the pad opening diameter can be reduced to 0.45 millimeters, providing 0.55 mm of ground plane between pads. This translates into a 55% reference plane area available for signal routing. The pad opening diameter can be reduced to about 0.16 mm using a dual layer thin film dielectric planarization method according to the present invention. This results in about 84% of the signal lines being able to be routed over the ground plane area of the first metal layer to achieve the desired characteristic impedance. Of course, the pad opening diameter could be made bigger, and in a particular embodiment the pad diameter is about 38 microns, resulting in about 62% of the ground plane area being available.
[0048] Alternatively, greater design latitude is provided when laying out the signal lines, if the lines are not so dense as to require the entire available ground plane area. Using current signal line routing techniques, a high-density printed wiring substrate incorporating the present invention can have over 90% of the signal lines within the design impedance tolerance limit, typically 10% of the target impedance. In a particular embodiment, 94% of the signal lines are 50±5 ohms. It is recognized that a pad footprint of 0.16 mm is given as an example when the pitch remains 1 mm. The pad size can be further reduced to accommodate a finer pitch, such as an integrated circuit chip with a solder-ball array, and the present invention can transition between one pitch and another.
[0049] [0049]FIG. 5 is a simplified graph 500 illustrating the portion of signal lines having a desired characteristic impedance for various layers in a printed wiring substrate. For purposes of illustration, a pad pitch of 1 mm will be used. As described above in conjunction with FIG. 3A, a laminated printed wiring substrate typically has a pad footprint of about 0.8 mm. For a typical, exemplary high-density wiring pattern, only about 15% of the signal lines will be able to be routed over a ground plane to achieve the desired design impedance of 50 ohms, as illustrated by the first curve 502 . The availability to form a signal line of the desired impedance is affected by both the pad footprint and the process limitations, i.e. critical dimension, of the laminated PWB technology. A second curve 504 shows that about 20% of the signal lines will meet the desired impedance if the PTHs are capped or filled. If a conventional build-up layer is used under the thin film metallization, a little over 50% of the signal lines, exhibit the desired characteristic impedance, as shown by a third curve 506 . If dual layer dielectric planarization method is used in conjunction with thin-film metal layers over 50% of the signal lines have the desired characteristic, as shown in a fourth curve 508 , depending on the designed pad dimensions.
[0050] What the percentages shown in FIG. 5 express is that, using a conventional printed wiring board for example, signal traces will run over the ground plane for their entire length only about 15 % of the time. The balance of the traces will run over the ground plane for only part of their length. Some traces will run over the ground reference plane for most of their length, some for a moderate segment of their length, and others for little of their length, yielding a very non-uniform impedance characteristic.
[0051] An additional advantage of using thin-film techniques on a planarized layer is that a transition can be made between the relatively coarse (i.e. 1 mm) pad pitch of the laminated printed wiring substrate to a much finer pitch of a solder bump array, which can be as close as 100 microns. It is understood that a minimum pad size may be required for a particular electrical connection technique. Another advantage of using a multi-layer dielectric planarization technique, versus a build-up layer, for example, is that the stresses created by the planarization layers is much less than a conventional build-up layer. Hence, it is not necessary to balance the stress by applying a similar layer or layers on the opposite side of the laminated wiring substrate, as is common with conventional build-up techniques.
[0052] From the above discussion it can be seen that uniformity of signal line impedance can vary as a result of the percent of reference plane available. As seen in FIG. 5, not only does the number of signal lines having the desired characteristic impedance vary according to the technology used, but the divergence, i.e. the difference between the target impedance and the highest impedance, varies with the technology used. Thus, the present invention provides for a greater number of signal lines within the design impedance tolerance, and signal lines falling outside of the design impedance tolerance are more likely to be closer to the design impedance than conventional signal lines. Stated differently, use of the present invention will allow maximum signal line routing freedom with a minimum of impedance variation among the total population of signal lines.
[0053] While the invention has been fully described above, those skilled in the art will recognize alternatives embodiments and equivalents. For example, while specific materials and dimensions have been described for a selected characteristic impedance, other materials and dimensions can achieve the same impedance, or another characteristic impedance. Similarly, the polymer-type liquid dielectric precursors are given as examples only, as are the methods of their application. Other liquid dielectric precursor materials exist or may be developed, and a positive-type material is specifically contemplated. Other metal systems and methods of layer formation might be used as well, such as physical vapor deposition, low temperature chemical vapor deposition, or other types of metals other than copper-based layers. These equivalents and alternative embodiments are intended to be within the scope of the invention. Accordingly, the scope of the invention should not be limited by the examples given above, but is to be interpreted according to the claims below.
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The present invention provides a solution to the problem of controlling the inter-layer impedance of a deposited thin film layer stack accommodating high-density interconnects. The invention enables high-density signal lines to be routed over a reference plane to achieve a desired characteristic impedance. In one embodiment, a first thin-film metal layer is formed on a planarized layer fabricated from multiple thin film dielectric layers. The reduced pad footprint in the first thin-film metal layer allows a major portion of the first thin-film metal layer to serve as a reference, or ground, plane to signal lines formed in a second thin-film metal layer that is separated from the first thin-film metal layer by a thin dielectric layer.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to co-pending U.S. patent application Ser. Nos. 11/829,900 filed Jul. 28, 2007, and 12/242,477 filed Sep. 30, 2008, which applications are incorporated by reference herein in their entireties.
TECHNICAL FIELD
[0002] This disclosure generally relates to fabrication of composite parts, and deals more particularly with a method and apparatus for forming and applying composite layups such as doublers, to part surfaces having complex geometries.
BACKGROUND
[0003] Automated fiber placement (AFP) machines may be used to layup composite laminate structures comprising multiple plies of one of more fiber orientations. Where the entire structure is fabricated using an AFP machine, the build rate may be dependant upon the speed of the AFP machine, since the plies are normally formed sequentially. In order to accelerate the build process, certain segments of the structure may be built by hand and applied to the structure as preassembled kits. For example, doublers may be preassembled and applied by hand as a subtask during the AFP build sequence. However, preassembling doubler layups by hand can be time consuming and difficult, particularly where the doublers must be applied to a structure having surface complex geometries, such as a multi-contoured nose or tail section of an airplane. Prior attempts to preassemble doublers using automated equipment have been limited to layups that are either flat or which have a constant curvature in one dimension.
[0004] Accordingly, there is a need for a method and apparatus for forming and applying layups such as doublers to composite structures having complex surface geometries which include multiple contours.
SUMMARY
[0005] The disclosed embodiments provide a method and apparatus for forming and applying layups on composite structures having complex shapes, such as multi-contoured parts. Layup, application and compaction requirements are integrated into a process that may use a single tool. The layups may be quickly formed to match the geometry of the part surface using an AFP machine to layup composite material on a tool having a multi-contoured tool face substantially matching the part surface. The tool may also be used to place and compact the layup on the part surface. The disclosed method and apparatus allows layups such as doublers to be fabricated off a main assembly line, thus permitting them to be reworked as necessary and inspected without slowing down the main assembly process.
[0006] According to one disclosed embodiment, a method is provided of forming and placing a composite layup on a contoured part. The method includes forming a contoured composite layup on a tool contoured to substantially match the contour of the part. The method also includes generating a set of location data representing the location of the part relative to the tool. The method uses a manipulator and the location data to move the tool into proximity to the part and place the contoured layup on the part. Forming the contoured composite layup may be performed using an automatic fiber placement machine to automatically place composite material on the tool. The layup may be compacted against the part by inflating a bladder on the tool and/or by inflating a bag on the tool. The bag may be separated away from the compacted layup by deflating the bag. Generating the location data may be performed by determining the three-dimensional (3-D) position of the tool contour relative to the 3-D position of the part contour in a common 3-D reference system.
[0007] According to another embodiment, a method is provided of applying composite doublers on a part having a multi-contoured surface. The method includes drawing a vacuum bag down onto a multi-contoured face of a tool substantially matching the contours of the part surface. Composite plies are laid up on the tool face over the bag. The method includes generating a set of location data representing the location of the tool face relative to the surface of the part. The method further comprises using the location data and a manipulator to automatically move the tool into proximity to the part and place the layup against the part surface. The method also includes compacting the layup against the part surface by inflating the bag. Drawing the bag down onto the tool face is performed by drawing a vacuum in the bag.
[0008] According to still another embodiment, a method is provided of applying a layup on a part having a multi-contoured surface. The method includes drawing a flexible bag down onto a multi-contoured face of a tool substantially matching the contours of the parts surface. The method includes placing a composite layup on the bag-covered tool face and moving the tool into proximity to the part and using the tool to place the layup on the parts surface. The method also includes compacting the layup against the parts surface by inflating the bag and separating the bag from the compacted layup by drawing a vacuum in the bag. The method may further comprise compacting the layup against the parts surface by inflating a bladder between the tool face and the bag.
[0009] According to still another embodiment, apparatus is provided for applying composite layups on a contoured substrate. The apparatus includes a tool, first and second compactors, and means for controlling the first and second compactors. The tool is adapted to be mounted on a manipulator for moving the tool into proximity to the substrate and includes a contoured tool face substantially matching the contour of the substrate. The first flexible compactor covers the tool face and is adapted to have a composite layup placed thereon. The second flexible compactor is disposed between the first compactor and the tool face for compacting the layup onto the substrate. The first compactor may include a vacuum bag sealed to the tool, and the second compactor may include a flexible, inflatable Bladder. The means for controlling the first and second compactors may include a pressure source, a vacuum source, and a controller for selectively pressurizing and depressurizing the first and second compactors using the pressure source and the vacuum source.
[0010] In accordance with another embodiment, apparatus is provided for forming and applying composite layups on a part having a multi-contoured surface. The apparatus includes a tool having a multi-contoured face substantially matching the contours of the part surface, a flexible bag on the tool, a manipulator, and a controller. The flexible bag covers and conforms to the contours of the tool face and is adapted to have a layup placed thereon and pressurized to compact the layup against the part surface. The manipulator manipulates the tool into proximity to the part and places the layup on the part surface. The controller controls the operation of the manipulator and pressurization of the bag. The apparatus may further comprise an inflatable bladder between the tool face and the bag for compacting the layup against the part surface. In one embodiment, the tool is formed of structural foam.
[0011] According to still another embodiment, apparatus is provided for forming and applying composite layups on a part having a multi-contoured surface. The apparatus includes a tool, a robotic manipulator, an automatic composite fiber placement machine, a locator system, a compactor, and control means. The tool includes a multi-contoured face substantially matching the contours of the part surface. The robotic manipulator has the tool mounted thereon for manipulating the tool. The automatic composite fiber placement machine includes a fiber placement head for forming a multi-ply composite layup on the tool face. The locator system generates a set of location data that locates the fiber placement head, the tool face and the part surface relative to each other in a common spatial reference system. The compactor on the tool compacts the layup against the part surface, and the control means controls the operation of the manipulator, the automatic fiber placement machine and the compactor, based on the location data.
BRIEF DESCRIPTION OF THE ILLUSTRATIONS
[0012] FIG. 1 is an illustration of a functional block diagram of apparatus for forming and applying composite layups having complex geometries.
[0013] FIG. 2 is an illustration of a perspective view of a multi-contoured nose section for an airplane having a composite doubler applied and compacted thereon in accordance with the disclosed embodiments.
[0014] FIG. 3 is an illustration of an isometric view of a tool used to form and apply the doubler shown in FIG. 2 , a compaction bag and bladder not shown for clarity.
[0015] FIG. 4 is an illustration of a side view of apparatus for forming and applying composite layups having complex geometries to the nose section shown in FIG. 2 .
[0016] FIG. 5 is an illustration of a combined sectional and diagrammatic view of the tool and locator system.
[0017] FIG. 6A is a sectional view of the tool when initially assembled.
[0018] FIG. 6B is an illustration of a perspective view of the tool shown in FIG. 6B .
[0019] FIG. 7A is an illustration similar to FIG. 6A but showing the bag having been drawn down against the tool surface.
[0020] FIG. 7B is an illustration similar to FIG. 6B but showing the bag having been drawn down against the tool surface.
[0021] FIG. 8A is an illustration of a sectional view of the tool showing an automatic fiber placement head forming a layup on the tool face.
[0022] FIG. 8B is an illustration of a perspective view of the tool, showing a layup having been partially formed on the tool face.
[0023] FIG. 9A is an illustration of a sectional view of the tool showing the layup having been placed on the part surface, and the tool bladder having been inflated to compact the layup against the part surface.
[0024] FIG. 9B is an illustration of a perspective view showing the tool placing the layup on the part surface.
[0025] FIG. 10 is an illustration similar to FIG. 9A but showing the bag on the tool having been inflated to further compact the layup against the part surface.
[0026] FIG. 11 is an illustration similar to FIG. 10 , but showing the bag having been separated from the layup as a result of a vacuum being applied to the bag.
[0027] FIG. 12 is an illustration of a flow diagram showing a method of forming and placing layups having complex geometries on a multi-contoured part surface.
[0028] FIG. 13 is an illustration of a flow diagram of aircraft production and service methodology.
[0029] FIG. 14 is an illustration of a block diagram of an aircraft.
DETAILED DESCRIPTION
[0030] Referring first to FIGS. 1-3 , the disclosed embodiments relate to a method and apparatus for forming and placing a composite layup 20 on a substrate 22 having a complex geometry, which may comprise a multi-contoured surface 22 of the part 24 shown in FIG. 2 . In the illustrated embodiment, the part 24 comprises the nose section of an airplane, and the layup 22 comprises a doubler 20 that reinforces an area 34 of the nose section 24 . The apparatus includes a tool assembly 25 mounted on a suitable manipulator 36 that is operated by one or more controllers 35 . The manipulator 36 may comprise a robot or similar automated device that moves the tool assembly 25 along multiple axes in a reference system 55 based on set of programmed instructions used by the controller 35 .
[0031] The tool assembly 25 includes a tool 26 having a multi-contoured tool face 28 that substantially matches the multi-contoured part surface 22 in the area 34 where the layup 20 is to be applied to the part 24 . The tool assembly 25 also includes first and second compactors 54 , respectively for compacting the layup 20 against the part surface 22 . The tool assembly 25 further includes a tool base 30 upon which the tool 26 is mounted. Each of the compactors 54 , 56 respectively, is inflated and deflated respectively using a pressure source 62 and a vacuum source 64 operated by the controller(s) 35 .
[0032] The layup 20 may be formed on the multi-contoured tool face 28 by an automatic fiber placement machine (AFP) which may also operated by the controller(s) 35 . A locator system 45 generates a set of location data 45 a that locates the position and orientation of the tool face 28 relative to the part surface 22 in the three dimensional special reference system 55 . Similarly, the locator system may be used by the controller 35 to locate and coordinate the movement of the AFP machine 42 relative to the tool face 28 .
[0033] Attention is now directed to FIGS. 4 and 5 which illustrate additional details of the apparatus. In this embodiment, the manipulator 36 comprises a robot 36 mounted for linear movement along a pair of rails 38 . The robot 36 includes a robot arm 40 having the tool assembly 25 mounted on the end thereof by means of a quick-change adapter 32 ( FIG. 5 ). The quick-change adapter 32 allows differently configured tools 26 to be quickly mounted on the arm 40 in order to place differently configured layups 20 on different areas of the part 24 that have differing geometries. As previously mentioned, the robot 36 is operated by one or more programmed controllers 35 ( FIG. 1 ) and is capable of displacing the tool assembly 25 along multiple axes within spatial reference system 55 ( FIG. 5 ). The robot 36 manipulates the tool assembly 25 to place a doubler or other layup 20 in a targeted area 34 on the multi-contoured surface 22 of the part 24 .
[0034] The AFP machine 42 may comprise a second robotic device 42 a mounted for linear movement along the rails 38 and includes an automatic fiber placement head 44 mounted on the end of a robotic arm 46 . As will be discussed below, the head 44 lays down multiple strips or courses of composite fiber tape or tows on the tool face 28 to form a multi-contoured layup 20 which is then placed and compacted onto the tool surface 22 by the tool assembly 25 positioned by the robot 36 . In an alternate embodiment, the layups 20 may be kitted and delivered to the robot on a conveyor (not shown) or carousel (not shown).
[0035] The locator system 45 ( FIG. 1 ) monitors and updates the position of the tool 26 , and thus the tool face 28 ( FIG. 1 ), relative to the part 24 , and specifically the part surface 22 . The use of the locator system 45 allows the tool assembly 25 and the robot 36 to be mobile, rather than being mounted in fixed positions. This mobility may improve placement accuracy while contributing to a lean manufacturing process. As previously mentioned, the locator system 45 ( FIG. 1 ) generates a set of location data 45 a ( FIG. 1 ) in order to coordinate the movements of the AFP machine 42 , the tool assembly 25 and the part 24 within the common spatial reference system 55 ( FIG. 5 ). The location data 45 a may be constantly updated and used in a closed feedback loop by the controller(s) 35 to achieve placement accuracy of the layup 20 on the part surface 22 .
[0036] The locator system 45 may comprise one or more laser trackers 48 which develops position data by directing a laser beam 52 onto reflective targets 50 placed on the tool assembly 25 and the part 24 . The locator system 45 may optionally further include photogrammetry cameras 33 which record the location of laser beam light reflected off of the reflectors 50 in order to measure the position of the tool assembly 25 relative to the parts surface 22 in the spatial coordinate system 55 . The photogrammetry cameras may comprise, for example and without limitation, commercially available cameras such as commercially available V-Star cameras. Using a combination of photogrammetry and laser tracker measurements of multiple targets 50 , a determination may be made of the position of the tool face 20 a relative to the part surface 22 in the common spatial reference system 55 . The photogrammetry and laser tracking measurements of the locations of the targets may be integrated together utilizing one or more computers and software programs which may comprise a part of the controllers 35 . The locator system 45 including the reflective targets 50 may be similar to that disclosed in U.S. Pat. No. 7,5897,258 issued Sep. 8, 2009 which is incorporated by reference herein in its entirety.
[0037] Referring now particularly to FIG. 5 , the tool 26 may comprise, for example and without limitation, a light-weight structural foam in which the tool face 28 may be formed by any of several well-known fabrication techniques such as, without limitation, machining and molding. The tool 26 may be fabricated from other low cost materials using low cost fabrication methods to reduce the cost of the tool 26 . The first compactor 54 may comprise an inflatable bladder 54 which may be positioned on the tool face 28 or recessed slightly within the tool face 28 , as shown at 54 a . The second compactor 56 may comprise a flexible vacuum bag 56 which is sealed around its periphery 56 a to the tool 26 , thereby forming a pressurizable, substantially vacuum tight chamber 65 over the tool face 28 . A breather 58 may be provided between the tool face 28 and the bag 56 to allow air movement under the bag 56 during evacuation. The bag 56 and the breather 58 both cover the tool face 28 thereby protecting the tool face 28 from damage, and facilitating removal of the layup 20 from the tool 26 . The bag 56 may have a surface texture that allows composite layup pre-preg to adhere to its surface during the layup process without distortion, yet is sufficiently elastic to inflate, compact and release the layup 20 onto the part surface 22 . The bag 56 may be formed from, for example and without limitation, latex film, poly packaging film, or urethanes having textured or non-textured surfaces.
[0038] In the embodiments illustrated in FIGS. 5 , 6 A, 7 A, 8 A, 9 A and 10 , the bladder 54 is illustrated as a series of generally parallel, separate but interconnected bladders 54 b that operate as a single bladder 54 . However in other embodiments, the bladder 54 may comprise a single bladder extending over substantially the entire tool face 28 . The bladder 54 may be shaped, sized and have its inflation sequenced to optimize compaction against the part surface 22 . The bladder 54 and the bag 56 are each connected through a series of flow control valves 72 and three way control valves 70 to a pressure source 62 and a vacuum source 64 . The control valves 70 are operated by the controller 74 which may be the same or different from the previously discussed controller(s) 35 ( FIG. 1 ), and function to selectively couple either the pressure source 62 or the vacuum source 64 to the bladder 54 and the bag 56 . Thus, the automatically operated control valves 70 may couple either or both the bladder 54 and the bag 58 with the pressure source 62 in order to pressurize and thereby inflate either the bladder 54 or the bag 56 . Similarly, the control valves 70 may couple the vacuum source 64 to either the bladder 54 or the bag 56 in order to deflate the bladder 54 , or evacuate the bag 56 which draws the bag 56 down onto the tool face 28 . In some embodiments, the tool face 28 may be provided with vacuum grooves 60 that may also be coupled with the control valves 70 in order to assist in pressurizing/depressurizing the chamber 65 .
[0039] FIGS. 6-11 illustrate use of the tool assembly 25 and sequential steps used to form a multi-contoured layup 24 , and then place and compact it onto the part surface 22 . Referring initially to FIGS. 6A and 6B , after securing the tool 26 on the tool base 30 , the bag 56 and breather 58 are installed over the tool face 28 , and the perimeter 56 a of the bag 56 is sealed to the tool 26 , forming a substantially vacuum tight, pressurizable chamber 65 ( FIGS. 5 and 6 ) between the bag 56 and the tool 26 . Vacuum lines 66 and pressure lines 68 ( FIG. 5 ) are then installed and connected with both the bladder 54 and the bag 58 . At this point, neither line 75 nor line 77 is connected to either the pressure source 62 or the vacuum source 64 through control valves 70 ( FIG. 5 ), but rather are open to the atmosphere, consequently the bladder 54 and the chamber 65 are substantially at atmospheric pressure.
[0040] Referring now to FIGS. 7A and 7B , the tool assembly 25 is readied by connecting the vacuum source 64 to both lines 75 and 77 using control valves 70 , which results in substantially full deflation of the bladder 54 and evacuation of air from the chamber 65 . Evacuation of air from the chamber 65 causes the bag 56 to be drawn down onto the tool surface 28 so that the bag 56 conforms substantially to the multiple contours of the tool face 28 .
[0041] Referring to FIGS. 8A and 8B , with the bag 56 drawn down onto the tool face 28 , the fiber placement head 44 may commence laying down composite fiber material onto the bag according to a prescribed ply schedule. The plies conform to the contours of the tool face 28 as they are being formed by the AFP machine 42 , consequently the layup 20 possesses contours substantially matching those of the part surface 22 . Lines 75 and 77 remain coupled with the vacuum source 64 as the layup 20 is being formed on the tool face 28 .
[0042] Referring to FIGS. 9A and 9B , after the layup 20 has been formed on the tool 26 , the robot 36 moves the tool assembly 25 into proximity with the part 24 , and applies the layup 20 at the desired position 34 (see FIG. 4 ) on the part surface 22 . With the layup 20 applied to and contacting the part surface 22 , the pressure source 62 is coupled with lines 75 , while the vacuum source 64 remains coupled with line 77 . Pressurization of lines 75 result in inflation of the bladder 54 , causing the bladder 54 to inflate and apply pressure to the layup 20 which compacts the layup against the part surface 22 . During this compaction of the layup 20 by the bladder 54 , the bag 56 remains deflated as a result of the vacuum applied through line 77 .
[0043] Next, as shown in FIG. 10 , the pressure source 62 is coupled with the line 77 which pressurizes and inflates the bag 56 , causing it to expand and apply pressure to the layup 20 which further compacts the layup 20 against the part surface 22 .
[0044] FIG. 11 illustrates the next step in the process in which the vacuum source 64 is coupled with both lines 75 and 77 , resulting in deflation of both the bladder 54 and the bag 56 . Deflation of bag 56 causes the bag 56 to separate and retract away from the layup 20 . Upon separation of the bag 56 from the layup 20 , the robot 56 returns the tool assembly 25 to a standby position (not shown) in readiness for the next layup/application cycle.
[0045] Attention is now directed to FIG. 12 which broadly illustrates the steps of a method of forming and applying composite layups to a multi-contoured part surface. Beginning at step 76 , a tool 26 is fabricated which, in the illustrated example, may be performed by forming a structural foam into the desired shape having a multi-contoured tool face 26 that substantially matches the part surface 22 . As previously mentioned, the structural foam may be formed into the desired tool shape using any of various known fabrication processes including but not limited to machining and molding. Next, at step 78 , the vacuum/pressure lines 75 , 77 are placed in the tool 26 and coupled with the flow control valves 72 . At step 80 , a set of location data is generated, using photogrammetry and/or laser tracking techniques previously described, or other techniques, in order to locate the tool face 26 relative to the part surface 22 . At step 82 , vacuum is applied to both the bladder 54 and the bag 56 , causing the bag 56 to be drawn down onto the multi-contoured tool face 26 . At step 83 , a composite layup is formed on the tool face 26 by using the AFP machine 42 to form one or more plies over the bag 56 which conforms to the tool face 26 .
[0046] With the multi-contoured layup 20 having been formed, then, at step 84 , the robot 36 or other manipulator moves the tool assembly 25 into proximity with the part 24 , and places the layup 20 onto the part surface 22 . Next, as shown at step 86 , the bladder 54 is pressurized, causing it to inflate and apply compaction pressure to the layup 20 while the vacuum bag 56 remains deflated. Then, at step 88 , the bag 56 is also pressurized, causing it to inflate and apply additional compaction pressure to the layup 20 which further compacts the layup 20 against the part surface 22 . Following compaction, vacuum is applied first to the bag 56 and then to the bladder 54 , causing each of them to deflate and draw away from the layup 20 . In one practical embodiment of the method, the bladder 54 is inflated for one minute while vacuum is applied to the bag 56 . Then, the bag 56 is inflated for one minute, following which vacuum is applied to the bag 56 assist in pulling the bag 56 away from the compacted layup 20 . Finally, at step 92 , the tool assembly 25 is retracted to a standby position, in readiness to repeat the layup formation and placement cycle.
[0047] Embodiments of the disclosure may find use in a variety of potential applications, particularly in the transportation industry, including for example, aerospace, marine and automotive applications. Thus, referring now to FIGS. 13 and 14 , embodiments of the disclosure may be used in the context of an aircraft manufacturing and service method 94 as shown in FIG. 13 and an aircraft 96 as shown in FIG. 14 . Aircraft applications of the disclosed embodiments may include, for example, a wide variety of assemblies and subassemblies such as, without limitation, structural members and interior components. During pre-production, exemplary method 94 may include specification and design 98 of the aircraft 96 and material procurement 100 . During production, component and subassembly manufacturing 102 and system integration 104 of the aircraft 96 takes place. Thereafter, the aircraft 96 may go through certification and delivery 106 in order to be placed in service 108 . While in service by a customer, the aircraft 96 is scheduled for routine maintenance and service 110 (which may also include modification, reconfiguration, refurbishment, and so on).
[0048] Each of the processes of method 94 may be performed or carried out by a system integrator, a third party, and/or an operator (e.g., a customer). For the purposes of this description, a system integrator may include without limitation any number of aircraft manufacturers and major-system subcontractors; a third party may include without limitation any number of vendors, subcontractors, and suppliers; and an operator may be an airline, leasing company, military entity, service organization, and so on.
[0049] As shown in FIG. 14 , the aircraft 96 produced by exemplary method 94 may include an airframe 112 with a plurality of systems 114 and an interior 116 . Examples of high-level systems 114 include one or more of a propulsion system 118 , an electrical system 120 , a hydraulic system 122 , and an environmental system 124 . Any number of other systems may be included. The disclosed method may be employed to fabricate components, structural members, assemblies or subassemblies used in the interior 116 or in the airframe 112 . Although an aerospace example is shown, the principles of the disclosure may be applied to other industries, such as the marine and automotive industries.
[0050] Systems and methods embodied herein may be employed during any one or more of the stages of the production and service method 94 . For example, components, structural members, assemblies or subassemblies corresponding to production process 102 may be fabricated or manufactured in a manner similar to those produced while the aircraft 96 is in service. Also, one or more apparatus embodiments, method embodiments, or a combination thereof may be utilized during the production stages 102 and 104 , for example, by substantially expediting assembly of or reducing the cost of an aircraft 96 . Similarly, one or more of apparatus embodiments, method embodiments, or a combination thereof may be utilized while the aircraft 96 is in service, for example and without limitation, to maintenance and service 110 .
[0051] Although the embodiments of this disclosure have been described with respect to certain exemplary embodiments, it is to be understood that the specific embodiments are for purposes of illustration and not limitation, as other variations will occur to those of skill in the art.
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A composite layup is formed on a tool and placed on a contoured part. The tool is contoured to substantially match the contour of the part. A set of location data is generated which represents the location of the part in space relative to the tool. An automated manipulator uses the location data to move the tool into proximity to the part and place the contoured layup on the part.
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BACKGROUND OF THE INVENTION
This invention relates generally to paint booths and more particularly to a system for reclaiming and distributing heat from such a booth for overall energy conservation.
DESCRIPTION OF PRIOR ART
The application of protective coatings to the surfaces of products is often done in so-called "paint booths". Where the product to be coated is a vehicle, as in an automotive body and paint shop, the booth is relatively large in size in order to accommodate the entire vehicle and an individual workman or workmen moving about in the booth as they spray paint a vehicle. The booth is provided with a system for collecting overspray and maintaining some level of cleanliness in the air. Some such booths also are provided with equipment for raising the atmospheric temperature in the booth following the spraying operation, to "bake" the paint on the vehicle.
Where a paint booth is provided with heating equipment for the paint curing step, relatively large amounts of heat are required to provide a temperature in the booth of between 120 and 160 degrees Fahrenheit. An air circulating system is provided to circulate hot air through the booth, and the various types of arrangements are provided to heat the air to maintain the air temperature in the booth within the above-mentioned range.
When the bake cycle is finished, the hot air is exhausted to atmosphere so the temperature can be reduced to accommodate entry of workmen for touch up, or any other steps to finish the operation, and then remove the vehicle from the booth. As hot air is exhausted from the booth to the surrounding atmosphere by the exhaust system, make-up air may enter the booth from the area within a heated building in which the booth is located, whether the booth be a stand alone structure, or a part of the building structure itself. In any case, this requires heating of the air in the building space if reasonable working temperatures are to be maintained in the building in a cold climate, thus consuming more energy for space heating purposes. Also, if the booth is to be later used for baking paint on another vehicle, heat must be added again to the air to be circulated in the booth, in order to raise the temperature adequately for the curing operation. The result is a very substantial consumption of energy to adequately heat the air in the booth and maintain the proper curing temperatures therein, plus any additional heat required for space heating in the area around the booth for the make-up air needed as the excessively hot air from the booth is discharged to atmosphere after the curing cycle.
Our invention is directed toward conservation of energy in establishments employing a paint booth.
SUMMARY OF THE INVENTION
Described briefly, according to a typical embodiment of the present invention, air circulating systems are provided for a paint booth and which employ two blowers and a combination of dampers and ducts which provide different air circulating circuits for the spraying and baking steps. A heat exchanging system is employed which uses a furnace to add heat directly to the air circulated through the system for raising the temperature for the curing cycle, but also enables transfer to a medium suitable for storage of heat over a prolonged period for subsequent use in a space heating system for the building with which the paint booth is associated.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a building with a system incorporated therein according to a typical embodiment of the present invention.
FIG. 2 is a pictorial view (partially cut-away), and showing the paint booth itself and the air circulating system.
FIG. 3 is a pictorial view partially exploded and partially cut-away, of the above ground cabinetry, ductwork and blowers for air supply and exhaust for the booth.
FIG. 4 is a pictorial view similar to FIG. 2 but showing the in-ground portion of the air circulating system.
FIG. 5 is a pictorial schematic diagram of that portion of the in-ground pit and air passageways that is in air circulation service during the paint spraying cycle of use of the booth.
FIG. 6 is a pictorial schematic diagram of that portion of the in-ground pit and air passageway that is in air circulation service during the paint baking cycle of use of the booth.
FIG. 7 is a pictorial view, partially cut away, of the heat exchanger assembly of the illustrated embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
For the purposes of promoting an understanding of the principles of the invention, reference will now be made to the embodiment illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated device, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates.
Referring now to the drawings in detail, particularly FIG. 1, a body and paint shop building 11 is shown schematically and should be understood to have therein the usual areas and equipment for the necessary cutting, welding, bending, straightening, sanding, parts and equipment and material storage, and offices. In addition, there is the paint booth 12 with the air circulating equipment 13 at the wall 14 thereof. The booth may be fourteen feet wide and twenty-four feet long, for example. According to one important feature of this invention, there is a heat reclamation system. The example shown includes a pump 15 taking hot water through line 16A from the equipment 13 and delivering it to an insulated storage tank 17. Several tanks connected in parallel would also be suitable. A pump 18 takes hot water through line 19 from the storage tank 17 and delivers it through three-way valve 20 to heat exchanging, air handling space heater units 21 spaced throughout the building, and to radiant heater tubes 22 which are for space-heating purposes.
Referring now to FIGS. 2 through 4, the paint booth 12 is shown mounted on floor 26 and has three entrance doors 27 at the front end 28. It can also have doors at the rear end 29, if desired, depending upon the layout of the building and the location of the booth in it. The air handling equipment for the booth is provided at the wall 14.
The locations of the aforementioned walls on the floor 26 are shown fragmentarily in FIG. 4, where a hole 30 is shown in the floor immediately outside the booth wall 14. A catch basin 31 is shown in the floor 26 inside the booth. Its floor 32 slopes slightly downward (about 4°) toward a central opening which is at the top of a pit 33. As shown schematically in FIGS. 4 and 5, this pit is Y-shaped, having the outside wall 34, inside wall 36, both of which converge to the bottom 37, the pit having front and rear end walls 38 and 39, respectively. The "stem" or trunk of the Y serves as sump 40 between two pump/filter stations 40A and 40B at opposite ends of the sump.
In FIG. 4, where the dirt or gravel under floor 26 is omitted from the drawing, there is shown a passageway 41 between vertical front and rear walls 42 and 43, respectively, and which opens through the catch basin wall into the catch basin 31. As shown in FIG. 4, and discernable upon comparing FIGS. 5 and 6, the floor 44 of this passageway is at a level about half the depth from the floor top surface 26, to the bottom 37 of the pit. There is an additional passageway 47 between walls 42 and 43 and under this floor and which communicates with pit 33 through a rectangular opening 48 in pit wall 36. This opening is bounded by the vertical walls 42 and 43, the horizontal partition wall or floor 44 and the bottom wall or floor 49. Floor 44 terminates at an edge 51, while floor 49 terminates at a vertical wall 52 extending up toward the floor 26 and meeting plate 52A mounted to the catch basin ductwork and hanging down from the surface of floor 26 to meet wall 52.
A steel grating 54 is mounted to the top of the catch basin 31 and is strong enough to support the vehicle being treated. The sump may be provided with a collector and/or separator system for any paint that may accumulate in it during a paint spray cycle, and a drain to sewer to permit scrubbing down of the floor of the paint booth and draining dirty water and the like from the pit. A perimeter water pipe 55 with longitudinally spaced water outlets is located at the outside wall of the catch basin all the way around it to sheet water onto the catch basin floor during spraying of paint. This pipe may be supplied by recirculating pump at station 40A under the pit at one end of the sump. Similarly, the pump at station 40B at the opposite end of the sump supplies water to pipe 40C extending the length of passageway 47 to provide a water spray across this passageway. The floor 49 of this passageway slopes down toward sump 40 at 4° so sprayed water and any paint thereby separated from air in the passageway, flows back to the sump. Each of the stations 40A and 40B has a filter to separate collected paint from the recirculating water for the sheeting system in the catch basin and the spraying system in passageway 47.
An L-shaped damper 53 is hinged at 51 to the catch basin frame structure at the center of the floor opening frame portion thereof so that, when the catch basin frame is in place in the floor, and floor opening 30 is properly framed, the damper is pivotable about a horizontal axis at the level of the top of floor 26. It is pivotable from the position shown by the dotted lines 53A in FIG. 3 when the system is in the spray mode of operation, to the position shown by the solid line 53B when the system is in the bake mode.
The air handling system for the paint booth according to the present invention includes two primary air movers. One is an exhaust blower 56 in a plenum 57 at wall 14 of the booth and discharging through the duct 58 to stack 59 outside the building. An electrically controlled damper 61 is in this exhaust stack. A supply blower 62 is located in the plenum 63 at the side wall 14 of the booth and has two alternate sources of intake air. One source is from an intake stack 64 through the roof of the building and through duct 65 to the fresh air intake duct components 65A, 65B and 65C into the plenum 63, for drawing in outside air. An electrically controlled damper 67 is located in the stack 64. Blower 62 can also take air from catch basin 31 through the passageway 41 and through the inboard portion of the floor opening 30 when the floor damper 53 is at its clockwise limit as shown in the solid line 53B in FIG. 3 and into duct components 65A, 65B and 65C to the plenum 63. The blower 62 takes air from duct cabinet portion 65C and blows it through a transition box 68 and up through the circular opening at the top of box 68 into a heat exchanger assembly in heat exchanger cabinet 69 containing a circular array of vertical tubes 70 comprising a heat exchanger "cylinder" 72 whose outer circular dimension corresponds to the circular outlet of the box 68.
A gas burner tube 71 proJects into this heat exchange cylinder 72, opening at 71A near the center, to heat air as it passes up through the vertically extending tubes 70 arranged continuously in a circle, the outer walls of the tubes forming the cylinder 72. The combustion products escape through the flue stack 73 which extend up through the roof to the atmosphere outside the building 11. A heat reclaiming coiled tube 74 is provided in the open center of the heat exchanger cylinder 72 and is coupled through the pipes 16A and 16B to the storage tank 17 (FIG. 1). An additional heat reclaiming coiled tube 75 is located in flue 73 and is connected at its upper and lower ends to tubes 16A and 16B, respectively, at 75A and 75B.
The air tubes 70 of the heat exchanger cylinder open at the top into plenum/duct 76 which opens through the paint booth wall 14 just under its roof, whereby blower 62 delivers hot air to the booth. This air can be directed however desired within the booth to best dry the paint on a vehicle in it. A wash down curtain wall or walls or whatever else might be desired can be used to encourage the collection of overspray and mist in the bottom of the sump 40.
Bake Cycle
Since an important feature of the invention is the thermal reclamation, the paint bake cycle will be described first. The damper 53 is put in the position shown at 53B in FIG. 3, preventing flow of air from the pit up through the outboard half of opening 30 into transition duct 77A. The exhaust blower 56 is off. The gas burner control is set for the desired temperature (somewhere between 105° F. and 175° F.) in the booth, to deliver heat to the air being delivered to the paint booth by the blower 62. With the damper 53 in position 53B in FIG. 3, and considering the location of the outer end wall 45 of passageway 41 from the catch basin 31, directly under the pivot axis of damper 53, the air is circulated only through the upper passageway 41 from the catch basin. The damper 67 is closed in the intake duct 65 as is the damper 61 in the exhaust duct 58. Consequently, during the bake cycle, all of the air is recirculated through the booth from the catch basin through passageway 41, duct portions 65A, 65B, 65C, blower 62, heat exchanger tubes 70, header 76, and back to the booth. A filter 65F in the inlet end of cabinet 65B filters all of this recirculating air. In this way, the temperature in the environment in the booth is raised to the desired level for curing, typically between 105° F. and 175° F. This continues as long as is needed for proper curing of the paint. The heat input at the burner tube 71 can be as much as one million BTU's per hour.
When it is no longer needed to maintain the high temperature in the curing booth, the furnace can be shut off by a thermostat sensing air temperature in the booth. Then the valves 77 can be opened and the pump 15 operated to pump water from the heating coils 74 and 75 through the pipe 16A into the storage tank 17. Consequently, the temperature of the water in the storage tank will rise. Pump 18 can be operated to pump this water throughout the rest of the system and deliver it through space heaters 21 and radiant heaters 22. This operation will take heat from the air being circulated through the booth and deliver it for storage in the storage tank 17. As the water continues to flow through the system, the temperature level of water in the storage tank increases. Consequently, that available for radiant heating can be used as needed by control of the pump 18 and/or the three-way by-pass valve 20. Control of the water flow through the individual space heaters can be handled by individual valves associated with them. If the space heating requirements are less than the total energy to be absorbed to cool down the air in the paint booth, pump 18 can be shut off, or valve 20 switched to by-pass the space heating water circulating system. Pump 15 can remain on, and valve 77 can remain open to permit continued circulation of water through the reclamation coils 74 and 75, and the temperature of the water in the storage tank 17 will continue to rise as heat is added from the reclamation coils. Thus, a heat sump is provided according to the present invention for utilization for the space heating needs whenever desired. It should be understood, of course, that the hot water stored in the tank 17 can be used for other purposes, if desired. Pressure relief valve R (FIG. 1) is provided for safety.
When a bake cycle has been completed, some amount of cool down will occur automatically if the reclamation system is using the heat. Essentially all of the heat can be used by the reclamation system, for total cool down, if desired. But if the weather is warm, the dampers 61 and 67 can be opened, and damper 53 switched 90° counterclockwise to the position 53A (FIG. 3). Blower 56 is turned on and pulls air from pit passageway 47, through duct part 77A, filter 78 therein, filter cabinet outer half 77B and up through filter 79 at the top of 77B, and into the blower intake 56A. The blower has a vertical axis and discharges in the direction of arrow 82 into the lower end of duct 58 from which it exits up through stack 59 into atmosphere outside the building roof 11R. Outside air enters stack 64, duct 65, 65A, 65B, 65C, blower 62, and is discharged thereby through tubes 70 (now unheated) and plenum 76 into the booth.
Spray Cycle
Now that the bake cycle, and cool down methods have been described, the paint spray cycle will be described. The air flow arrangement is slightly different, depending on whether outside temperature is above or below 75° F.
Ambient Above 75° F.
When the outside temperature is above 75° F., all dampers are situated as in the above-mentioned warm weather cool down cycle. Thus, the air circulation is the same. But water is turned on to the pipes 55 in the catch basin and 40C in the passageway 47. This can be done by pumping from the sump, if there is water clean enough therein. Otherwise fresh water can be supplied to these tubes from water mains. Thus, the water wash down in the catch basin, and spray in passageway 47 are intended to prevent movement of paint mist and solids into the intake transition duct 77A. Filters 78 and 79 prevent discharge of contaminants to atmosphere. Filter 79 may be a charcoal filter, for example.
Ambient Below 75° F.
The dampers are arranged as for the above 75° F. spray cycle but, if the outside air is too cold, dampers 61 and 67 may be partially closed. Both blowers are on.
The booth thermostat is adJusted for the desired temperature, and will control the burner accordingly. But heat can be conserved in this mode by opening the shutters 83 and permitting air pulled from pit passageway 47, after filtering at 78 and 79, to be pushed from the bottom of exhaust duct 58 directly to the bottom of intake duct 65, as these shutters are in aligned openings in the adJoining walls 65J and 58J of these ducts. The air is taken from the bottom of duct 65 through ducts 65A, B, C, blower 62 and pushed up through tubes 70, plenum 76 and into the booth. Thus, most of the air is recirculated, depending on the extent of opening of shutters 83.
As can be appreciated upon inspection of FIG. 3, there is some small horizontal space from the dampers 67 and 61 to the walls 65J and 58J respectively, of these ducts. Since these walls touch each other, there is some heat exchange between them as a small amount of fresh air enters duct 65 and a like amount of warm air from blower 56 departs from duct 58. Thus, there is some pre-heating of the fresh air that enters, by the air that exits along the adJoining walls of the ducts, as dictated by the location of the spaces between the dampers and their respective duct walls, even when the dampers are fully closed. During this "below 75°" cycle, water is to be used in the tubes 55 and 40C in the same way as in the "above 75°" cycle.
For all of the cycles, the control of dampers and shutters can be powered, and handled by automatic control to the extent desired for optimum performance.
From consideration of FIGS. 2 and 3 in the light of the foregoing description, it can be appreciated that the present invention enables modular construction for a paint booth. Duct components 65A and 77A can actually be provided by a single cabinet four feet high, four feet wide and six feet long, divided by vertical partition extending lengthwise down the middle and having the cut out in it to accommodate damper 53. Components 65B and 77B can be a single cabinet which is 4×4×4 feet, with a partition down the middle, providing separated intake air passageways for the two blowers. Components 65C and 63 can be a single 4×4×4 cabinet, with part of the top open for discharge of air from blower 62 into the transition box 68. The cabinet 57 is 4×4×4. The ducts 58 and 65 are 2×2 in cross section, but could be a single tube with central longitudinal partition having an opening in it to accommodate the shutters 83. The heat exchanger cabinet is 4×4×4 and can accommodate the indirect firing approach as described above, or a direct firing (furnace combustion products entering the air flow to the plenum 76) approach. As a result of this modular construction, the air circulating system can be employed on either side of the booth. Also the catch basin, pit, sump and in-ground passageway arrangement lend themselves readily to pre-fabricated sheet metal construction, useful in form work prior to pouring concrete for the sub-structure and floor slab. The reclamation system can be employed with other types of paint booths such as Spraybake, Lutro and Binks, for example, locating the reclamation coils where most convenient and where they can pick up heat continuously both during the bake cycle (if desired) and during the cool down cycle.
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 embodiment has been shown and described and that all changes and modifications that come within the spirit of the invention are desired to be protected.
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A paint spray and bake booth has an air heating and circulating system with two blowers and a combination of dampers and ducts which provide different air circulating circuits for the spraying and baking steps. A gas fired furnace with heat exchanging system adds heat directly to the air circulated through the booth to bake paint on a vehicle in it. The heat exchanging system also includes reclamation coils for heat transfer from the circulating air to water in the coils and which is piped to a storage tank for storage of heat over a prolonged period. The storage tank supplies the water through pipes to space heating units in the building in which the paint booth is located. Water is returned from the space heating units to the paint booth heat exchanging system.
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FIELD OF THE INVENTION
[0001] The present invention relates to a method of controlling a closed loop performing a Rankine cycle and to a loop using same.
[0002] As it is well known, a Rankine cycle is a thermodynamic cycle through which heat coming from an external heat source is transmitted to a closed loop that contains a fluid.
BACKGROUND OF THE INVENTION
[0003] There are many types of Rankine cycle loops and more particularly those involving a (liquid/vapour) phase change of a working fluid.
[0004] This type of cycle generally consists of a stage wherein the working fluid used in liquid form is compressed in an isentropic manner, followed by a stage where this compressed liquid fluid is heated and vaporized on contact with a source of heat.
[0005] This vapour is then expanded, in another stage, in an isentropic manner in an expansion machine, then, in a last stage, this expanded vapour is cooled and condensed on contact with a cold source.
[0006] To carry out these various stages, the loop comprises a compressor pump for circulating and compressing the fluid in liquid form, an evaporator that is swept by a hot fluid for at least partial vaporization of the compressed fluid, an expansion machine for expanding the vapour, such as a turbine that converts the energy of this vapour to another energy such as a mechanical or electric energy, and a condenser by means of which the heat contained in the vapour is yielded to a cold source, generally outside air that sweeps this condenser so as to convert this vapour to a fluid in liquid form.
[0007] In this type of loop, the fluid used is generally water but other types of fluid can also be used, for example organic fluids or organic fluid mixtures.
[0008] By way of example, these organic fluids can be butane, ethanol, hydrofluorocarbons, ammonia, carbon dioxide, etc.
[0009] It is also well known, notably through document FR-2,884,555, to use the calorific energy conveyed by the exhaust gas of internal-combustion engines, in particular those used for motor vehicles, as the hot source providing heating and vaporization of the fluid flowing through the evaporator.
[0010] This allows to improve the energy efficiency of this engine by recovering a large part of the energy lost at the exhaust in order to convert it to an energy that can be used for the motor vehicle through the Rankine cycle loop.
[0011] In some instances, the working fluid is caused to circulate at high pressures (up to about 40 bars or even 80 bars) and very high temperatures, close to 400° C. These fluid pressures and temperatures are maintained within the operating range for which the system is dimensioned by means of a control system that acts notably upon the pump, the expansion machine and on the actuators driving the various elements of the loop.
[0012] Furthermore, when using certain working fluids, this fluid may also appear to be intrinsically dangerous, notably flammable.
[0013] Thus, in case of an abnormal situation of the vehicle, an accident for example, the system controlling the Rankine cycle loop can become inoperative, either as a result of a malfunction of the control system itself or of a malfunction of the sensors or the driving actuators.
[0014] Due to the thermal inertia of the hot source or after a vehicle fire that may occur during an accident, the pressure and the temperature of the working fluid can continue to increase. In this case, temperature or pressure levels of this fluid incompatible with the dimensioning of the Rankine system can be reached. These levels can lead to a sudden break in one or more elements of the loop (fluid circulation line, exchanger, etc.), thus causing yet another accident.
[0015] The present invention aims to overcome the aforementioned drawbacks by means of a method allowing to take preventive measures so as to limit or even to prevent a closed loop break.
SUMMARY OF THE INVENTION
[0016] The present invention therefore relates to a method of controlling a closed loop performing a Rankine cycle for a motor vehicle, said loop comprising a circulation and compression pump for a working fluid, a heat exchanger swept by a hot source for heating said working fluid, expansion means for expanding the hot fluid and a cooling exchanger swept by a cooling fluid for cooling this working fluid, characterized in that it consists, after detecting a vehicle accident situation, in communicating the inside of the loop with the ambient air.
[0017] The method can consist in communicating the loop with the ambient air after detecting violent impacts on the vehicle.
[0018] The method can consist in communicating the loop with the ambient air after detecting a car fire.
[0019] The method can consist in controlling throttling means for an opening provided on the loop for communicating said loop with the ambient air.
[0020] The invention also relates to a closed loop performing a Rankine cycle for a motor vehicle comprising a circulation and compression pump for a working fluid, a heat exchanger swept by a hot source for heating said working fluid, expansion means for expanding the hot fluid, a cooling exchanger swept by a cooling fluid for cooling this working fluid and circulation lines for said fluid, characterized in that it comprises a device for communicating the inside of the loop with the ambient air, said device being operative in a vehicle accident situation.
[0021] The device can comprise an opening located on at least one element of the loop and throttling means controlling this opening.
[0022] The opening can be provided on at least one of the exchangers and/or on at least one of the circulation lines.
[0023] The throttling means can comprise a valve switching between an extreme position closing the opening and another extreme position of clearing the opening.
[0024] The hot source can come from the exhaust gas of an internal-combustion engine,
BRIEF DESCRIPTION OF THE SOLE FIGURE
[0025] Other features and advantages of the invention will be clear from reading the description hereafter, given by way of non limitative example, with reference to the sole FIGURE showing a closed loop performing a Rankine cycle with its control system according to the invention.
DETAILED DESCRIPTION
[0026] The present description relates more particularly to a closed loop with a phase change fluid, but any other Rankine cycle loops, such as those referred to as supercritical fluid loops (with CO 2 for example), can be used.
[0027] In FIG. 1 , Rankine cycle closed loop 10 comprises a circulation and compression means 12 for a working fluid, water here, circulating clockwise (arrows A) in this loop. This means, referred to as pump in the rest of the description, allows to compress this water between the pump inlet and its outlet where this water, still in liquid form, is at high pressure.
[0028] This pump is advantageously driven in rotation by any known means such as an electric motor (not shown).
[0029] This loop also comprises a heat exchanger 14 , referred to as evaporator, traversed by the compressed water coming from the pump that flows out of this evaporator in form of hot compressed vapour.
[0030] This evaporator is swept by a hot source 16 coming from the exhaust gas circulating in exhaust line 18 of an internal-combustion engine 20 .
[0031] Preferably, this engine is an internal-combustion engine of a motor vehicle.
[0032] This loop also comprises a receiving expansion machine 22 receiving at the intake thereof the high-pressure compressed water vapour, from where the water vapour flows out of this expander in form of low-pressure expanded vapour.
[0033] By way of example, this expansion machine is an expansion turbine whose rotor (not shown) is driven in rotation by the water vapour. This rotor is advantageously connected to any known device allowing to use the mechanical energy recovered, for example to a transmission system of a vehicle driving the wheels, or to convert the mechanical energy recovered to another energy, such as an electric generator 24 for example.
[0034] The loop also comprises a cooling exchanger 26 , referred to as condenser in the rest of the description. This condenser allows to convert the expanded low-pressure vapour coming from the turbine to water in liquid form after passing through this condenser.
[0035] By way of example, this condenser consists here of an assembly of cooling tubes and fins swept by a cooling fluid 28 that flows through the condenser between its inlet face and its outlet face while cooling and condensing the expanded vapour.
[0036] This cooling fluid is here outside air at ambient temperature, but any other cooling fluid such as water can be used for condensing the vapour.
[0037] The various elements of the loop are connected to one another by fluid circulation lines 30 , 32 , 34 , 36 allowing to connect successively the pump to the evaporator (line 30 ), the evaporator to the turbine (line 32 ), the turbine to the condenser (line 34 ) and the condenser to the pump (line 36 ) so that the working fluid circulates, in liquid or vapour form, in the direction shown by arrows A.
[0038] As it is widely known, this loop is connected to a control system 38 allowing management thereof. Notably, this system receives information on the operation of this loop through lines 40 . More particularly, some of these lines receive information from various detectors provided in this loop, such as the pressure or the temperature of the water (or of the water vapour). From the information received, system 38 controls elements of the loop through control lines 42 necessary to obtain the desired operating range. These control lines notably allow to act upon pump 12 and turbine 22 .
[0039] The loop illustrated in the sole figure also comprises a closed loop venting device 44 allowing partial or total preventive discharge of the fluid contained in this loop.
[0040] This device comprises an opening 46 provided on one of the circulation lines, here circulation line 30 provided between pump 12 and evaporator 14 .
[0041] Without departing from the scope of the invention, this opening can also be provided on one or more elements of the loop such as the heating and/or cooling exchangers, the pump, the turbine.
[0042] Throttling means are arranged on this opening so as to seal or clear it.
[0043] Advantageously, these throttling means include a valve 48 , preferably bistable, which tilts around a tilt axis 50 . Tilting of this valve is controlled by any known means, by way of example here an electric motor (not shown).
[0044] Tilting of this valve is advantageously controlled by control lines 42 of control system 38 acting upon the electric tilt motor.
[0045] This control system 38 also receives, through a line 40 , information from a vehicle abnormal situation management unit.
[0046] By way of example, this unit can be an accident controller 52 , commonly referred to as crash line, provided to reduce the consequences in case of a car crash, such as a collision, a fire, a vehicle overturn, etc.
[0047] This controller thus allows to carry out many preventive actions intended to reduce the consequences of this accident situation and in particular in case of a violent impact against a stationary or moving obstacle.
[0048] More precisely, this controller comprises information lines 54 some of which are connected to detectors 56 such as shock detectors and/or sudden vehicle deceleration detectors.
[0049] After receiving the information relative to this car crash situation, the controller transmits, through one or more control lines 58 , one or more signals for triggering vehicle safety elements. These elements can be air bags and/or seat belt pre-tensioners.
[0050] These signals can also trigger vehicle power cut, hood raising so as to provide a shock-absorbing device, notably in case of a collision with a pedestrian, retraction of the wiper blades so as to prevent a pedestrian from being hurt, etc.
[0051] After receiving the signal coming from the controller that has detected an accident situation, control system 38 also controls loop venting.
[0052] This system controls, through a line 42 , the motor of valve 48 so that it switches from an initial closed position of opening 46 , as shown in thick line in the figure, to an open position of this opening 46 (shown in dotted line in the figure).
[0053] Thus, the inside of the loop is communicated with the ambient air by venting it.
[0054] Opening 46 is thus no longer sealed and the working fluid contained in loop 10 can be discharged, totally or partly, through this opening, either through gravity or under the effect of the pressure prevailing in the loop.
[0055] This working fluid can of course be discharged in liquid or gas form in the direction of circulation of arrows A. This fluid can also be discharged in an opposite direction of circulation (arrow A′) if the fluid contained in the loop cannot circulate in the conventional direction, for example due to the obstruction of one or more circulation lines.
[0056] This preventive discharge can thus prevent a loop break that might occur long after detecting this abnormal vehicle situation, an accident as it happens here.
[0057] This helps avoid worsening of the situation, notably during the intervention of a rescue team operating on the car.
[0058] Alternatively, valve 48 can also be controlled by one of lines 58 coming directly from accident controller 52 .
[0059] Of course, this vehicle accident situation can concern any other circumstance such as a fire, in which case communication with the ambient air allows preventive emptying of the loop so as to avoid any sudden loop break.
[0060] This fire can be detected by any known means such as fume detectors or temperature detectors connected to accident controller 52 .
[0061] Without departing from the scope of the invention, opening 46 can also be arranged on other circulation lines and/or on one of the loop elements: exchangers, pump, turbine, etc.
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The present invention relates to a method of controlling a closed loop ( 10 ) performing a Rankine cycle for a motor vehicle, said loop comprising a circulation and compression pump ( 12 ) for a working fluid, a heat exchanger ( 14 ) swept by a hot source ( 16 ) for heating said working fluid, expansion means ( 22 ) for expanding the hot fluid and a cooling exchanger ( 26 ) swept by a cooling fluid ( 28 ) for cooling this working fluid.
According to the invention, the method consists, after detecting a vehicle accident situation, in communicating the inside of the loop with the ambient air.
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FIELD OF INVENTION
[0001] This invention is concerned with improvement in fiberfill batts, sometimes referred to as batting, and processes whereby such improved batts with desirable uniformity, balanced tensile strength in all directions, stretchability, and high loft may be obtained.
DESCRIPTION OF RELATED ART
[0002] U.S. Pat. No. 3,747,162 issued to Watson on 24 Jul. 1973 discloses a conventional apparatus for producing a cross-lapped structure of crimped continuous filaments. This conventional apparatus includes a banding device, a threaded roll device, a series of air spreaders, a pair of delivery rolls, a pair of rolls, a chute, a pneumatic or hydraulic cylinder, and an apron.
[0003] A tow of some 30,000 adjacent crimped continuous filaments is delivered from a container (not numbered) to the banding device. From the banding device, the tow is delivered to the threaded roll device, where the crimped continuous filaments are de-registered. From the threaded roll, the crimped continuous filaments are delivered to the air spreaders, where air jets are used to spread the crimped continuous filaments to form a spread web. From the air spreaders, the spread web is delivered to the delivery rolls, about which the spread web makes an S-wrap. From the delivery rolls, the spread web is delivered to the pair of rolls, where the spread web makes an S-wrap. From the rolls, the spread web is delivered to the chute made of doors. The chute is oscillated via the pneumatic or hydraulic cylinder connected with one of the doors. From the chute, the spread web is laid onto the apron in the form of a roll-driven endless belt. The oscillated chute and the roll-driven endless belt together produce a cross-lapped structure of crimped continuous filament. In the use of this conventional apparatus, several problems have been encountered. Firstly, after leaving the chute, the spread web billows out transversely. This makes the spread web thinner towards its lateral edges.
[0004] Secondly, the chute is oscillated, i.e., the lower end of the chute is reciprocated between two dead ends.
[0005] The speed of the lower end of the chute reaches its minimum value, i.e., 0 , at two end points of its travel, and reaches its maximum value at a midpoint between the end points. By doing so, the lower end of the chute stays longer at the end points than at the midpoint. Since the spread web is delivered at a constant rate, the chute releases more weight of less-extended crimped continuous filaments when reaching the end points than when reaching the midpoint. Hence the cross-lapped structure is thinner along a midline than along the two sides. Thirdly, since the speed of the lower edges of the doors is much greater than that of a point of the roll-driven endless belt, the cross-lapped intersect angle between layers of spread web is very small. In other words, the spread web from crimped continuous filaments actually extends substantially transverse to a longitudinal direction, or machine direction (MD), of the cross-lapped structure. Thus, little strength is provided in the machine direction of the cross-lapped structure. Furthermore, the cohesion between layers of spread web in the cross-lapped structure is poor, and they cannot adequately hold on to each other. The cross-lapped structure also exhibits poor dimensional stability, especially along the midline where the weight and thickness are lowest. Therefore, resin bonding, needle punching, or thermal bonding must be used to minimize these problems.
[0006] The present invention is therefore intended to obviate or at least alleviate these problems.
SUMMARY OF THE INVENTION
[0007] The present invention provides a new machine and process to make a cross-lapped flat-tube structure or batting of crimped continuous filaments with optimum balance of tensile strength in all directions, especially in machine (MD) and cross-machine (CD) directions, with good stretch recovery properties, dimensional stability, and high loft, and overcomes the important deficiencies mentioned above in the prior art.
[0008] This invention uses crimped continuous filaments tow band wrapping at constant tension and speed around a batt-forming device which spreads, extends, and cross-laps this tow continuously to form a uniform batting having balanced tensile strength and to provide structural stability and stretch recovery properties. Uncrimped continuous filaments having extendible properties, such as elastic fibers or latent crimped fibers, etc., which can be spread, extended, and cross-lapped can also be used with this invention. By adjusting the traveling speed of the tow band wrapping around the batt-forming device and the spread belt surface speed in the spreading zone as described below as a spread ratio in the batt-forming device, the fiber orientation can achieve between a 10- and 70-degree angle, preferably a 30- to 60-degree angle, vs. the CD direction, and achieve a fiber orientation between cross-lapped layers of close to a 20- to 140-degree angle, preferably a 60- to 120-degree angle. As an example, when the traveling speed of the tow band wrapping around the batt-forming device and the spread ratio are optimized, the fiber orientation can be maintained at about a 45-degree angle vs. the CD direction, and the fiber orientation between cross-lapped layers at close to a 90-degree angle. This combination of fiber orientation in a spread flat-tube structure provides the best balance in MD and CD strength with a ratio of 1:1 so that there are essentially no weak spots in the cross-lapped flat-tube structure regardless of which direction the structure is pulled. The resulting cross-lapped flat-tube structure also exhibits excellent stretch recovery properties, dimensional stability, and high loft. Since the cross-lapped structure is formed from continuous filaments into an endless flat tube with good cohesion between individual fibers and between spread tow layers, one can use it directly without additional bonding process for insulated apparel, sleeping bags, bedding articles, and furniture applications, thus eliminating the deficiencies of the conventional cross-lapped batting made by the prior art mentioned above.
[0009] The advantage of wrapping the batt-forming device under constant tension and speed throughout the spreading, extending, and cross-lapping process eliminates the deficiency of the prior art of forming a thinner web on the lateral edges and the weight uniformity problem, especially in the midline of the final batting. By adjusting the traveling speed of the feeding device and the spread ratio of the forming device, a complete balance of the tensile strength and stretchability in MD and CD directions can be achieved, hence eliminating the deficiencies of the prior art, which has poor tensile strength and dimensional stability in the MD, or longitudinal, direction. Also the need for resin bonding, needle punching, or thermal bonding to improve cohesion between layers in the conventional cross-lapped structure can be eliminated, resulting in a stretchable, softer, and thicker structure to improve the aesthetics and warmth of the sleeping bags, insulated apparel, etc. These aspects of the present invention may be used separately or in combination to solve deficiencies of the conventional cross-lapped structure.
[0010] Because of the unique fiber orientation achieved by this invention and the precision control of the batting width, the cross-lapped flat-tube structure maintains the strength advantage of the spun bonded fabric but with improved stretchability, loft, and softness vs. spun bonded fabric. No resin, or thermal bonding, or mechanical entanglement such as needle punching is required for the cross-lapped flat-tube structure of this invention. If desired, one can also use the above conventional bonding processes to even further increase the batting strength but with increased stiffness.
[0011] Because the cross-lapped structure by this invention is formed under pre-determined constant tension and precise mechanically controlled spreading, extending, and cross-lapping, the stress applied on each filament is similar. Once the cross-lapped structure is released from the spread belt and is delivered to the conveyor, it maintains its dimensional stability and uniformity in this relaxed state. This cross-lapped flat tube structure can be used for insulated apparel, sleeping bags, bedding, and furniture applications without further bonding steps such as resin bonding, needle punching, and thermal bonding with low-melting binder fiber, which normally reduce softness and/or loft. Due to the unique stretchability property of the cross-lapped flat tube structure of this invention, it can easily regenerate its loft and resiliency from compression during shipping and storage by slightly stretching or fluffing the final products. Particularly useful when a stretchable cover fabric or shell fabric is used is the ability of the flat-tube structure of this invention to conform to the stretching of the fabric without deterioration. The conventional resin bonded, needle-punched, and thermally bonded batting or cross-lapped structure cannot provide this regeneration property because individual fibers and cross-lapped layers are bonded and locked with each other and are not free to separate from the compressed bonded structure.
[0012] The differences between the cross-lapped flat-tube structure of this invention and spun bonded fabric are significant. The present invention allows fiber orientation at a 45-degree angle vs. the CD direction and a 90-degree angle between cross-lapped layers of spread tow for balanced strength. The resulting structure can be used directly without bonding vs. spun bonded batting, which must be bonded to stabilize the structure. Hence the cross-lapped flat-tube structure of this invention is softer and provides higher loft. In addition, the continuous filaments used in this invention can be crimped as an option vs. no crimp for spun bonded filaments directly extruded from spinnerets, therefore exhibiting its stretch recovery properties. Spun bonded battings are limited to low fiber orientation angles, no crimp in each filament, and a rigidly bonded structure leading to rigid and low-loft nonwoven fabric or batting.
[0013] As will be described below, the unique design of the batt-forming device allows multiple numbers of tows of crimped continuous filaments to be simultaneously fed onto the feeding zone and subsequently to be spread in the spreading zone. If desired, each tow fed from a different feeding device can be different in fiber type, denier, fiber cross-section, and other variables, resulting in a heterogeneous batt in one single step by the present invention, whereas an expensive multiple-step process or complicated layering mechanism is required to achieve a similar composition by other methods. Almost any kind of fiber, such as nylon, polyester, polypropylene, and elastic fibers, just to name a few, can be used in this invention. There is no fiber denier limitation in this invention. Various cross-sections of fiber, for example, round, trilobal, tetralobal, etc., can be used with this invention. Other variables, such as fiber surface modification, additive in polymer, etc., to provide special properties or functions in the batting can be used with the present invention.
BRIEF DESCRIPTION OF DRAWINGS
[0014] The present invention will be described through a detailed illustration of embodiments, referred to in the attached drawings.
[0015] FIG. 1 perspective view of the machine for producing a cross-lapped flat-tube structure from two tows of crimped continuous filaments according to the first embodiment of the present invention.
[0016] FIG. 2 front view of a batt-forming device used in the machine of FIG. 1 .
[0017] FIGS. 3 and 4 front and side views of the components of a batt-forming device used in the machine of FIG. 1 .
[0018] FIG. 5 enlarged sectional view of a pinwheel between the conveyers of the feeding zone and the spreading zone as used in the machine of FIG. 1 .
[0019] FIG. 6 front view of a modified batt-forming device used in the machine of FIG. 1 .
[0020] FIG. 7 drawing of spreading step 1 of each tow of crimped continuous filaments at 0 second according to the first embodiment of the present invention.
[0021] FIG. 8 drawing of spreading step 2 of each tow of crimped continuous filaments at 8 seconds according to the first embodiment of the present invention.
[0022] FIG. 9 drawing of spreading step 3 of each tow of crimped continuous filaments at 16 seconds according to the first embodiment of the present invention.
[0023] FIG. 10 drawing of spreading step 4 of each tow of crimped continuous filaments at 24 seconds according to the first embodiment of the present invention.
[0024] FIG. 11 graphic demonstration of no filament orientation angle change with either two or four groups of conveyors in the batt-forming device.
[0025] FIG. 12 perspective view of a machine for producing a cross-lapped flat-tube structure from two tows of crimped continuous filaments which are separated into many small bundles of filaments according to the first embodiment of the present invention.
[0026] FIG. 13 illustration of using a wide tow band to make flat-tube structure with minimal or no cross-lapped marks with the present invention.
[0027] FIG. 14 illustration of usual tow band width to make flat-tube structure with the present invention.
[0028] FIG. 15 illustration of a flat-tube structure made by the present invention.
[0029] FIG. 16 illustration of a cross-lapped structure made by the conventional process.
[0030] FIG. 17 perspective view of a machine for producing a cross-lapped flat tube from a tow of crimped continuous filaments according to the second embodiment of the present invention.
[0031] FIG. 18 perspective view of a machine for producing a cross-lapped flat-tube structure from four tows of crimped continuous filaments according to the third embodiment of the present invention.
[0032] FIG. 19 perspective view of a machine for producing a cross-lapped flat-tube structure from multiple tows of crimped continuous filaments according to the fourth embodiment of the present invention.
[0033] FIG. 20 perspective view of a machine for producing a cross-lapped flat-tube structure from tows of crimped continuous filaments with batt-forming device moving upward instead of downward as shown in FIGS. 1, 17 , 18 and 19 .
[0034] FIG. 21 perspective view of a machine for producing a cross-lapped flat-tube structure from tows of crimped continuous filaments according to the fifth embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0035] Referring to FIG. 1 , according to the first embodiment of the present invention, a machine and process for producing a cross-lapped flat-tube structure of crimped continuous filaments includes two separate feeding devices 2 a and 2 b located 180 degrees apart from one another; a spreading, extending, and cross-lapping device 4 , which will be called the batt-forming device 4 ; and a conveying device 6 . A tow 1 of crimped continuous filaments is fed from each of the feeding devices 2 a and 2 b to the batt-forming device 4 , where the tow 1 is spread, extended, and cross-lapped. From the batt-forming device 4 , a cross-lapped flat-tube structure of crimped continuous filaments is delivered to the conveying device 6 and subsequently to the windup equipment. The feeding devices 2 a and 2 b each consist of a container 8 a and 8 b respectively in which the tow is stored and a series of rolls 10 a and 10 b respectively for spreading and feeding the tow 1 from the containers 8 a and 8 b to the batt-forming device 4 . Although not shown, a mechanism is used to carry and drive the feeding devices 2 a and 2 b wrapping around the batt-forming device 4 continuously either in a clockwise or counter-clockwise direction for producing a continuous cross-lapped flat-tube structure of crimped continuous filaments. Such a mechanism is not shown since it is not the spirit or an essential part of the present invention.
[0036] Referring to FIGS. 2 to 5 , the batt-forming device 4 includes two groups of pin-covered conveyors 12 a and 12 b , and two curved plates 14 a and 14 b between which the two groups of conveyors are arranged. The first group 12 a is arranged near one edge of each of the plates 14 a and 14 b , and the second group 12 b is arranged on the opposite edge of each of the plates 14 a and 14 b . Each group of the conveyors 12 a and 12 b extend a portion beyond the edges of plates 14 a and 14 b for engagement with the tows 1 of crimped continuous filaments, which are wrapped around the batt-forming device 4 . As shown in FIGS. 3 and 4 , 12 a and 12 b each consist of two groups of conveyors. A slower-moving conveyor is in the feeding zone located in the upper section of the batt-forming device 4 , and a faster-moving conveyor in the spreading zone is located in the lower section of the batt-forming device 4 . As shown in FIGS. 3 and 4 , the conveyors in the upper section of the batt-forming device 4 within the feeding zone, indicated as Fca and Fcb, which comprise two separate but identical conveyors, are driven by rolls of slower but identical rotating speed in both 12 a and 12 b . Therefore, the surface speeds of conveyors in the feeding zone are identical at 12 a and 12 b . The advantage of the two separate conveyors in the feeding zone is to provide additional anchor points and supports of the engaged tow band in the feeding zone so that they can prevent a potential filament entanglement problem within the tow band during the engaging and transferring processes within the feeding zone. These two conveyors identified in each of Fca and Fcb respectively as shown have identical construction and surface speed, and the conveyors are parallel to each other. The conveyor belt surfaces are covered with coarse pins extended on the surfaces to provide enough friction to hold filaments of the tow 1 in place and transport them to the spreading zone. Because there are two conveyors for each side of the feeding zone, there are also two corresponding pin-wheels for each of La and Lb respectively at the bottom of each conveyor Fca and Fcb in the feeding zone in 12 a and 12 b having fine pins on the surface with surface speed faster than that of the conveyors in the feeding zone to pick up filaments from the respective conveyors as shown in FIGS. 3 and 4 .
[0037] As the tow 1 of crimped continuous filaments is engaged by coarse pins on the conveyors Fca and Fcb in the feeding zone and moved downward at slow speed, filaments maintain their positions parallel to each other in the tow i without separation or spreading. When the leading edge of the tow 1 reaches the joining line between the bottom of Fca and Fcb and the pin-wheels La and Lb, the filaments in the leading edge of the tow 1 are caught by fine pins on the surface of the fast-rotating pin-wheels La and Lb.
[0038] FIG. 5 shows that, because the surface speed of the pin-wheel La is faster than that of the conveyor Fca in the feeding zone, the filaments are caught and picked up from the tow band and are separated from the majority of the filaments in the tow 1 , which is still being held by coarse pins on the conveyors in the feeding zone. In a continuous operation, the rest of the tow band is moved downward continuously by conveyors in the feeding zone toward the fast-moving pin-wheel La until all filaments are picked up. Since the pin-wheel La picks up filaments in sequence and at a faster speed, the filaments on pin,wheel La are also parallel to each other but are further apart. The resulting spread batt on pin-wheel La's surface is much thinner than the thickness of the original tow 1 fed onto the conveyors in the feeding zone. As the leading edge of the spread batt moving downward reaches the joining line between the pin-wheels La and Lb and the top of the conveyors Sca and Scb in the spreading zone, the filaments in the leading edge of the spread batt on pin-wheels La and Lb are caught by the finer pins on the surface of the even faster-moving conveyors Sca and Scb in the spreading zone. The conveyors Sca and Scb are different from the conveyors Fca and Fcb in the feeding zone, and each forms only a single wider conveyor.
[0039] Once again, because the surface speed of the conveyors Sca and Scb in the spreading zone is faster than that of the pin-wheels La and Lb, the filaments are caught and picked up by finer pins on conveyors Sca and Scb in the spreading zone from the leading edge of the spread batt and are separated from the majority of the filaments in the spread batt which are still being held by fine pins on the pin-wheels La and Lb. In a continuous operation, the rest of the spread batt is moved downward continuously by pin-wheels La and Lb toward the faster-moving conveyors Sca and Scb in the spreading zone until all filaments are picked up by finer pins in conveyors Sca and Scb in the spreading zone. The resulting spread structure on conveyors Sca and Scb in the spreading zone is a uniform, thin batt of spread crimped continuous filaments which are parallel to each other.
[0040] The ratio of the surface speed of the conveyors Sca and Scb in the spreading zone to that in the feeding zone is defined as the spread ratio. The spread ratio determines the filament orientation angle and the cross-lapped layer angle, as will be described later. The surface speed of the pin-wheels La and Lb is faster than that of the conveyors Fca and Fcb in the feeding zone, but is slower than that of the conveyors Sca and Scb in the spreading zone. Since the pin-wheels La and Lb act as a separating wheel to separate filaments from the tow bundle and to transfer the resulting thinner batt to the conveyors Sca and Scb in the spreading zone for further spreading, the speed of the pin-wheels La and Lb does not change the spread ratio of the final product. However, the pin-wheel speed is adjusted based on the tow denier, crimp level, and cohesiveness of the filaments so that the filaments can be separated from the tow bundle without entanglement or damage for the uniform spreading operation.
[0041] In another aspect of the present invention, referring to FIG. 6 , the batt-forming device 4 consists of four groups of conveyors 12 a , 12 a - 1 , 12 b , and 12 b - 1 instead of the two described above; each group has two conveyors in the feeding zone and one conveyor in the spreading zone. The composition of each group of conveyors in FIG. 6 is identical to that described in FIG. 2 identified as 12 a and 12 b . The components of these two additional groups of conveyors 12 a - 1 and 12 b - 1 are the same as those of 12 a and 12 b described in FIGS. 3 to 5 with the exception that 12 a - 1 and 12 b -l are opposite to each other but are located 90 degrees away from 12 a and 12 b respectively. Identical to that of 12 a and 12 b shown in FIG. 3, 12 a - 1 and 12 b - 1 each has a group of pin-wheels La- 1 and Lb- 1 respectively in between the feeding zone and spreading zone. With these two additional groups of conveyors and wheels, the principle operation of the batt-forming device 4 is identical to that described above, but a wider flat-tube structure can be made evenly from a wider batt-forming device 4 . Because the tow of crimped continuous filaments has very good cohesion between the filaments, it is difficult to separate the individual filaments from each other if the distance between the two conveyors in which the tow 1 is engaged is large. By reducing the distance between the two adjacent conveyors as illustrated in FIG. 6 , the filament cohesive force between the two supporting conveyors can be overcome by the spreading force asserted on the filaments. And as the filament cohesive force is overcome, the crimped continuous filaments can be spread evenly and smoothly, instead of sporadically, when cohesive force is overridden to form a uniform flat-tube structure. More detailed illustrations will be given below.
[0042] As the width of the batt-forming device 4 increases, further additional groups of conveyors can be installed evenly around the surfaces of the two curved plates 14 a and 14 b , to a total of 6, 8, 10, etc., groups of conveyors. There is no limitation to the number of groups of conveyors that can be used in the batt-forming device 4 .
[0043] Referring to FIG. 1 , the conveying device 6 includes two rolls 16 and an endless belt 18 mounted on and driven by the rolls 16 for delivering the cross-lapped flat-tube structure produced by the batt-forming device 4 .
[0044] The operation of the first embodiment of the present invention is described in FIG. 1 in the following sequences.
[0045] (1) There are two separate feeding devices 2 a and 2 b located opposite to each other relative to the batt-forming device 4 . In a continuous operation, a first portion of the tow 1 of crimped continuous filaments is delivered from the container 8 a through feeding and spreading rolls 10 a to conveyor 12 a in the feeding zone. Soon after the first portion of the tow 1 is engaged with the moving conveyor 12 a , it is transported downward at a speed slower than that of the tow 1 delivery speed from 10 a . In an identical operation, and travelling in the same clockwise direction around the batt-forming device 4 simultaneously, a first portion of the tow 1 of crimped continuous filaments is delivered from container 8 b through feeding and spreading rolls 10 b to conveyor 12 b in the feeding zone. Soon after the first portion of the tow 1 is engaged with moving conveyor 12 b , it is transported downward at a speed slower than that of the tow 1 delivery speed from 10 b . When the feeding device 2 a is rotated 180 degrees clockwise in front of the batt-forming device 4 , a second portion of the tow 1 of crimped continuous filaments is delivered from container 8 a through feeding and spreading rolls 10 a and is engaged with conveyor 12 b in the feeding zone. In the meantime, the feeding device 2 b is also rotated 180 degrees clockwise around the back of the batt-forming device 4 , and a second portion of the tow 1 of crimped continuous filaments is delivered from container 8 b through feeding and spreading rolls 10 b to conveyor 12 a in the feeding zone.
[0046] (2) The leading edge of the tow 1 of crimped continuous filaments at the bottom of the conveyors in the feeding zone is picked up by pin-wheels La and Lb respectively at faster surface speed. Therefore, filaments are being spread under tension and deposited onto conveyors in the spreading zone on both 12 a and 12 b having an even faster surface speed than La and Lb. As the tows 1 of crimped continuous filaments are delivered continuously from conveyors in the feeding zone of 12 a and 12 b , a continuous spread flat tube of continuous filaments is formed in conveyors in the spreading zone of 12 a and 12 b . By adjusting the ratio of the surface speed of the conveyors in the spreading zone to that in the feeding zone, which is expressed as the spread ratio, and adjusting the width of tow bands and the delivery speed of the tows 1 to the batt-forming device 4 , one can change the basis weight of the flat-tube structure and the inclined angle A of the filaments relative to the CD direction as shown in FIG. 1 . Ideally, a 45-degree angle will provide equal tensile strength in MD and CD directions at a ratio close to 1:1 for best balance of tensile strength. The present invention can achieve such an ideal angle of 45 degrees. To meet the specific requirements of the end product, one can adjust the angle A between approximately 10 and 70 degrees to provide the desired tensile strength, stretchability, and loft.
[0047] (3) In a continuous rotating motion, the feeding device 2 a is moving to the back of the batt-forming device 4 in FIG. 1 or facing the curved plate 14 b in FIG. 2 , while the feeding device 2 b is moving to the front of the batt-forming device 4 in FIG. 1 or facing the curved plate 14 a in FIG. 2 . A third portion of the tow 1 of crimped continuous filaments is delivered from container 8 a through feeding and spreading rolls 10 a and is engaged with moving conveyor 12 a in the feeding zone. Simultaneously, in an identical operation, a third portion of the tow 1 of crimped continuous filaments is delivered from container 8 b through feeding and spreading rolls 10 b and is engaged with moving conveyor 12 b in the feeding zone. This process is repeated many times exactly as described in sequences (1), (2), and (3) above; therefore, a continuous flat-tube structure of spread crimped continuous filaments is formed in the batt-forming device 4 and subsequently delivered to conveyor device 6 .
[0048] Referring to FIGS. 7 to 10 as the illustrations of one aspect of the present invention, two 0.25-meter-wide tows of crimped continuous filaments are delivered from 8 a and 8 b respectively, wrapping around a 2-meter-wide batt-forming device 4 at a speed of 0.25 meter per second, which is identical to that of the conveyor speed in the spreading zone. The conveyor speed in the feeding zone is ⅛ of that of the conveyors in the spreading zone, or 0.03125 meter per second, resulting in a spread ratio of 8. As shown in FIGS. 7 to 10 , in every eight seconds, tows 1 delivered from containers 8 a and 8 b have traveled the distance of 2 meters between conveyors 12 a and 12 b , with FIG. 7 showing the first 0 second of traveling, FIG. 8 showing the 8th second of traveling, FIG. 9 showing the 16 th second of traveling, and FIG. 10 showing the 24 th second of traveling. During this period, the first portions of the engaged tows 1 have been spread from 0.25 meter to 2 meters in the spreading zone. Because 8 a and 8 b are traveling in the same direction but are 180 degrees apart, each spread tow pattern is also the opposite and mirror image of the other. However, when the two spread tow patterns are super-imposed on each other as in the continuous operation involving two separate feeding devices in the present invention, a continuous flat tube of spread crimped continuous filaments, as shown in FIG. 1 , is formed continuously.
[0049] Referring to FIG. 6 as another illustration of other aspects of the present invention using four groups of conveyors instead of two as described above, two 0.25-meter-wide tows 1 of crimped continuous filaments are delivered from 8 a and 8 b respectively, wrapping around a 2-meter-wide batt-forming device 4 at a speed of 0.25 meter per second, which is identical to that of the conveyor speed in the spreading zone. Since all four pin conveyors in the feeding zone are moving at the same speed and all four pin conveyors in the spreading zone are moving at the same but faster speed, the operation is the same as in the above illustration. For example, after 8 seconds, the first portion of tow 1 engaged with 12 a in FIGS. 7 to 10 having a 2-meter-wide batt-forming device 4 has been spread from 0.25 meter to 2 meters in the spreading zone, forming a 45 degree filament orientation angle between 12 a and 12 b . But adding two more groups of pin conveyors 12 a - 1 and 12 b - 1 as in FIG. 6 , after 8 seconds, the engaged tow at 12 a also has been spread from 0.25 meter to 2 meters in the spreading zone, and the engaged tow at 12 b - 1 is only spread from 0.25 meter to 1 meter in the spreading zone because tow 1 engaged with 12 b - 1 is 4 seconds late after engaging with 12 a . Therefore, the filament orientation is still maintaining 45 degrees, the same as the above, as is shown in FIG. 11 . Because of this time delay to reach 12 b - 1 , the spread tow formation is the same whether 12 b - 1 is installed in the batt-forming device 4 or not. The same situation can be applied with 12 a - 1 relative to the spread tow formation. The advantage of the additional two groups of conveyors 12 a - 1 and 12 b - 1 as described previously is reducing the distance between engaging conveyors to override the cohesive force exhibited in the tow 1 of crimped continuous filaments so that uniform and smooth spreading can be achieved to form a uniform flat-tube structure. With a much wider batt-forming device to make a wider flat-tube structure, additional groups of conveyors in the feeding zone and the spreading zone are beneficial to overcome the cohesive force of the crimped continuous filaments for a successful spreading operation.
[0050] In yet another aspect of the present invention, referring to FIG. 12 , the two separate tows 1 being fed from containers 8 a and 8 b respectively have a different configuration compared to that shown in FIG. 1 . The tows 1 shown in FIG. 1 and described in this embodiment are very uniform tow bands which can be characterized as having essentially the same thickness, density, and continuity across the width of the tow band. The resulting cross-lapped flat-tube structure is a homogeneous, uniform structure in appearance and in properties, having balanced tensile strength in all directions and providing structural stability and stretch recovery properties. However, the tow bands shown in FIG. 12 are separated into many small bundles of filaments by an additional special device, such as separating guide pins or guide rolls in 10 a and 10 b respectively, before feeding them to the batt-forming device 4 . The resulting bundles of filaments within the tow band are separated from each other with a definite gap between them, with the distance depending on the design of the separating device. These heterogeneous tow bands consisting of many small bundles of filaments and space in between them can form a heterogeneous cross-lapped flat-tube structure of crimped continuous filaments using the same machine and process of the present invention. The resulting heterogeneous cross-lapped flat-tube structure has essentially the same structure and characteristics, mainly having a balance of tensile strength in all directions and providing structural stability and stretch recovery properties with some exceptions. There are many empty spaces without filaments formed along each layer of the batt and many holes created within the cross-lapped structure, as shown in FIG. 12 . The resulting cross-lapped flat-tube structure has the appearance of a loosely woven structure in the form of mesh wire or fishing net, with many holes between filament cross-over points. This structure provides unique attributes, such as high air permeability through open holes for good breathability with low density, resiliency, and good support, which can be used as components to satisfy important requirements in mattress and furniture applications. This further demonstrates the flexibility and versatility of the present invention. This aspect of the present invention can be used singularly or in combination with other aspects of the present invention as described in all embodiments of the present invention.
[0051] In yet another aspect of the present invention, referring to FIGS. 13 and 14 , there are no limitations on the denier, homogeneity, and width of the tow bands to be used with the present invention. Contrary to the aspect described above as illustrated in FIG. 12 , the present invention can also provide a very uniform flat-tube structure with very little or no cross-lapped marks as normally appear in a conventional cross-lapped structure described in prior art. Instead of using the usual thick and narrow tow band, a thin but wider tow band can be used to achieve a much more uniform flat-tube structure with essentially no cross-lapped marks between layers. For example, by using a tow band width of 75 cm (H) (as shown in FIG. 13 ) instead of the usual 25 cm (h) (as shown in FIG. 14 ) as described above for the feeding tow for the batt-forming device 4 , one can minimize or eliminate the cross-lapped marks on the flat-tube structure. Because the feeding tow as shown in FIG. 13 is three times wider, it will overlap three times in the feeding zone of the batt-forming device before reaching the spreading zone; hence, the marks on the over-lapped layers in the feeding zone are virtually eliminated compared to the obvious heavy marks appearing on the two adjacent thick and narrow tow bands. The resulting flat-tube structure from this wide tow band has essentially no cross-lapped marks. This further demonstrates the flexibility and versatility of the present invention.
[0052] The cross-lapped angle between the two cross-lapped layers is ideally 90 degrees for equal strength in MD and CD directions. Other cross-lapped layer angles can be achieved by this invention by adjusting the traveling speed of feeding devices 2 a and 2 b wrapping around the batt-forming device 4 and the spread ratio of the conveyor speeds between spreading zone and feeding zone. To meet the specific requirements of the end use, one can achieve the cross-lapped layer angles between about 20 and 140 degrees for specific desired tensile strength, stretchability, and loft. It is desirable that the spread tow leaves the batt-forming device 4 for the conveying device 6 when the section of the tow 1 between the first and second portions is at an appropriate angle from the section of the tow 1 between the second and third portions. The angle will determine the tensile strength ratio between MD and CD directions of the cross-lapped flat-tube structure.
[0053] There is a very important distinction between the spread cross-lapped flat-tube structure of the present invention compared to conventional cross-lapping batting by the process described in the prior art mentioned earlier. The flat tube of the present invention is an endless tube structure with very good uniformity throughout the entire structure, including edges and center, with dimensional stability, good stretchability, and high loft as shown in FIG. 15 , whereas the batt created by a conventional cross-lapping method is a folding-layer structure which has the appearance of fish scales which can be peeled off layer by layer as shown in FIG. 16 , with deficiencies of uniformity, poor cohesion between layers, poor balance of MD and CD tensile strength, and inadequate dimensional stability.
[0054] As shown in FIG. 1 , the feeding devices 2 a and 2 b are located at identical height in the feeding zone relative to the batt-forming device 4 , and they are separated by 180 degrees and rotate around the batt-forming device 4 in a clockwise direction. However, the feeding devices 2 a and 2 b can be at different heights in the feeding zone relative to the batt-forming device 4 , be different degrees apart, and rotate in different directions around the batt-forming device 4 . As long as both feeding devices are located above the dividing line between the feeding zone and spreading zone, a flat-tube structure from spread tow 1 of crimped continuous filaments can be produced by the present invention.
[0055] Referring to FIG. 17 , according to a second embodiment of the present invention, a machine and process for producing a cross-lapped flat-tube structure of crimped continuous filaments includes a single feeding device 2 ; a spreading, extending, and cross-lapping device 4 , which will be called the batt-forming device 4 ; and a conveying device 6 . A tow 1 of crimped continuous filaments is fed from the feeding device 2 to the batt-forming device 4 , where the tow 1 is spread, extended, and cross-lapped. From the batt-forming device 4 , a cross-lapped flat-tube structure of crimped continuous filaments is delivered to the conveying device 6 .
[0056] The feeding device 2 consists of a container 8 in which the tow 1 is stored and a series of rolls 10 for spreading and feeding the tow 1 from the container 8 to the batt-forming device 4 . Although not shown, a mechanism is used to carry and drive the feeding device 2 wrapping around the batt-forming device 4 continuously, either in a clockwise or counterclockwise direction for producing a continuous cross-lapped flat-tube structure of crimped continuous filaments.
[0057] The batt-forming device consists of two groups of pin-covered conveyors 12 a and 12 b and two curved plates as shown in FIGS. 2 to 4 . The description of the composition and operation of the batt-forming device 4 is identical to that in the first embodiment of the present invention and is shown in FIGS. 2 to 4 .
[0058] The operation of the second embodiment of the present invention is similar to that of the first embodiment of the present invention except a single container is needed as described as container 8 a in the first embodiment of the present invention. The other exception is that the conveyor speed of 12 a and 12 b in the feeding zone is even slower than that of the tow delivery speed from the series of rolls 10 , for example, {fraction (1/16)} instead of ⅛, as in the case of the first embodiment. Because of the speed difference, a single feeding device can cover the total area needed for two feeding devices as shown in FIGS. 7 to 10 . In order to keep a spread ratio of 8, the conveyor speed in the spreading zone is eight times faster than that of the conveyor speed in the feeding zone. As result, unlike the illustration in FIGS. 7 to 10 , the tow 1 speed from container 8 wrapping around the batt-forming device 4 is actually twice (2×) that of the conveyor speed in the spreading zone. In other words, in eight seconds, container 8 has made one complete circle (360 degrees) around the batt-forming device 4 and engaged a third portion of the tow 1 with 12 a instead of just traveling half a circle (or 180 degrees) or engaging a second portion of tow 1 with 12 b . This illustrates the flexibility and versatility of this machine and process to make flat-tube structures with various basis weights, filaments and cross-lapped angles, and productivity by adjusting various combinations of the tow 1 denier, the feeding speed from container 8 , and the spread ratio of the batt-forming device 4 .
[0059] Referring to FIG. 18 , according to a third embodiment of the present invention, a machine and process for producing a cross-lapped flat-tube structure of crimped continuous filaments includes four separate feeding devices 2 a and 2 b located at the same height relative to the batt-forming device 4 , both rotating in the same direction as shown in FIG. 1 , and 2 c and 2 d located at the same height but higher than that of 2 a and 2 b relative to the batt-forming device 4 , both rotating in the same direction, which could be the same as or different from the direction of 2 a and 2 b.
[0060] As shown in FIG. 18, 2 a and 2 b rotate clockwise around the batt-forming device 4 and both are located just above the dividing line between the feeding zone and the spreading zone. The other two feeding devices 2 c and 2 d rotate counter-clockwise around the batt-forming device 4 and are located higher above both 2 a and 2 b and also further away from the dividing line between the feeding zone and the spreading zone.
[0061] The procedure of engaging and spreading the tows 1 of crimped continuous filaments from containers 8 a and 8 b is identical to that of the three sequences (1), (2), and (3) described previously in the first embodiment of the present invention shown in FIG. 1 . The other two feeding devices 2 c and 2 d are located opposite to each other but above 2 a and 2 b relative to the batt-forming device 4 . In a continuous operation, a first portion of the tow 1 of crimped continuous filaments is delivered from the container 8 c through feeding and spreading rolls 10 c to conveyor 12 a in the feeding zone. Soon after the first portion of the tow 1 is engaged with the moving conveyor in the feeding zone 12 a , the engaged portion of the tow 1 is being transported downward at a slower speed than that of the tow 1 delivery speed from 10 c . Simultaneously in an identical operation, and traveling in the same counter-clockwise direction around the batt-forming device 4 , a first portion of the tow 1 of crimped continuous filaments is delivered from container 8 d through feeding and spreading rolls 10 d to conveyor 12 b in the feeding zone. Soon after the first portion of the tow 1 is engaged with the moving conveyor 12 b in the feeding zone, the engaged portion of the tow 1 is being transported downward in similar fashion as the engaged tow 1 from container 8 c . When feeding device 2 c is rotated 180 degrees counterclockwise around the back of the batt-forming device 4 , or facing the curved plate 14 b in FIG. 2 , a second portion of the tow 1 of crimped continuous filaments is delivered from container 8 c through feeding and spreading rolls 10 c and is engaged with conveyor 12 b in the feeding zone. In the meantime, the feeding device 2 d is also rotated 180 degrees counterclockwise around the front of the batt-forming device 4 or facing the curved plate 14 a in FIG. 2 , and a second portion of the tow 1 of crimped continuous filaments is delivered from container 8 d through feeding and spreading rolls 10 d and engaged with conveyor 12 a in the feeding zone. The process is repeated with the third and fourth portions of tows 1 of crimped continuous filaments from feeding devices 2 c and 2 d and the process is repeated continuously.
[0062] The engaged tows 1 in the feeding zone delivered from containers 8 c and 8 d are transferred along the downward moving conveyors 12 a and 12 b in the feeding zone for a distance until they reach close to the dividing line of the feeding zone and spreading zone and are laid over and combined with tows 1 from feeding devices 2 a and 2 b.
[0063] The leading edges of the combined tows 1 of crimped continuous filaments at the bottom of the conveyors in the feeding zone are picked up by pin-wheels La and Lb, as shown in FIGS. 3 to 5 , at faster surface speed. Therefore, filaments are being spread under tension and deposited onto conveyors 12 a and 12 b in the spreading zone, with both having faster surface speed than that of La and Lb. As the tows 1 of crimped continuous filaments are delivered continuously from conveyors 12 a and 12 b in the feeding zone, a continuous cross-lapped flat-tube of spread crimped continuous filaments is formed in conveyors in the spreading zone of 12 a and 12 b of the batt-forming device 4 , and subsequently delivered to conveying device 6 . This part of the spreading, extending, and cross-lapping process is identical to that described in the first embodiment of the present invention.
[0064] The locations of the feeding devices 2 a and 2 b can be at the same or different heights above the dividing line between the feeding zone and the spreading zone. They may rotate in the same or different direction either clockwise or counterclockwise around the batt-forming device 4 . The locations of feeding devices 2 c and 2 d are higher than those of 2 a and 2 b but each can be at the same or different heights and rotate in the same or different directions around the batt-forming device 4 . Once again, the ratio of surface speed of the conveyors in the spreading zone to that in the feeding zone is expressed as the spread ratio. The spread ratio determines the filament orientation angle vs. the CD direction and the cross-lapped angle between layers of the flat-tube structure.
[0065] Referring to FIG. 19 , according to a fourth embodiment of the present invention, a machine and process for producing a flat-tube structure of spread crimped continuous filaments includes two separate feeding devices 22 a and 22 b . Each consists of multiple containers 9 a , 10 a , and 11 a in 22 a , and 9 b , 10 b , and 11 b in 22 b ; a spreading, extending and cross-lapping device 4 , now called the batt-forming device 4 comprising a feeding zone and spreading zone, with composition identical to that in FIGS. 2 to 4 , and a conveying device 6 . The number of containers in feeding devices 22 a and 22 b varies from 2 to 100, depending on the denier and the width of the tow 1 in each container. A tow 1 of crimped continuous filaments is fed from each of the containers in feeding devices 22 a and 22 b to the batt-forming device 4 where the tow 1 is spread, extended and cross-lapped into a flat-tube structure and is finally delivered to conveying device 6 . The batt-forming device 4 and conveying device 6 in FIG. 19 are identical to that in FIGS. 1 and 18 . The mechanism of spreading, extending and cross-lapping according to this embodiment of the present invention is the same as described in FIG. 1 , except multiple numbers of tows 1 are fed to the batt-forming device 4 from each of the feeding devices 22 a and 22 b.
[0066] More than two additional feeding devices as described as 22 a and 22 b in FIG. 18 can be used with the present invention to make various basis weights and compositions of the flat-tube structure.
[0067] To illustrate the flexibility and versatility of the present invention, referring to FIG. 20 , a feeding mechanism can consist of a track circle around the batt-forming device 4 , which is fed by feeding devices 2 moving around the track at a pre-determined speed. If desired, for convenience, as shown in FIG. 20 , the conveyors in the batt-forming device 4 can move upward instead of downward as shown in FIG. 1 , so that the conveyors in the feeding zone are at the lower level and the conveyors in the spreading zone are at the upper level. As a result, the conveying device 6 and windup rolls 61 are also located at the higher level of the machine. The composition of the batt-forming device 4 is identical to that in FIG. 1 with the same components as in FIGS. 2 to 4 , except the conveyors in the feeding zone and the spreading zone are moving upward instead of downward. The principle of spreading, extending, and cross-lapping is exactly the same as that of the first embodiment of the present invention.
[0068] Referring to FIG. 21 , according to a fifth embodiment of the present invention, a commercially feasible and economically viable machine and process for producing a flat-tube structure of spread tow 1 of crimped continuous filaments includes a system composed of a batt-forming device 4 , a conveying device 6 , and a windup device 61 , all connected to a rotating platform, and two or more stationary feeding devices 2 . The composition of the batt-forming device 4 is identical to that in FIG. 1 , with the same components as in FIGS. 2 to 4 , except the conveyors in the feeding zone and spreading zone are moving upward instead of moving downward. The principle of spreading, extending, and cross-lapping is exactly the same as that of the first embodiment of the present invention. As the platform rotates in either a clockwise or counterclockwise direction at a pre-determined speed, tows 1 of crimped continuous filaments are fed from stationary feeding devices 2 wrapping around the conveyors in the feeding zone at the lower level of the rotating batt-forming device 4 . These engaged tows 1 are then spread in the spreading zone on the upper level and subsequently delivered to conveying device 6 , followed by windup device 61 . The ratio of the surface speed of the conveyors in the spread zone to that in the feeding zone is expressed as the spread ratio. Once again, the basis weight of the flat-tube structure, the angle between the filaments and the CD direction of the flat tube, and the cross-lapped angle between layers are determined by the combinations of the feeding speed of the tows, the width of the tow 1 , and the spread ratio. The feeding devices 2 can be at the same level as shown in FIG. 21 , or in different platforms with various heights so that each tow 1 can be fed in different heights in the feeding zone of the batt-forming device 4 . The number of containers in each feeding device 2 can vary from 2 to 100, depending on the denier and the width of the tow 1 in each container.
[0069] The rotating batt-forming device in FIG. 21 can be driven by some other means other than the rotating platform as shown. The batt-forming device 4 also can be arranged in the same configuration as in FIG. 1 , where the conveyors in both the feeding zone and the spreading zone are moving downward, so that tows can be fed from the stationary feeding devices 2 to the feeding zone and transferred to the spreading zone one floor below. Subsequently, the spread flat tube is delivered to the conveying device 6 and windup unit 61 at the lower floor.
[0000] Definition of Terms:
[0070] A. Stretch recovery: A batting or nonwoven fabric is stretched to 150% to length L 2 from the original length, Lo, and the stress is released. The recovery length, L 1 , is measured after 10 minutes' relaxation.
The percent recovery, R, is calculated as:
R={ 1−( L 1 − Lo )/( L 2 − Lo )}×100
When L 1 =L 2 , there is 0% recovery. When L 1 =Lo, there is 100% recovery. The measurement is determined in both MD and CD directions of the sample. The higher the percent recovery. the better the stretchability.
[0075] B. Loft: Loft is defined as thickness per unit weight. For example, inch per oz. per square yard, or mm. per gram per square meter.
[0076] C. Dimensional stability: The ability to maintain the size, i.e., width, length and height, during processing and in use.
[0077] D. Tensile strength: The ability to withstand the stress applied on a sample without breaking.
EXAMPLES
Example 1
[0078] Referring to FIG. 1 , a tow 1 of crimped continuous filaments with 100,000 filaments and total denier of 600,000 having a width of 0.125 meter is fed from container 8 a through a series of feeding and spreading rolls 10 a which widen it to a 0.25-meter tow band, then wrap it clockwise around a 2-meter-wide batt-forming device 4 and engage it with conveyor 2 a in the feeding zone at a speed equal to 0.25 meter per second. The feeding zone conveyor surface speed is about 0.03125 meter per second, which is about ⅛ of the feeding speed of the tow 1 wrapping around the batt-forming device 4 . The tow 1 is spread by conveyor 12 a in the spreading zone at a surface speed of 0.25 meter per second, resulting in a spread ratio of 8, which is equal to the conveyor surface speed in the spreading zone divided by the conveyor surface speed in the feeding zone. By the time the tow band travels 2 meters to reach and engage with conveyor 1 2 b in the feeding zone, the first portion of the tow 1 at 12 a has already been spread from 0.25 meters to 2 meters wide to form a batt with a 45-degree angle relative to the CD direction. Therefore, the original crimp in the continuous filaments is being extended, and the individual filaments in the tow 1 are spread and separated from each other. The first portion of the original 0.25-meter-wide tow band becomes a 2-meter spread and extended batt. Simultaneously, a second tow band of crimped continuous filaments with 100,000 filaments and total denier of 600,000 having a width of 0.25 meters is fed from container 8 b through a series of feeding and spreading rolls 10 b wrapping from the opposite position around the same 2-meter-wide batt-forming device 4 and engaged with conveyor 12 b in the feeding zone at a speed equal to that of container 8 a . A second spread, extended batt is formed similar to that of the first spread, extended batt. The two spread, extended batts form a cross-lapped structure with a cross-lapped angle about 90 degrees between the two batts. At this 90-degree angle, the cross-lapped structure has equal strength in both MD and CD directions, good stretch recovery properties, and high loft. In a continuous operation, these two tow bands from two separate feeding devices 8 a and 8 b make a continuous flat-tube structure as shown in FIG. 13 , with basis weight of about 100 grams per square meter. This flat-tube structure has layers wrapping around in continuous tubular form which cannot be peeled off, in contrast to the case of the conventional cross-lapped structure.
Example 2
[0079] Referring to FIG. 1 , a tow 1 of crimped continuous filaments with 100,000 filaments and total denier of 600,000 as in Example 1 is fed to the batt-forming device 4 at the same speed as in Example 1. A second tow 1 is also identical to that of Example 1 and is fed to the batt-forming device 4 as described in Example 1. The only exception is that the spread ratio is 4 instead of 8 as in Example 1. The resulting spread flat-tube structure has filament orientation of about a 27-degree angle relative to the CD direction. The flat-tube structure has a cross-lapped angle between layers of about 54 degrees.
Example 3
[0080] Referring to FIG. 1 , a tow 1 of crimped continuous filaments with 100,000 filaments and total denier of 600,000 as in Example 1 is fed to the batt-forming device at speed as in Example 1. A second tow 1 identical to that of Example 1 is fed to batt-forming device 4 as described in Example 1. The only exception is that the spread ratio is 12 instead of 8 as in Example 1. The resulting spread flat-tube structure has a filament orientation of about a 56-degree angle relative to the CD direction, and a cross-lapped angle between layers of about 112 degrees.
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Improved batts for sleeping bags, insulated apparel, bedding, and other uses are made from a tow of crimped continuous filaments by a machine and process which spreads, extends, and cross-laps the tow into an endless flat-tube structure with desired uniformity, balanced tensile strength, dimensional stability, stretchability, and high loft.
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[0001] This is a continuation application of U.S. patent application Ser. No. 10/866,126 filed Jun. 11, 2004, which claims priority to Korean Patent Application 10-2003-0046737, filed Jul. 10, 2003; all are hereby incorporated by reference herein.
BACKGROUND
[0002] The present invention is directed to automobile wallpaper, such as is typically used on seats, door trims and so on, in automobiles, and to methods for manufacturing such wallpaper. Material used for automobile wallpaper can be made from cloth, non-woven fabric, or PVC (polyvinyl chloride), and various processes are carried out with these materials so as to achieve various external appearances and colors. For example, by dyeing and performing print processing on cloth or non-woven fabric, various patterns and colors can be applied to achieve a luxurious effect. In the case of PVC, various surfaces and luxurious effects are achievable by means of embossed processing.
[0003] However, foam printing processes, to provide a three-dimensional effect on the surface of the wallpaper, have not been possible for use with materials used as automobile wallpaper. The reason for this is that automobile wallpaper is typically manufactured in mass quantities, at the same size and shape, through the use of molds. Because most mold processing is performed at high temperatures and pressures, printing patterns having three-dimensional effects, formed by means of foam printing, become crushed, and the three-dimensional effect is lost.
SUMMARY OF THE INVENTION
[0004] An object of the present invention is to provide an automobile wallpaper having a three-dimensional effect, and methods for manufacturing such a wallpaper.
[0005] In one preferred embodiment of the present invention, a wallpaper for use in an automobile and having a three-dimensional surface effect is provided. The wallpaper is formed by providing a wallpaper, and a printing liquid having a foaming agent comprising constituent parts, each comprising a thermoplastic polymer layer forming a cavity having a hydrocarbon gas. According to the present invention, the printing liquid is printed onto the surface of the wallpaper. Thereafter, heat is applied to the printed surface of the wallpaper to cause the hydrocarbon gas of the foaming agent to expand, to thereby provide a three-dimensional appearance to the wallpaper.
[0006] In another embodiment of the present invention, a method for manufacturing a wallpaper for use in an automobile is provided. The method comprises the steps of providing a wallpaper, and providing a printing liquid having a foaming agent comprising constituent parts, each comprising a thermoplastic polymer layer forming a cavity having a hydrocarbon gas. Moreover, the method of the present invention includes the steps of printing the printing liquid onto the surface of the wallpaper, and applying heat to the printed surface of the wallpaper to cause the hydrocarbon gas of the foaming agent to expand, to thereby provide a three-dimensional appearance to the wallpaper.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a schematic diagram illustrating a foam printing process for manufacturing wallpaper, according to an embodiment of the present invention.
[0008] FIG. 2 is a cross-sectional diagram of a constituent part of a preselected foaming agent used in an exemplary embodiment of the present invention.
[0009] FIG. 3 is a diagram illustrating the expansion of the foaming agent constituent used in an exemplary embodiment of the present invention.
[0010] FIG. 4 is an optical microscope photograph of the foaming agent used in an exemplary embodiment of the present invention, shown in a granular state before foaming.
[0011] FIG. 5 is an optical microscope photograph of the foaming agent used in an exemplary embodiment of the present invention, shown after it has been heated, foamed and expanded.
[0012] FIG. 6 is an electron microscope photograph, expanded 200 times, of a wallpaper printed according to the prior art.
[0013] FIG. 7 is an electron microscope photograph, expanded 200 times, of a wallpaper printed according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] Referring now to the drawings, and initially to FIG. 1 , there is illustrated a schematic diagram showing a foam printing process for manufacturing wallpaper, according to an embodiment of the present invention. A roll of automobile wallpaper 1 is feed to a printing device comprising a pair of opposed printing heads 2 . According to a feature of the present invention, the ink or printing liquid used at the printing heads 2 comprises a mixture that contains a preselected foaming agent that is able to expand. In the preferred embodiment, the preselected foaming agent contains constituent parts that are able to increase in volume by 30 times upon the application of heat, to give the wallpaper finish a three-dimensional effect.
[0015] As shown in FIG. 1 , the automobile wallpaper 1 , after printing via the printing heads 2 , is passed through a heating unit or dryer 3 to apply heat to the foaming agent contained in the ink or printing liquid printed onto the wallpaper 1 , so that it expands to provide automobile wallpaper having a three-dimensional effect, that is taken up in a roll 4 .
[0016] In the preferred embodiment of the present invention, the weight of the wallpaper 4 is from approximately 30 g/m 2 to approximately 300 g/m 2 . Moreover, the printing ink comprises a resin selected from the group consisting of acryl, stylene, polyvinylchloride, polyvinylalcohol, polyester, ethylenevinylchloride, ethylenevinyl acetate or polyurethane and combinations thereof. The resin comprises a base component of the printing ink or liquid applied to the wallpaper 1 in the printing process. It performs the function of attaching the ink and other additives of the ink, such as the preselected foaming agent, to the surface of the wallpaper during the printing process. Moreover, the resin, when it dries, wraps around the foaming agent constituent parts. This helps prevent the destruction of the foaming agent during high-temperature and high-pressure molding processes which the automobile wallpaper is typically exposed to during the manufacturing process.
[0017] Various dyes and color inks can be added to the resin, to provide a color effect, as may be desired by an automobile manufacturer. The printing ink can also include various additives, in addition to the foaming agent, dyes and color inks, that are mixed into the resin, such as silicon stabilizers, lubricants, fire retardant agents, thickening agents, and other additives, as is generally known in the art.
[0018] Referring now to FIG. 2 , there is shown a cross-sectional diagram of a constituent part of the preselected foaming agent used in this exemplary embodiment of the present invention. The preselected foaming agent comprises spherical constituent parts, as shown in FIG. 2 , each having a diameter, before expansion, of from approximately 5-50 mm. The exterior layer 5 of each constituent part comprises a thermoplastic polymer layer that provides a cavity containing a hydrocarbon gas 6 . The exterior layer 5 is approximately 2-15 mm thick. The thermoplastic polymer comprises a material with sufficient strength to withstand high-temperature and high-pressure exposure during the automobile wallpaper manufacturing process, and thereby protect the three-dimensional effect provided by the expanded foaming agent. To that end, the hydrocarbon gas 6 can expand, upon application of heat in the heating unit or dryer 3 , to expand the corresponding foaming agent part 30 times its original volume.
[0019] In the preferred embodiment of the present invention, the foaming agent comprises, for example, Expencel Microsphere brand foaming agent, manufactured by Akzo of Sweden, or Micropearl brand foaming agent, manufactured by Matsumoto, Inc. of Japan. The foaming agent is added to the resin of the printing ink, to comprise approximately 0.2 to 30 percent by weight of the printing liquid applied to the wallpaper 1 .
[0020] As shown in FIG. 3 , upon the application of heat, the hydrocarbon gas 8 expands the thermoplastic exterior layer 7 , to increase the volume of each constituent part of the foaming agent approximately 30 times the parts original size. The expansion of the constituent parts of the foaming agent causes the ink layer applied to the wallpaper 1 via the printing heads 2 to acquire a three-dimensional effect for the surface of the wallpaper.
[0021] According to the present invention, the print heads 2 can comprise any number of heads, for example, 1-10 print heads. Moreover, it is advantageous to conduct the printing and heating operations of the process continuously. Also, any of the following printing processes can be used to apply the printing liquid to the wallpaper 1 : a rotary screen method, a flat screen method or an offset printing method.
[0022] FIG. 4 to 7 provide various photos to illustrate the present invention. FIG. 4 is an optical microscope photograph of the foaming agent used in the exemplary embodiment of the present invention, shown in a granular state before foaming caused by the application of heat. FIG. 5 is an optical microscope photograph of the foaming agent, shown after it has been heated, foamed and expanded.
[0023] FIGS. 6 and 7 are electron microscope photographs of automobile wallpapers. FIG. 6 is an electron microscope photograph, expanded 200 times, of a wallpaper printed according to the prior art. FIG. 7 is an electron microscope photograph, expanded 200 times, of a wallpaper printed according to an embodiment of the present invention. The expanded spherical constituent parts of the foaming agent can be seen.
[0024] As described above, automobile wallpaper manufactured according to the exemplary embodiment of the present invention utilizes a foaming agent selected for its exterior polymer which expands 30 times in volume when heat is applied, and provides strength to structure forming a three-dimensional print pattern. The use of the selected foaming agent enables the achievement of various desirable results, as follows.
[0025] First, when using the selected foaming agent to achieve a three-dimensional effect when printing, the three-dimensional effect of the surface does not change at all during the high-temperature and high-pressure molding process. In existing foam printing, the foaming agent is normally mixed within the printing liquid, and nitrogen gas is given off by the foaming agent when heat is applied, so that the gas is trapped within the printing liquid to form the foam. Therefore, the foam in this kind of foaming agent is destroyed, and breaks down during high-temperature and high-pressure molding. Thus, the three-dimensional effect is lost. However, the foaming agent used in the present invention uses a gas which expands when heat is applied, and is surrounded in a polymer that has a high degree of strength and flexibility so that after the foam forms, there is no destruction of the foam even during the high-temperature and high-pressure molding processes typically encountered in manufacturing the wallpaper. Therefore, the three-dimensional effect of the wallpaper surface can be maintained.
[0026] Second, the automobile wallpaper manufactured according to the present invention has improved properties relative to wear resistance and sound absorption of the surface. The foaming agent used in this invention is a polymer with a high degree of strength and flexibility, so that it is very durable against external shocks such as friction. Also, the three-dimensional effect achieved on the surface of the wallpaper results in a two times or greater increase to the size of the surface area, which thereby improves the sound absorption properties of the wallpaper manufactured according to the present invention. It is common knowledge that, if the surface area of a material is large, the sound absorption properties of the material improve. Therefore, if the automobile wallpaper manufactured according to the present invention is applied to automobiles, it will be possible to experience a quieter interior than in automobiles which use currently available types of wallpaper.
[0027] Third, automobile wallpapers currently being used have a high defect rate. In the case of cloth, there are many defects and impurities that occur in the weaving process, and these parts are usually discarded as defective. In the case of non-woven fabrics, consecutive sheets are manufactured by joining the fibers using needle punching or water-flow bonding, but partially striped patterns occur due to the needle marks and traces left from water-flow bonding, so that the product quality is reduced. However, if the foam printing process of this invention is carried out to the surface of the wallpaper, the printed patterns expand to a fixed volume, bringing about a three-dimensional form, and this has the effect of covering over the aforementioned defects and reducing the defect rate, rendering it possible to manufacture wallpaper more inexpensively.
[0028] Furthermore, the foaming agent used in the present invention is able to achieve the same foaming effect as with existing foaming agents, but does so using a lesser quantity of the agent. The reason for this is that bubbles within existing foaming agents are formed only by the gas caught in the printing liquid, giving off nitrogen gas brought about by heat, so that the remainder of the foaming agent is absorbed by air, which makes it necessary to mix a large amount of foaming agent at the beginning. However, the entire amount of foaming agent selected for use in the present invention contributes to the foam, so the same foaming results can be achieved by using only a relatively small amount of agent. Another advantage is that there are hydrocarbons contained within the thermoplastic resin of the foaming agent used in the present invention. The hydrocarbon content contains fire retardant properties, so separate fire retardant processing is not necessary.
[0029] In the preceding specification, the invention has been described with reference to specific exemplary embodiments and examples thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention as set forth in the claims that follow. The specification and drawings are accordingly to be regarded in an illustrative manner rather than a restrictive sense.
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An automobile wallpaper, and an exterior surface finishing agent for the door trim, seats, and so on, of automobiles, as well as its manufacturing method. To manufacture such automobile wallpaper, a printing process is performed on the surface of a surface material which is currently being used, in order to render a three-dimensional effect to the surface, so as to achieve various luxurious appearances. The three-dimensional effect of the printing is maintained even during the molding process, and it also possesses excellent properties relative to sound absorbency, due to the three-dimensional effect of the surface.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention concerns a metallic gasket disposed between the joining faces of a cylinder head and a cylinder block that constitute an internal combustion engine to prevent combustion gas, cooling water, lubricant or the like from leaking.
2. Description of the Prior Art
In an internal combustion engine, a gasket is interposed between a cylinder block and a cylinder head to provide a seal therebetween. The materials of the gasket for a gasoline engine use a mixture of asbestos and rubber and have a spiked steel sheet embedded therein. A bore site peripheral edge covered with a stainless steel sheet and a peripheral edge of bolt holes covered with a copper sheet, respectively, are used as a countermeasure for a gap between the seal and the joining faces of the cylinder block and the cylinder head.
Further, for a diesel engine, a material comprising asbestos, rubber and a wire gauge embedded therein is used as a countermeasure for a gap at the edges and the joining faces as described above and a fire ring is further engaged along the edge of the bore.
Such gaskets are referred to as soft gaskets. However, since asbestos is used in gaskets of this type, its use has become restricted, particularly in view of environmental problems.
As far as the inventor knows, synthetic fibers are used instead of asbestos in a gasoline engine. Further, for a diesel engine, a structure comprising a steel laminate including a steel sheet base plate formed with a minute bead, a stainless steel subplate stacked thereon and a steel wire core disposed to the bore peripheral edge is used. The subplate is folded back to cover the wire on the inside and extends along the upper surface of the edge of the bore holes. A baked rubber seal ring is disposed at the bolt holes.
The soft gaskets are not satisfactory for providing reduced thickness, endurance to cope with decreasing distance between bores, engine weight and size reduction, material recycling, heat resistance, high performance, cost reduction and freedom of design. Eventually the demand for metallic gaskets will increase in the automobile industry.
By the way, in a metallic gasket, a bead is formed along the periphery of holes, in particular, at the periphery of combustion chamber holes (hereinafter referred to as a bore hole or bore holes). When a metallic gasket is tightened between a cylinder head and a cylinder block, the bead is elastically deformed to function as a seal. Further, a stopper is formed, together with the bead, at the periphery of the bore hole in the metallic gasket. The stopper suppresses vibrations at the joining face area between the cylinder block and the cylinder head caused by the operation of the engine, so that it also functions as a sealing member to prevent fatigue failure on account of engine vibrations. In the metallic gasket, a complete sealing effect is intended by attaining a primary seal with the stopper and a secondary seal with the bead compensated with the durability by the stopper.
The stopper may be formed by folding back a subplate described above so as to cover the inner circumferential surface of the bore hole, or it may be formed by arc plasma spray on a gasket base plate or as a metal shim.
In any case, the stopper must have a thickness corresponding to a gap in the engine, that is, a gap between the joined surfaces of the cylinder block and the cylinder head.
Recently, with the performance improvement owing to the progress in engine technology, fuel economy and the size and weight reduction, the distance between bores has been narrowed. In addition, the combustion temperature and the explosive pressure have increased due to the adoption of super-chargers. Accordingly, with the prior art, the width of the stopper cannot be increased and it is difficult to impede the bead vibrations. Further, as the engine temperature becomes higher, the pressure exerted on the gasket surface increases because of the combustion expansion, and denting into the aluminum cylinder head is caused when a narrow shim stopper is used. Further, complete sealing has become difficult. A double seal with a stopper primary seal and a bead secondary seal cannot be obtained. In addition, since the shim stopper is not fixed to the base plate, it sometimes slides or becomes detached.
This invention has been accomplished in view of the foregoing situation and it is an object thereof to provide a metallic gasket with a shim, even if a distance between bores is narrow, which is also capable of adjusting the bead spring force.
As an example of the metallic gasket in the relevant prior art, the invention has accomplished an invention as disclosed in Japanese Patent Publication Hei 2 (1990)-58502 and, further is well aware of Japanese Patent Laid-Open Sho 62 (1987)-155376 and Japanese Patent Publications Hei 3 (1991)-20626 and Hei 4 (1993)-40540.
SUMMARY OF THE INVENTION
To attain the foregoing object, the invention provides a metallic gasket in which a bead is formed on at least one elastic metal sheet base plate, whereon a shim is secured to a flat portion of the base plate on the bore hole edge of the concave bead at a position away from the center thereof, with the ends of the base plate and the shim being aligned on the side of the bore hole. The shim extends into the bead with a matching concave contour of the bead to compensate for the spring constant of the bead.
Then, the extended width of the shim varies from 110% to about 200% of the width of the flat portion depending on the attaching position of the shim.
That is, the extension width of the shim is reduced near bolt holes, while the width is increased between the bolt holes. This is because the spring constant of the bead can be small near the bolt holes since the tightening surface pressure is large and the gap is small at the joint area of the cylinder block and the cylinder head. However, the spring constant of the bead has to be increased in the portion between the bolt holes since the tightening surface pressure is smaller and the gap is larger.
Thus, the shim is disposed with a contour matching the concave surface of the bead, and the shim extension into the bead is made larger between the bolt holes where the surface pressure is the lowest, and it is reduced near the bolt holes where the surface pressure is high, thereby making the spring force uniform.
However, according to the experience of the inventor, in a case where the flat portion of the base plate to which the shim is attached is extremely narrow as in the case of an engine with a narrow inter-bore gap, the shim width has to be narrowed corresponding and, if the extension of the shim into the bead is smaller than about 110% of the width of the flat portion, it is impossible to prevent a dent from being formed by the shim on the engine. That is, unless the extension of the shim into the bead is at least about 110% of the flat portion of the base plate, it is so narrow that a dent is formed on the engine.
On the other hand, if the extension of the shim into the bead exceeds about 200% of the width of the flat portion, it causes undesirable interference of the shim in a narrow inter-bore gap engine.
Further, the shim can be applied where the flat portion near the bolt hole has to be very narrow. This can be accomplished by fixing the shim to the base plate so that the shim edge extends into the bead and a flat portion is secured to the flat portion of the base plate.
Then the thickness of the shim is usually made less than the thickness of the base plate, and it can be conformed to an uneven gap at the joint of the cylinder head and the cylinder block.
Further, another base plate may be disposed to the base plate described above with the recess of the bead of another base plate facing the recess of the bead of the baseplate described to form a structure wherein the shim is sandwiched between the two base plates so that it can cope with engine temperature deformation.
In addition to the constitution described above, if an intermediate plate is placed between the shimmed base plate and the base plate, it can enhance the sealing effect of the base plate and also function as a spacer.
Then, in addition to the constitution described above, the combined state of the shim and the base plate may be turned over and another base plate stacked thereover with the recesses of the beads being in the same direction. The amount of spring restoration is reduced and the spring rigidity is increased.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a plan view of a typical embodiment of a metallic gasket of the present invention;
FIG. 2(a) is a cross sectional view taken along line A--A in FIG. 1;
FIG. 2(b) is a cross sectional view taken along line B--B in FIG. 1;
FIG. 2(c) is a cross sectional view illustrating a preferred embodiment of shim edge which protrudes into a bead;
FIG. 3 is a cross sectional view of another embodiment;
FIG. 4 is a cross sectional view of yet another embodiment; and
FIG. 5 is a cross sectional view of a different embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Example 1
As shown in FIG. 1, a metallic gasket, which is entirely depicted as reference number 100, comprises an elastic metallic sheet (hereinafter referred to as a base plate) 1. A bore hole (for a combustion chamber bore) 5 corresponds to the cylinder bore number of a cylinder block, not shown.
A bead 2 is formed in the base plate 1 along a periphery of the bore hole and the circle 21 shown by a chain line represents the crest of the bead 2.
A shim 24 is an annular plate having an inner diameter equal to the diameter of the bore hole 5 in the base plate 1, with the inner diameter aligned with the bore hole 5. As shown in FIG. 1, the base plate 1 has bolt holes 29 at a position determined by dividing the circumference of the bore hole 5 into four even parts. Oil holes 30 are situated near two of the four bolt holes 29 and a cocoon-shaped water hole 31 is formed between the bolt holes 29.
As can be seen from FIG. 1, the outer diameter of the shim 24 is smaller close to the bolt holes 29 and is larger at a portion between the bolt holes 29. In this embodiment, a portion of the shim 24 protruding into the bead 2 extends to the maximum, i.e., at crest line 21, while a portion thereof protrudes slightly into the edge of the bead 2 where it is close to one bolt hole 29.
That is, in this embodiment, assume the width of a flat portion 1a of the base plate 1 as 100%, the width of the protruding portion of the shim 24 that extends as far as the crest line 21 of the bead 2 is 200%, and the width of the slightly protruding portion thereof is 110%.
As described above, the outer diametrical shape of the shim 24 is not true circular while the bore hole 5 is a true circle. The shim diameter is smaller at portions 26-1, 26-2, 26-3 and 26-4 near the bolt holes 29 and the shim diameter is larger at portions 25-1, 25-2, 25-3 and 25-4 corresponding to the intermediate area between the bolt holes 29.
FIG. 2(a) shows the intermediate area between the bolt holes 29, taken along line A--A in FIG. 1. In this portion, the shim 24 extends as far as the crest of the bead 2. The width of the shim 24 is depicted by W 1 . FIG. 2(b) shows a portion near the bolt hole 29, taken along line B--B in FIG. 1, in which the shim 24 extends slightly into the bead 2. The width of the shim 24 is depicted by W 2 . Then, as shown in FIGS. 2(a) and 2(b), it is apparent that the width or extending amount of the shim 24 has a relationship: W 1 >W 2 for the area between the bolt holes 29 and the portion near the bolt holes 29. FIGS. 2(a) and 2(b) also show that the shape for the outer edge of the shim 24 varies along the circumferential edge thereof.
By the way, as shown in FIGS. 2(a) and 2(b), the thickness T 2 of the shim 24 is about one-half the thickness T 1 of the base plate 1. Since the shim 24 is used to reinforce the base plate 1, it is preferred to keep the thickness thereof as necessary for the reinforcement and to make it as thin as possible so that it will conform to the joint area between the cylinder block and the cylinder head.
FIGS. 2(a) and 2(b) show an embodiment in which an edge 34a of the shim 24 protruding into the bead 2 and a flat portion is stacked and secured to the base plate 1 and is aligned with the edge 34b of the base plate 1 which is contiguous from a flat portion 1a on the side of the bore hole 5 to the bead 2. In a case where the flat portion near the bolt hole 29 is extremely narrow as shown in FIG. 1, the border edge 34a of the shim 24 may be displaced from the edge portion 34b of the base plate 1 to the bead 2 so as to overhang in the bead 2 as shown in FIG. 2(c).
In this way, the flat portion of the shim 24 is secured to the flat portion 1a of the bore hole 5 of the base plate 1 as shown by reference number 27 in FIGS. 2(a), 2(b) and 2(c) by bonding or welding. In this case, the end of the flat portion 1a of the base plate 1 near the bore 5 and the end of the flat portion of the shim 24 have to be aligned.
Thus, when the shim 24 is appended to the base plate 1, insufficient or uneven surface pressure caused by a gap variation at the joint area between the cylinder head and the cylinder block can be eliminated. The necessary spring constant can be attained and effectively ensures a seal without over tightening the shim 24 which could cause a dent in the cylinder head. In this arrangement, since the flat portion of the shim 24 covers the edge 34b of the base plate 1 on the side of the bore hole 5, the pressure exerted on the surface at the edge becomes highest to improve the sealing effect.
Example 2
FIG. 3 shows another embodiment of the present invention. In this embodiment, two base plates 1-1 and 1-2 are joined with the recesses of the beads 2-1 and 2-2 facing each other. A shim 24 is secured at a flat portion 1a of the base plate 1-1. Another base plate 1-2 is appended to the lower surface of the shim 24 so that the shim 24 is sandwiched between the two base plates 1-1 and 1-2. FIG. 3 shows an intermediate position between the bolt holes 29 shown in FIG. 1, in which the extended shim 24 reaches the crest of the bead 2-1.
This embodiment is effective in coping with engine deformation due to the temperature.
Example 3
FIG. 4 shows an addition to the construction of the embodiment shown in FIG. 3. An intermediate plate 33 is interposed between the shim 24 and a base plate 1-2. This can provide an effective seal and also function as a spacer.
Example 4
FIG. 5 shows another addition to the construction of the embodiment shown in FIG. 3. The combined shim 24 and base plate 1-1 is turned over and a base plate 1-2 is stacked thereover such that the recesses of the beads 2 are in the same direction. This embodiment is suitable to reduce the restoration force and to increase the spring rigidity.
As has been described above, it can be understood that the spring constant can be varied by controlling the width of the shim and the surface pressure of the edge at the bore hole can be increased on the concave side of the bead so that the sealing effect can further be improved by this invention.
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A metallic gasket of a structure in which a bead is formed to a base plate having at least one elastic metallic sheet, wherein a shim is secured to a flat portion of the base plate on the concave side of the bead at a position displaced from the center of the bead toward a bore hole of the base plate, with the ends of the base plate and the shim being aligned on the side of the bore hole, and the shim is extended into the bead with a contour matching the concave surface of the bead.
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This is a division of copending application Ser. No. 861,892 filed Dec. 19, 1977, now U.S. Pat. No. 4,172,151, Ser. No. 861,892 being a division of copending application Ser. No. 797,137 filed May 16, 1977 (now abandoned).
BACKGROUND OF THE INVENTION
This invention relates to the use of 2,6-di(t-butyl)-4-phenylphenols as anti-inflammatory agents and to certain novel compounds.
The compound 2,6-di(t-butyl)-4-phenylphenol itself is known (see, for example, J. Am. Chem. Soc. 95:4698, 1973), and the synthesis of 2,6-di(t-butyl)-4-(4'-nitrophenyl)phenol has been reported (J. Org. Chem. 33:1245, 1968). 2,6-Di(t-butyl)-4-phenylphenols in which the 4-phenyl ring is substituted by other groups are, however, novel insofar as is known. No physiological use of any of these compounds has been reported, however.
DETAILED DESCRIPTION OF THE INVENTION
Specifically the invention relates to a method for combatting inflammatory processes in mammalian animals which comprises administering thereto an effective dose, less than the toxic amount, of a compound of the formula: ##STR1## wherein R is selected from hydrogen, amino, alkanamido containing from 2 to 4 carbon atoms, trifluoroacetamido, halogen, methoxy, methyl and 4-nitro. The invention also relates to anti-inflammatory compositions comprising one or more such compounds (in which R is as just recited) together with a suitable pharmaceutical extending medium. The compounds of formula I wherein R is hydrogen, amino or methoxy are presently preferred for use in the anti-inflammatory method and compositions of the invention, particularly those in which R is hydrogen, 4'-amino or 2'-methoxy.
In another aspect, the invention relates to new chemical compounds of structure I but wherein R is amino, alkanamido containing from 2 to 4 carbon atoms or trifluoroacetamido. It is noted that when R is nitro, only the compound wherein R is 4'-nitro has been found to be useful as an anti-inflammatory agent. Novel compounds wherein R is 2'-nitro or 3'-nitro form part of the invention, however, since they can be reduced to 2'-amino or 3'-amino compounds which are useful as anti-inflammatory agents.
In addition to their anti-inflammatory activity, some of these compounds are also analgesic and antipyretic agents and some have mild immunosuppressant activity.
In order to determine and assess pharmacological activity, testing in animals is carried out using various assays known to those skilled in the art. Thus, the anti-inflammatory activity of the compounds can be conveniently demonstrated using an assay designed to test the ability of these compounds to antagonize the local edema which is characteristic of the inflammatory response (the rat foot edema test). Anti-inflammatory activity may also be detected by other assays known to the art such as the cotton pellet granuloma test and the adjuvant arthritis test and the inhibition of the enzyme prostaglandin synthetase.
Leading references to the rat foot edema method are:
(1) Adamkiewicz et al, Canad. J. Biochem. Physio. 33:332, 1955;
(2) Selye, Brit. Med. J. 2:1129, 1949; and
(3) Winter, Proc. Exper. Biol. Med. 111:554, 1962.
The edema test is performed on adult female rats. One group of 10 rats serves as non-medicated controls, while another group of 10 rats receives the test compound at various times prior to the induction of the edema, usually 15 minutes, one hour and/or 18 hours. The test compound is administered orally as a suspension in 4 percent aqueous solution of acacia. Edema is induced by the plantar injection of 0.5 percent carrageenin (0.1 ml/foot) into the right hind foot. The left hind foot receives a like volume of 0.9 percent saline solution. One hour later, the volume of each hind foot is determined plethysmographically. The edema is expressed as the increase in the volume of the edemogen-injected foot (volume of the "edemogen foot" less the volume of the "saline foot"). The percent inhibition is calculated by dividing the mean increase in the edema of the edemogen foot of the medicated group by the mean increase in the non-medicated group, multipled by 100. An active dose is that giving a statistically significant inhibition of the induced edema, usually in the range of about 25-35 percent inhibition.
The compounds are preferably administered orally as anti-inflammatory agents but other known methods of administration are contemplated as well, e.g. dermatomucosally (for example dermally, rectally and the like) and parenterally, for example by subcutaneous injection, intramuscular injection, intra-articular injection, intravenous injection and the like. Ocular administration is also included. Dosages ordinarily fall within the range of about 1 to 500 kg/mg of body weight of the mammal to be treated although oral dosages are not usually above 100 mg/kg. Suitable forms for oral administration include liquids (such as 4 percent acacia and polyethylene glycol solutions), tablets (which may contain anhydrous lactose, microcrystalline cellulose, modified starch, calcium stearate and talc, as well as other conventional compounding agents together with the active anti-inflammatory agents), solid suspensions and capsules. Suitable carriers for topical application include creams, gels, tapes and the like. Liquid formulations, such as solutions or suspensions of the active ingredient in inert carriers, are contemplated for dosage by injection.
The compounds which are presently preferred for use in the process of the invention (due to their high activity in the rat foot edema test) are:
2,6-di-(t-butyl)-4-phenylphenol,
4-(4'-aminophenyl)-2,6-di(t-butyl)phenol and
2,6-di(t-butyl)-4-(2'-methoxyphenyl)phenol.
The preparation of compounds of the invention may be carried out as described in the prior art or by chemical reaction of compounds described in the prior art. Alternatively, novel compounds of the invention, for example, compounds wherein R is amino, may be further utilized as intermediates to prepare other compounds of the invention. Many compounds of the invention are conveniently prepared by reaction of 2,6-di-(t-butyl)benzoquinone with an appropriate Grignard reagent, followed by reduction of the intermediate substituted cyclohexadienone. The necessary starting materials are well known to the art. The reduction step may be carried out using hydrogen gas and a catalyst such as palladium on charcoal or Raney nickel, using a metal hydride reducing agent such as lithium aluminum hydride or using hydrogen iodide.
Conventional reactions of aromatic substituent groups are generally applicable to the compounds of the invention. For example, nitro groups can be reduced, amino groups can be acylated, amino groups can be diazotized and replaced and the like.
Preparation of novel compounds of the invention and known compounds useful in the method of the invention are described in the following illustrative examples.
EXAMPLE 1
Magnesium metal (0.55 g.) and 50 ml. of diethyl ether are treated with a few ml. of a solution of 4.25 g. of 4-bromoanisole in 50 ml. of ether. An iodine crystal is added, and the mixture begins to react upon warming. The remainder of the solution is added, and the mixture is heated at its reflux temperature for 15 minutes. It is then added over 30 minutes to a solution of 2,6-di(t-butyl)benzoquinone in 50 ml. of ether. This mixture is heated at its reflux temperature for two hours, then stirred at room temperature for 16 hours. The product is 2,6-di-(t-butyl)-4-hydroxy-4-(4'-methoxyphenyl)-2,5-cyclohexadienone.
To this product is added 1.5 g. of lithium aluminum hydride dissolved in diethyl ether. After stirring for 30 minutes, the solution is acidified with 10 percent hydrochloric acid and extracted with dichloromethane. The extracts are dried over magnesium sulfate, then evaporated to provide an oil which is chromatographed on 125 g. of 60-200 mesh silica gel, eluting with 1:3 benzene-hexane. The first 500 ml. of solvent is evaporated to provide an oil which crystallizes when petroleum ether is added. Recrystallization from petroleum ether provides 2,6-di(t-butyl)-4-(4'-methoxyphenyl)phenol, m.p. 109°-110° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.21 H.sub.28 O.sub.2 : 80.7, 9.0Found: 80.9 9.2.______________________________________
EXAMPLE 2
Using the method described in the art (J. Org. Chem. 33:1245, 1968) 2,6-di(t-butyl)-4-(4'-nitrophenyl)phenol, m.p. 154°-156° C., is prepared. Using this method and starting with 2-chloronitrobenzene, 2,6-di(t-butyl)-4-(2'-nitrophenyl)phenol, m.p. 101°-102.5° C. is prepared.
EXAMPLE 3
A solution of 50 g. (0.152 mole) of 2,6-di(t-butyl)-4-(4'-nitrophenyl)phenol in 350 ml. of ethyl acetate is reduced with hydrogen gas at about 45 psig in a Paar apparatus using 10 percent palladium on charcoal as catalyst. The mixture is allowed to stand for about 16 hours, filtered, and the filtrate evaporated under vacuum. The residue is cooled, dissolved in ethanol and triturated with water. The resulting off-white solid is recrystallized from petroleum ether to provide 4-(4'-aminophenyl)-2,6-di(t-butyl)phenol, m.p. 113°-114.5° C.
______________________________________Analysis: % C % H % N______________________________________Calculated for C.sub.20 H.sub.27 NO: 80.7, 9.1, 4.7Found: 81.1, 9.1, 4.7.______________________________________
EXAMPLE 4
A solution of 10 g. (0.0336 mole) of 4-(4'-aminophenyl)-2,6-di(t-butyl)phenol in 50 ml. of dichloromethane is reacted with 7.1 g. (0.034 mole) of trifluoroacetic anhydride. The immediate reaction is followed by evaporation of the solvent to provide a residue which is recrystallized from a benzene-hexane mixture. The white product is 2,6-di(t-butyl)-4-(4'-trifluoroacetamidophenyl)phenol, m.p. 155°-156° C.
______________________________________Analysis: % C % H % N______________________________________Calculated for C.sub.22 H.sub.26 F.sub.3 NO.sub.2 : 67.1, 6.7, 3.6Found: 67.1, 6.7, 3.5.______________________________________
EXAMPLE 5
A solution of 15 g. (0.050 mole) of 4-(4'-aminophenyl)-2,6-di(t-butyl)phenol in 100 ml. of glacial acetic acid is treated with 5.2 g. (0.050 mole) of acetic anhydride. The resulting solution is heated gently for 10 minutes, diluted with water, cooled, and the solid product is separated by filtration. Recrystallization from a benzene-hexane mixture provides 4-(4'-acetamidophenyl)-2,6-di(t-butyl)phenol, m.p. 173°-174.5° C.
______________________________________Analysis: % C % H % N______________________________________Calculated for C.sub.22 H.sub.29 NO.sub.2 : 77.8, 8.6, 4.1Found: 77.8, 8.8, 4.0.______________________________________
EXAMPLE 6
To a stirred solution of 15 g. (0.0504 mole) of 4-(4'-aminophenyl)-2,6-di(t-butyl)phenol in 75 ml. of dichloromethane is added dropwise 5.37 g. (0.0504 mole) of n-butyroyl chloride. The reaction is immediate. The solvent is removed by evaporation, and the solid residue is recrystallized, first from aqueous ethanol, then from heptane to provide 4-(4'-butyramidophenyl)-2,6-di(t-butyl)phenol, m.p. 180°-181° C.
______________________________________Analysis: % C % H % N______________________________________Calculated for C.sub.24 H.sub.33 NO.sub.2 : 78.4, 9.0, 3.8Found: 78.4, 8.9, 3.7.______________________________________
EXAMPLE 7
Using the method described in Example 1, 2-bromomethoxybenzene is reacted with 2,6-di(t-butyl)hydroquinone to provide 2,6-di(t-butyl)-4-hydroxy-4-(2'-methoxyphenyl)-2,5-cyclohexadienone. This product is dissolved in ethanol and reduced with hydrogen gas on a Parr apparatus using palladium on charcoal as the catalyst. The white solid product is recrystallized from benzene to provide 2,6-di(t-butyl)-4-(2'-methoxyphenyl)phenol, m.p. 98.5°-100° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.21 H.sub.28 O.sub.2 : 80.7, 9.0Found: 81.1, 9.1.______________________________________
EXAMPLE 8
Using the method of Example 7, but starting from 3-bromomethoxybenzene, one obtains 2,6-di(t-butyl)-4-(3'-methoxyphenyl)phenol, m.p. 96°-98° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.21 H.sub.28 O.sub.2 : 80.7, 9.0Found: 80.9, 9.2.______________________________________
EXAMPLE 9
Using the method of Example 1, but starting from 2-bromotoluene, one obtains 2,6-di(t-butyl)-4-hydroxy-4-(2'-methylphenyl)-2,5-cyclohexadienone, m.p. 168°-171° C. This product is reduced as described in Example 7 to provide 2,6-di(t-butyl)-4-(2'-methylphenyl)phenol, m.p. 85.5°-87.5° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.21 H.sub.28 O: 85.1, 9.5Found: 84.7, 9.5.______________________________________
EXAMPLE 10
Using the method described in Example 1, 4-bromofluorobenzene is reacted to provide 2,6-di(t-butyl)-4-hydroxy-4-(4'-fluorophenyl)-2,5-cyclohexadienone, m.p. 123°-125° C. This product is reduced as described in Example 1 to provide 2,6-di(t-butyl)-4-(4'-fluorophenyl)phenol, m.p. 97°-99° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.20 H.sub.25 FO: 80.0, 8.4Found: 79.7, 8.5.______________________________________
EXAMPLE 11
Using the method of Example 7, 4-bromotoluene is converted to 2,6-di(t-butyl)-4-(4'-methylphenyl)phenol, m.p. 119.5°-121° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.21 H.sub.28 O: 85.1, 9.5Found: 85.2, 9.5.______________________________________
EXAMPLE 12
Using the method of Example 1, 2-bromochlorobenzene is reacted to provide 2,6-di(t-butyl)-4-(2'-chlorophenyl)-2,5-cyclohexadienone. This product (5.0 g., 0.015 mole) is treated with 125 ml. of concentrated hydroiodic acid and stirred for about 16 hours. The mixture is filtered, the residue rinsed with water and then dried to provide an off-white powder. The product is recrystallized from petroleum ether to provide 2-(2'-chlorophenyl)-2,6-di(t-butyl)phenol, m.p. 89.5°-91° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.20 H.sub.25 Cl0: 75.8, 7.95Found: 76.1, 8.1.______________________________________
EXAMPLE 13
To a solution of 7.0 g. (0.0235 mole) of b 4-(4'-aminophenyl)-2,6-di(t-butyl)phenol in 3 ml. (0.0706 mole) of concentrated sulfuric acid is added about 15 ml. of water, and the mixture is chilled to about 5° C. To this mixture a cold solution (about 5° C.) of 1.62 g. (0.0235 mole) of sodium nitrite in 8 ml. of water is added dropwise with stirring. The mixture is stirred for another ten minutes, and a cold solution of 3.37 g. (0.0235 mole) of cuprous bromide in 20 ml. of 48 percent hydrobromic acid is added slowly. After stirring for an additional hour, the mixture is extracted with about 100 ml. of dichloromethane. The extracts are dried, then evaporated. The residue is mixed with heptane, then filtered to provide a solid product which is purified by dissolving in hexane, eluting through a silica gel column with methanol-water and recrystallized from petroleum ether. The product is 4-(4'-bromophenyl)-2,6-di(t-butyl)phenol, m.p. 139.5°-141° C.
______________________________________Analysis: % C % H______________________________________Calculated for C.sub.20 H.sub.25 BrO: 66.5, 7.0Found: 66.6, 7.2.______________________________________
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Compounds in which 2,6-di(t-butyl)phenol is substituted in the 4 p;osition by an optionally substituted phenyl group have valuable pharmacological activity as anti-inflammatory agents.
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ORIGIN OF THE INVENTION
The invention described herein was made in the performance of work under a NASA contract and is subject to the provisions of Section 305 of the National Aeronautics and Space Act of 1958, Public Law 85-568 (72 Stat. 435; 42 USC 2457).
FIELD OF THE INVENTION
The invention relates to electromagnetic, wireless power transmission systems, and more particularly to apparatus and methods for controlling an electromagnetic transmission beam in accordance with power distribution profiles which are altered by an object entering the beam.
BACKGROUND OF THE INVENTION
Systems for transmitting rather low levels of power in the form of electromagnetic energy from one location to another have been extensively utilized such as in radio, TV and radar systems. These systems have also been proposed for much higher levels of power transfer between ground station and spacecraft, ground station and aircraft, and ground station and ground station. However, one problem inherent in such systems, especially as microwave beam power level increases, has been the potential hazard to life and property due to accidental intrusion into the power beam. The effects of high level microwave radiation (greater than 10 mW/cm 2 ) on personel and property are known to be at least thermal for long term exposure and can result in dehydration, cataract formation, and, at very high intensities, "steam" explosions in trapped fluid situations. However, near perfect reflectors, such as aluminum sheets, are unaffected at least up to flux densities as high as kilowatts per square centimeter as in Cassegrainian antenna reflectors.
The effects of medium level microwave radiation (1-10 mW/cm 2 ) on personnel are controversially theorized to be cardiovascular symptoms, white body cell shifts, temporary sterility, tension, nausea, brain arrhythmia and reduced sound perceptions. At lower levels (less than 1 mW/cm 2 ) there are certain brain wave and central nervous system responses, selected chromosone breaks and behavior modifications attributed to microwave radiation. These levels may be encountered in sidelobes or grating lobes of beamed power antenna patterns. Since a person cannot see or hear an approaching microwave beam or high level sidelobe, a system to protect personel and property from the damaging effects of an encounter with a microwave power transmission beam is desirable. As the power of these systems increases, protection becomes more and more important. The present invention provides a microwave power transmission beam control apparatus and method which solves the safety problem associated with conventional microwave beam systems by diminishing the level of or by removing microwave radiation from the vincinity of an object intersecting the beam, thus providing a capability for increasing the power transmitted by microwave beams without increasing the hazard to personnel and property encountering such beams.
SUMMARY OF THE INVENTION
Although reference has been and will be made to a microwave power transmission beam, it will be recognized that the method and means disclosed will be applicable to laser beams as well. For example, in the case of laser beam transmission, a power microwave beam may be simultaneously and coaxially transmitted and used to sense the presence of an object to reduce or shut off the laser power beam. Consequently, the term power beam will be used in the claims as a generic term to encompass the microwave power beam or a laser power beam. The term pilot beam then refers to a low power microwave beam, although for a microwave power beam, the pilot beam will be disposed within a power beam, and for a laser beam will be disposed around the laser beam.
In accordance with one embodiment of the present invention, a pilot beam transmitter is centrally disposed within a power beam receiving antenna array located at a ground station. Pilot beam receivers are diplexed to power beam radiator array elements located on a spacecraft, the power beam radiator array being positioned so that a microwave beam radiated therefrom will irradiate the power beam receiving antenna array at the ground station. A power distribution profile of the pilot beam as received at the spacecraft is compared to a predetermined power distribution profile by a power beam control computer located on the spacecraft in order to determine whether the beam path between the spacecraft and the ground station is unobstructed. An example would be to determine if maintenance personnel and their associated equipments or vehicles were removed from the face of a transmitting or receiving array. If it is unobstructed, the power beam radiator array on the spacecraft can be activated for transmission of microwave energy to the receiving antenna array located at the ground station. The received power distribution profile over the receiving antenna array is transmitted to the spacecraft via a data link subsystem and compared to a predetermined received power distribution profile, this comparison then indicating whether or not the beam path between the spacecraft and ground is being interrupted.
The invention also provides for comparison of a reflected power distribution profile at the power beam radiator array and a predetermined reflected power distribution profile, the results of which are indicative of whether a nearby intruding object is reflecting microwave energy back to the spacecraft. In order to further enhance sensitivity the invention also provides for use of a series of spaced-apart receiving antenna subarrays at power beam sidelobe null locations in the vicinity of the ground station receiving antenna array. Power scattered by an object in the power beam will change the power distribution profile seen by these subarrays. The scattered power distribution profile of these receiving antenna subarrays is also transmitted to the power beam control computer on the spacecraft via the data link subsystem and compared to a predetermined scattered power distribution profile. The invention further provides for the placing of receiving antenna subarrays apart from the power beam radiator array located on the spacecraft, the scattered power distribution profile of these subarrays again being compared to a predetermined scattered power distribution profile. The results of all the above-mentioned power distribution profile comparisons are used to generate signals for controlling the power, shape and direction of the microwave power beam being transmitted from the spacecraft to the ground, thereby insuring that an object intruding into the microwave power transmission beam will not be harmed. A beam penetration tester is also provided, the tester comprising a microwave opaque object to be inserted in the power beam. If a response due to the insertion is not within predetermined limits, the power beam is immediately turned off.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates schematically the major components of a system according to the present invention.
FIG. 2 is a block diagram of a microwave power transmission beam control system according to the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
As required, a specific embodiment of the invention is disclosed herein. This embodiment exemplifies the novel concepts of the invention, and is currently considered to be the best mode for practicing the invention. However, it is to be recognized that modifications and equivalents may readily occur to those skilled in the art, such as other power distribution profiles which could be utilized for detection of an object entering the microwave power transmission beam. Accordingly, the specific embodiment disclosed is only representative in providing a basis for the claims which define the scope of the present invention.
As noted hereinbefore, the invention provides a means and method for controlling an electromagnetic power beam in accordance with the presence of an object being irradiated by the beam. Control of the beam may take the form of reducing the power, changing the shape, diverting or dousing the beam, i.e., turning the beam off completely. Control is initiated by comparing a predetermined power distribution profile and an actual power distribution profile of transmitted, reflected, and scattered microwave energy across various receiving antenna surfaces of the system. These profiles are affected by the presence of an object within the microwave power transmission beam which reflects, absorbs or scatters some of the microwave energy. The profile comparisons provide the information necessary to generate control signals for altering the characteristics of the microwave power transmission beam.
Referring to FIG. 1, an orbiting spacecraft 10 has positioned therein a power beam radiator array 12 which is oriented so that microwave energy radiated therefrom will irradiate a power beam receiving antenna array 14 located at a ground station 15. A radiator array positioning means 16 on the spacecraft is provided so that radiation from the radiator array 12 will continuously irradiate the receiving antenna array 14 regardless of the position of the spacecraft with respect to the ground station. Solar energy collected at the spacecraft, which could be derived from a solar cell array not shown, is converted to microwave energy and transferred from the spacecraft 10 to the ground station via a microwave power beam 18 for subsequent use.
In the specific embodiment shown, an orbiting spacecraft is utilized as an energy collector, and a ground station is used as an energy receiver. However, the invention is not limited to a spacecraft to ground station application. The concepts are equally applicable for energy transmission from a ground station to a spacecraft, from a ground station to an aircraft, from an aircraft to a ground station, and from one ground station to another ground station.
As previously explained, sufficient energy levels can be obtained within the microwave power transmission beam 18 to seriously injure, and perhaps kill living organisms which remain within the beam for any length of time. By way of example, an aircraft 20 is shown entering the microwave beam 18. As the aircraft enters the beam, it reflects some of the microwave energy as shown at 22 and either absorbs or scatters some of the energy as shown at 24. The absorbed or reflected energy will alter a reflected power distribution profile across the face of the power beam radiator array 12 and a received power distribution profile across the face of the receiving antenna array 14. A comparison of the power distribution profiles being experienced with predetermined power distribution profiles, both from the radiator array and receiving antenna array, will produce characteristics indicative of the aircraft entering the power transmission beam. The characteristics include size, absorption, reflectivity, and speed. Means to alter the power transmission beam, either by reducing the power of the beam, changing the beam shape, diverting the beam so that it no longer irradiates the intruding object, or dousing the beam is provided as will be discussed more fully below.
In addition to the reflected power distribution profile across the face of the radiator array 12, and the received power distribution profile across the receiving antenna array 14, another power distribution profile is provided by a pilot beam transmitter 26 centrally disposed in the power beam receiving antenna array 14 and a series of pilot beam receivers 28 diplexed to central elements of the power beam radiator array 12. Energy is transmitted from the pilot beam transmitter 26 as shown at 30. The purpose of the pilot beam is to provide an alternate or additional indication of the intrusion of an object, its presence being indicated by a reduced signal received by the pilot beam receivers 28. The transmitter 26 radiates at a frequency close to but not exactly equal to that of the microwave power transmission beam 18. The difference allows the pilot beam receivers 28 to discriminate between changes in the pilot beam 30 and reflected radiation from the aircraft 20 as shown at 22.
In order to further enhance sensitivity of the system, a plurality of receiving antenna subarrays 32 are spaced apart but near the power beam receiving antenna array 14 so that as energy (shown at 24) is scattered by the aircraft 20, the power distribution profile at the spaced-apart subarrays 32 will change. It is felt that it is particularly useful to place the receiving antenna subarrays 32 at sidelobe nulls of the power transmission beam 18. Thus, as energy of the power transmission beam is scattered, the receiving antenna subarrays 32 will experience an upward level change indicative of an object entering the transmission beam 18. In a similar manner, another plurality of receiving antenna subarrays 34 are disposed on the spacecraft so that energy scattered by the intruding aircraft 20 can also be detected.
The received power distribution profile of the receiving antenna array 14 and the scattered power distribution profile of the spaced-apart antenna subarrays 32 are transmitted to the spacecraft by a data link subsystem comprising a ground station transmitter 36 and a spacecraft receiver 38. The data link transmitter function could be provided by the pilot beam transmitter, and the function of the receiver could be provided by the pilot beam receiver 28. A computer on the spacecraft compares predetermined power distribution profiles with the actual power distribution profiles of the receiving antenna array 14 and the spaced-apart receiving antenna subarrays 32. The results of the comparison indicate whether an object is in the power transmission beam 18. It would be equally possible to have the power distribution profile comparisons made on the ground. The results of the comparisons would then be transmitted to the spacecraft via a data link beam 40.
In order to properly check operation of the system, a beam penetration tester 42 is provided to interrupt the power beam, the beam tester being a mechanical device opaque to microwave energy that can be moved at preset speed and with a predetermined direction or distance into the power transmission beam 18 by a mechanism 44. The resulting power distribution profiles can then be used to verify proper operation of the system. The mechanism shown schematically is so constructed that it can be positioned over any portion of the receiving antenna array 14 in order to test the beam shape alteration circuitry on the spacecraft 10. One arrangement for this mechanism could consist of a nylon line stretched across the array 14. The opaque device suspended on the nylon line could then be pulled across the array as required, and dollys on tracks parallel to the sides of the array 14 could be used to move the line to different positions across the array. Alternatively, a pilotless vehicle could be flown across the array.
Operation of the system can be understood by referring to the functional blocks shown in FIG. 2. The power beam radiator array 12 is positioned by the positioning means 16 so that the power transmission beam 18 irradiates the receiving antenna array 14. The power beam radiator array 12 is constructed to minimize the angle subtended by the power transmission beam 18, and the receiving antenna array 14 is large enough to intersect substantially all of the energy radiated from the radiator array 12. For the spacecraft application herein described, a typical receiving antenna array might be 100 meters square. Although many types of array elements could be utilized both for the radiator array 12 and the receiving antenna array 14, typical elements are dipoles, waveguide slots, or parabolic dishes.
Referring now to the ground station 15, shown in block diagram on the right of FIG. 2, the received power distribution profile across the face of the receiving antenna array 14 is transferred to a data link control unit 46 via a transmission line 48. In addition, the scattered power distribution profile from the receiving antenna subarrays 32 is also transferred to the data link control unit 46 via a transmission line 50. Location of the beam penetration tester 42 with respect to the power beam receiving antenna array 14 is also provided to the data link control unit 46. The data link control unit multiplexes these three inputs, plus other information necessary for timing and synchronization, the multiplexed signal being supplied to the data link transmitter 36. The data link beam 40 is radiated by the data link transmitter 36 and received by the data link receiver 38 on the spacecraft 10. The ground station 15 further provides standard processing equipment including a power conditioning system 52 which converts microwave energy from the receiving antenna array 14 to other energy forms appropriate for a specific application, examples of which include conversion of microwave energy to heat energy, electrical energy and radiation energy. A load for the energy is represented at 54, and should storage of the energy be desirable, an energy storage capability is shown at 56.
On the spacecraft 10, pilot beam receivers 28, which are diplexed to appropriate power beam radiator array elements, receive the pilot beam 30 radiated from the pilot beam transmitter 26 and transfer a pilot beam received power distribution profile to a power beam control computer 58 via a pilot beam transfer line 60. The reflected power distribution profile across the face of the power beam radiator array 12 is also transferred to the power beam control computer 58 via a transfer line 62. The scattered power distribution profile of the receiving antenna subarrays 34 spaced-apart from the power beam radiator array 12 is also transferred to the power beam control computer 58 via a transfer line 64. The output of the data link receiver 38 is supplied to the power beam control computer 58 via a transfer line 66. Thus, inputs to the power beam control computer 58 comprise the received power distribution profile across the ground station power beam receiving antenna array 14, a scattered power distribution profile across the ground station receiving antenna subarrays 32, the pilot beam received power distribution profile from the diplexed pilot beam receivers 28, the reflected power distribution profile across the face of power beam radiator array 12, the scattered power distribution profile across the spacecraft receiving antenna subarrays 34, and the location of the beam tester 42 with respect to the receiving antenna array 14. Through digital processing techniques well known in the art, the power beam control computer 58 takes all of the above-mentioned profile inputs and compares them to corresponding predetermined power distribution profiles stored in the computer 58. Results of this comparison will show if deviations from predetermined profiles are present, and will pin-point those specific areas in which any deviations are occuring. For example, if the receiving antenna array 14 shows a received power distribution profile anomaly in one quadrant, while other quadrants are indicating normal profiles, the computer may conclude that the intruding object is entering the power beam 18 in that quadrant. If the object is moving at an extremely slow rate, the power beam control computer 58 may conclude that the beam 18 should not be interrupted but rather should be reshaped to avoid the intruding object. Such a redirection can be effected by a phase controller 70 which controls the phase of RF energy supplied by an RF converter 72 to the power beam radiator array 12. However, if a substantial portion of the microwave power transmission beam 18 is blocked the power beam control computer 58 can cause a power source interrupter 74 to either cut-off all power to the power beam radiator array 12 by deactivating the RF converter 72, or can reduce the power level of the RF converter output 72 by control of a dual level power supply 76.
In operation, the system is activated by turning on the ground station pilot beam transmitter 26 and orienting the spacecraft radiator array 12 by the array positioning means 16 so that the signal received by the pilot beam receivers 28 is maximized, thus ensuring that the power transmission beam 18 will be directed at the receiving antenna array 14. The initial energy level of the pilot beam 30 is chosen so that living organisms within the beam 30 will not be harmed. Also, the pilot beam received power profile from the diplexed pilot beam receivers 28 is compared by the power beam control computer 58 to a predetermined profile, this comparison indicating whether the beam path between the space station 10 and the ground station 15 is unobstructed. Having thus ascertained through use of the pilot beam 30 that the power beam radiator array 12 is oriented properly with respect to the receiving antenna array 14 and the power beam 18 path is unobstructed, the power beam control computer 58 provides a signal to the power source interrupter 74 to pass a low power level from the dual-level power supply 76 to the RF converter 72 whose output is radiated as microwave energy from the power beam radiator array 12. The power beam control computer 58 then compares the received power distribution profile across the face of the receiving antenna array 14 to a corresponding predetermined power distribution profile. Upon determining that there is still no obstruction in the path between the power beam radiator array 12 and the receiving antenna array 14, the power beam control computer 58 sends a second signal to the interrupter 74 thereby activating a high level power output from the dual-level power supply 76 to the RF converter 72 for radiation from the radiator array 12. Thus, one can appreciate that through the above-described sequence, the power beam radiator array 12 can begin transmitting a high power microwave transmission beam 18 without fear of having the beam damage an object in the beam path. Having thus established the high power transmission beam 18, the power beam control computer 58 then continues to monitor the preprogrammed beam tester intrusions into the beam and all of the received power distribution profiles, the reflected power distribution profile and the scattered power distribution profiles as above described, and to compare those profiles with corresponding predetermined power distribution profiles. The computer 58 uses the results of these comparisons to control the phase controller 70 and the interrupter 74.
In summary, the invention provides a means and method to control an electromagnetic power beam system by comparing power distribution profiles across various receiving elements of the system and predetermined power distribution profiles. The results of these comparisons are used to shape, divert, dim or douse the power transmission beam. Thus an object entering the beam, through its effect on the various power distribution profiles, will result in the system rendering the beam harmless with respect to the entering object.
Although particular embodiments of the invention have been described and illustrated herein, it is recognized that modifications and variations may readily occur to those skilled in the art, and consequently it is intended that the claims be interpreted to cover such modifications and equivalents.
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A system in which the characteristics of a microwave power transmission beam are controlled in accordance with power distribution profiles altered due to the detected presence or entrance of an object into the beam which causes changes that are perceived in various received, reflected and scattered power distribution profiles resulting over various receiving elements of the system. An analysis of these changes is made, the results of which are used to reshape, dim or douse the power beam in accordance with predetermined criteria. Additionally, a "FAIL SAFE" condition is obtained by employing a beam penetration tester, whose function is to repeatedly test the correct performance of the beam intrusion detecting scheme by presenting a minimal threshold scattering or absorbing cross section while crossing the power beam. If the beam penetration tester is undetected by the beam safety system, then the beam control is preconditioned to turn off the power beam. Conversely, if the beam penetration tester is successfully detected, then the power beam is allowed to remain on. The system comprises a microwave power beam radiator array, a microwave power beam receiving antenna array, the radiator array in one embodiment being located on an orbiting spacecraft and the receiving array being located at a ground station. Another embodiment provides a ground based transmitting array and a receiving array aboard an aircraft or airship.
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FIELD OF THE INVENTION
[0001] The invention relates to a transportation container as defined in the preamble of claim 1 preferably for storage and transportation of raw material such as charcoal, peat, timber, woodchips, grain, bio mass, sand or plastic pellets etc. or various products such as bulk products by sea, land, rail and air.
BACKGROUND OF THE INVENTION
[0002] Previously, raw material and bulk products have been transported in fixed open-type cisterns and pickups of trucks, trains and ships. Typically, raw materials have not been transported in movable units such as containers as the unloading of previously known hard containers has been troublesome. Various hard containers have been used for the transportation of finished products and parcelled goods, as is well-known.
[0003] The problem with the previously known manner of transporting raw materials is the multi-phaseness of the transportation system, including several loading and unloading steps, and thus the complexity and non-cost-effectiveness of the system. It has been possible to use the known open-type cisterns and pickups in the transportation of raw materials only at a certain step of the transportation journey, not during the entire transportation or in the intermediate storage. Often, the raw material, such as charcoal, is first heaped up near the production site, from which it is transported in an open-type cistern of a waggon to the port, where it is again intermediate stored as a heap of charcoal. From the heap of charcoal at the port, the charcoal is loaded into the open-type cisterns of a ship and is transported by ship to the destination, where it is re-unloaded to form a heap of charcoal, after which it may be further transported e.g. in a pickup of a train or truck to a power plant. In that case the problem is the increase in the humidity and dust and particle emissions of the raw material, as well as the raw material loss.
[0004] One further problem has been the slowness of the unloading of the raw materials and bulk products and the long unloading time e.g. from ships and barges. Still one further problem has been the small number of suitable ship, barge and train unloading sites for particular products.
[0005] Moreover, known in prior art is to use various big sacks in the transportation of a bulk product, such as e.g. pellets, catalysts or the like. The problem with the usage of big sacks is their small size and low load-carrying capacity, wherein in the transportation of a bulk product one must use a quantitatively big number of sacks to transport the goods.
OBJECTIVE OF THE INVENTION
[0006] The objective of the invention is to eliminate the drawbacks referred to above.
[0007] One specific objective of the invention is to disclose a new, more robust and better foldable transportation container for the transportation and storage of goods, raw material or a product in a more simple, advantageous and efficient manner.
SUMMARY OF THE INVENTION
[0008] The transportation container in accordance with the invention is characterised by what has been presented in the claims.
[0009] The invention is based on a transportation container which includes a container part, into which container part the goods to be transported and stored can placed, the container part having two ends, two flanks and a bottom and a top part. According to the invention, the transportation container is substantially foldable, and the container part consists of a substantially shaping material. The container part includes at least one openable and closable hatch for unloading the goods; and arranged in conjunction with the container part, at its angles, are angle pieces; and arranged substantially about the container part are supporting means, at least part of them being arranged to pass through the angle pieces for arranging the shaping material and supporting thereof into the desired container form.
[0010] In one preferred embodiment, the transportation container is elongated having the length e.g. of 6 m and width of about 2 to 3 m. In an alternative embodiment, the length of the transportation container is about 8 to 12 m.
[0011] In one preferred embodiment, the container part consists of a substantially continuous casing. In an alternative embodiment, attached to the casing of the container part are predetermined components to form the total casing.
[0012] In one embodiment, the casing of the container part consists of one material layer. In an alternative embodiment, the casing of the container part consists of one or more material layers. The material layers can consist of the same or different material.
[0013] In one embodiment of the invention, the supporting means is substantially a flexible ribbon, strap, beam, cable wire or the like. Alternatively, the supporting means, which preferably is flexible, can be in the form of a tube, hose, rope, narrow plate or the like.
[0014] In one embodiment of the invention, the container part includes at least three types of supporting means. In one preferred embodiment, the container part includes six types of supporting means, which are arranged about the container part for supporting thereof and for improving the load-carrying capacity thereof.
[0015] In one embodiment of the invention, the container includes eight angle pieces arranged at each angle of the container. In one alternative embodiment of the invention, the container includes twelve angle pieces, eight of which are arranged at each angle of the container, and four of which are arranged in the centre of the horizontal edges of the container part's flanks.
[0016] In one embodiment of the invention, the angle piece preferably includes a fastening element consistent with a standard, such as e.g. the ISO 1611, by means of which the angle piece can be attached, making the container better arrangeable into a transportation means consistent with the standard. Furthermore, the angle piece includes means through which the supporting means can be placed, preferably passed through the angle piece.
[0017] The invention has the advantage that the angle piece in accordance with the invention is interchangeable, whereas the previous, so-called standard angle pieces were welded to the containers, and thus were not interchangeable.
[0018] In one embodiment of the invention, the container part includes at least three types of supporting means arranged through the angle pieces, the first of them being arranged to encompass the end of the container part, encircling the edges of the end via four angle pieces, and the second of them being arranged to encompass the bottom or top part of the container part, encircling the edges of the bottom or top part via four angle pieces, and the third of them being arranged to encompass the flank of the container part, encircling the edges of the flank via four angle pieces.
[0019] In one embodiment of the invention, the means through which the supporting means can be placed to pass through the angle piece are passages or channels, and the supporting means that pass through the angle pieces are each arranged to pass through a predetermined channel or passage of their own in the angle piece without contacting the other supporting means.
[0020] In one embodiment of the invention, part of the supporting means are arranged in conjunction with the container part without passage through the angle pieces. Advantageously, these supporting means are arranged to encompass the container part.
[0021] In one embodiment of the invention, the container part includes at least three types of supporting means, which are arranged in conjunction with the container part without passage through the angle pieces, of which supporting means the first one is arranged to encompass the entire container part in the horizontal direction, the second one is arranged to pass vertically at the ends and longitudinally in the bottom, and the third one is arranged to pass in parallel to the cross section of the container part about the flanks and the bottom.
[0022] In one embodiment, the supporting means, which is arranged to encircle the container in the flank-bottom-flank direction, has at both ends thereof a hoisting/supporting ring or the like, which preferably is visible in conjunction with the upper edge of the container part's flank.
[0023] In one embodiment of the invention, the supporting means are arranged to pass in parallel at a distance from each other.
[0024] In one embodiment of the invention, the supporting means are arranged to pass crosswise in such a manner that the first supporting means are arranged to pass into a first direction and the second supporting means are arranged to pass into a second direction in conjunction with the container part. In one embodiment, arranged at the crossing point of the supporting means is a fasting means, preferably e.g. a bonding lock, for attaching the supporting means to one another and for strengthening the supporting structure that consists of supporting means without breaking the supporting structure.
[0025] Thanks to the fastening means, preferably a bonding lock, it is easy to change an individual strap.
[0026] In one embodiment of the invention, the container part includes at least one channel, which is arranged in conjunction with the casing. Advantageously, the channel is arranged inside or outside the casing in conjunction with the casing, or between the material layers of the casing.
[0027] In one embodiment of the invention, the container part may contain a number of channels. In one embodiment, the channels are arranged at a distance from one another. In an alternative embodiment, the channels are arranged substantially side by side. Separate channels may have been formed by welding, sewing, hot melting, etc.
[0028] In one embodiment, the channels are arranged substantially horizontally or vertically in the casing. In one embodiment, the channels are arranged to pass crosswise. In one embodiment, the channel that passes into the first direction is arranged to pass into the channel that passes into the second direction. In an alternative embodiment, the channel that passes into the first direction is arranged to be discontinuous at the point at which it intersects the continuous channel that passes into the second direction. In another alternative embodiment, the channels that pass into the first and second directions are arranged between different material layers.
[0029] In one embodiment of the invention, at least one supporting means is arranged in the formed channel, preferably inside it. The supporting means can have the width of the channel or be narrower.
[0030] In one embodiment of the invention, the casing is made of polymer fibre, synthetic fibre or mixtures thereof. The casing may consist of e.g. polyester, polyamide, polyurethane, polyethylene teraphthalate or other suitable strong polymer fibres or mixtures thereof. In a preferred embodiment, the casing consists of polyester which has a carefully predetermined shock resistance and tensile strength. Advantageously, the material of the casing is woven-type, and its surface can be smooth or alternatively e.g. soft, bubble-like, bellows-like, frictional or the like, depending on the purpose of use of the transportation container. A non-smooth surface may have been obtained by treating the surface structure or by arranging on the surface different material to obtain the desired surface, or by arranging between the uppermost material layers a filling such as e.g. cellular plastic, foam rubber or the like. In one preferred embodiment, the casing has seams or joints as few as possible.
[0031] In one embodiment, the casing of the container consists of single-use material, e.g. in conjunction with a transportation application of messy agents. In that case, the casing part can be easily changed.
[0032] In one embodiment of the invention, the supporting means consists of polymer, synthetic fibre, plastic, aluminium, other metal, carbon fibre, steel cable or the like. As the polymer material it is possible to use the corresponding materials that were mentioned above in conjunction with the materials for casing. The material of the supporting means can be recycling material. Alternatively, it is possible to use e.g. gas such as air, or silicone or polystyrene at least as a part of the supporting means. In that case, the channels have been filled with the material in question, thus supporting the transportation container structure. A combination of different materials can also function as the supporting means.
[0033] By the selection of the supporting means and the material of the casing as well as by arranging the supporting means in a particular manner, e.g. at a distance from one another or in a latticed form, it is possible to affect the load-carrying capacity of the transportation container. In one embodiment, the load-carrying capacity of the transportation container can be up to about 60 tonnes.
[0034] In one embodiment of the invention, the openable and closable hatch is arranged in the bottom part. Advantageously, the hatch of the bottom part functions as the unloading hatch of goods. In one embodiment, arranged in conjunction with the hatch is a funnel-shaped structure for facilitating the unloading of goods.
[0035] In one embodiment, the hatch consists of the material of the casing. In an alternative embodiment, the hatch is of a different material than the casing. In one embodiment, the hatch is arranged in conjunction with the casing, either as being a part of the continuous casing material or as being combined with the casing material.
[0036] In one embodiment of the invention, the top part of the container is a lid. In one embodiment of the invention, the upper edges of the container part's casing flanks and ends are so shaped that they can be folded to form a lid in the top part of the container part, preferably on top of the hatch therein. In one preferred embodiment, the filling of the transportation container is performed via the opening in the top part. In an alternative embodiment, the container part includes a separate lid for covering the opening in the top part, which lid can be arranged substantially in conjunction with the casing. The lid can consist of the same or different material than the casing of the container part. The lid can be rigid or flexible, e.g. fixed, tarpaulin-like, bellows-like, rollable or padded.
[0037] In one embodiment of the invention, the container part's casing flank and/or end is arranged to be openable and/or closable for loading and/or unloading the container.
[0038] In one embodiment, arranged in the container part are preferably opening and locking means in conjunction with the container part for opening and closing of the hatch and/or lid, as well as for locking the fastening of the hatch and/or lid. The opening and locking means can be any locking means known per se and/or suitable for its purpose.
[0039] In one embodiment, arranged at the ends, flanks, bottom and/or lid is a stiffener in conjunction with the shaping material, e.g. in between the material layers. The stiffener may have been arranged to have the form of the container part's end, lid, flank and/or bottom. In one embodiment, the ends are connected to one another with at least one rigid supporting beam for supporting the transportation container. The beam can be connected with the supporting means included in the container part. In one alternative embodiment, the end, flank, bottom and/or lid may have been formed of a substantially rigid material.
[0040] Advantageously, the transportation container can be folded flat and/or so as to take up less space, depending on the fact of whether the container part includes a stiffener or not.
[0041] In one embodiment, the container part is coated, either wholly or partially, with e.g. a suitable polymer such as e.g. polyurethane, Teflon or the like at least on one side for strengthening the material or for improving the properties of the material, e.g. for improving the resistance to rain. In one embodiment, the points of the transportation container that are subjected to a lot of stress, such as the angles and the bottom, are reinforced by coating.
[0042] In one embodiment, the transportation container includes rigid or flexible partitions for dividing the container part's space into smaller parts.
[0043] In one embodiment, the transportation container includes external supporting beams arranged in conjunction with the container part of the transportation container outside the container, e.g. in the bottom of the container. Advantageously, the purpose of the supporting beams is, for their part, to support the transportation container, and for their part to facilitate its loading e.g. inside a hard transportation container or waggon. Beneath the supporting beams arranged in the bottom one may have installed e.g. wheels to facilitate the moving of the transportation container.
[0044] Furthermore, the transportation container in accordance with the invention can be used in a transportation in which the goods to be transported are kept in the same container during the entire transportation, but the transportation means can change.
[0045] The transportation container in accordance with the invention preferably fulfils the transportation standards, e.g. the ISO 668 and ISO 1611, and the transportation regulations, e.g. No 1145/1998.
[0046] The invention enables one to achieve a manner more preferable, efficient and environmentally friendly than before for the transportation and intermediate storage of e.g. raw material or bulk product, such as charcoal, peat, timber, woodchips, grain, bio mass, sand or pellets or the like or finished products.
[0047] The invention has the advantage that one achieves a very light but nevertheless a very robust transportation container that is easy to handle and transport in a confined space. Several empty folded transportation containers in accordance with the invention can be transported at the same time, e.g. in one waggon, container or the like.
[0048] The invention enables one to achieve a foldable transportation container whose load-carrying capacity is considerably better than that of the previous transportation containers. Furthermore, the loading capacity of the transportation container of the invention in relation to the load-carrying capacity and vice versa is bigger than before. The transportation container of the invention is able to carry even up to 60 tonnes of goods, normally 35 tonnes of goods with a capacity of 35 m 3 , whilst in the known hard transportation containers it is possible to carry about 28 tonnes with a capacity of 31 m 3 . The load-carrying capacity of the previously known big sacks has been no more than 1 to 2 tonnes.
[0049] The transportation container of the invention is very simple and thus advantageous to implement. Similarly, the operating costs are low. The transportation container does not rust, and the container part is easy to patch.
[0050] The transportation container of the invention is applicable to the transportation and intermediate storage of various raw materials, bulk products and parcelled goods without several loading and unloading steps, which makes the loss of the goods being transported small, and the goods maintain their original properties. The same transportation container can be used during the entire transportation and transfer system. The loading of the transportation container and particularly the unloading thereof is fast and cost-efficient. The unloading time preferably is no more than about a fifth of the unloading time of known containers. Furthermore, when using transportation containers in accordance with the invention in the transportation of raw material or bulk goods, the unloading time compared e.g. to barge transportations is about 25 to 50% shorter. Furthermore, the transportation container can be unloaded anywhere with no need for a separate unloading place. Thus, the unloading place can be selected. The empty transportation containers can be returned from their destination back to the production site in different transportation means and packed in the minimum of space. This increases the utilisation ratio of the transportation means themselves.
[0051] The transportation container of the invention also quickens the turnover time of waggons, trucks, ships and barges because thanks to the transportation container of the invention, a waggon, truck, ship or barge is needed just during the transportation journey. The transportation container can be quickly and easily hoisted aboard a waggon, truck, ship or barge and away from them, in which case the transportation means need not be at a standstill in terminals, railway yards or unloading places. Furthermore, the transportation container of the invention can be filled in advance and just hoisted into the transportation means.
[0052] The transportation container can be easily modified according to use. The transportation container of the invention can be arranged aboard any transportation means. Furthermore, the transportation container can be arranged inside a hard transportation container. Furthermore, the transportation container can be arranged inside a hard transportation container when necessary.
LIST OF FIGURES
[0053] In the following, the invention will be described by means of detailed examples of its embodiments with reference to the accompanying drawings, in which
[0054] FIG. 1 represents one transportation container in accordance with the invention;
[0055] FIG. 2 represents an angle piece of the transportation container as shown in FIG. 1 ;
[0056] FIG. 3 represents the transportation container as shown in FIG. 1 in a situation in which the unloading hatches are opened;
[0057] FIG. 4 represents a casing structure of the transportation container as shown in FIG. 1 , the casing structure being foldable to form a lid; and
[0058] FIG. 5 represents a bonding lock to be used in the supporting structure of the transportation container as shown in FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
[0059] The transportation container as shown in FIG. 1 is designed for the intermediate storage of charcoal in a production site, for the transportation from the production site to the destination, e.g. to a power plant, and for the intermediate storage along the transportation journey. The charcoal is loaded into the transportation container already at the production site of the charcoal, and is disposed in the same transportation container all the way to the exploitation object. The transportation means, e.g. a combination train-ship-train, can sometimes change but the charcoal remains in the same transportation container during the entire transportation journey.
[0060] The transportation container as shown in FIG. 1 includes a container part 1 , inside which the charcoal to be transported and stored is placed. The container part includes two ends 2 , two flanks 3 , a bottom part 4 and a top part 5 . The top part 5 is arranged to be open or openable, and the container can be filled via it.
[0061] Furthermore, the container part 1 as shown in FIG. 1 comprises eight angle pieces 6 (shown in FIG. 2 ), which are arranged at each angle of the container part 1 , and six flexible supporting ribbons 7 a - c and 8 a - c , which are arranged to encompass the container at different points and from different directions. The supporting ribbons 7 a - c are arranged to pass via the angle pieces 6 , and the supporting ribbons 8 a - c are arranged to encompass the container without passage via the angle pieces 6 .
[0062] The angle piece 6 contains a so-called standard part 9 for standardised transportation means, as well as three separate passages through which the supporting ribbons 7 a - c can be passed. The passages are arranged to cross in a predetermined manner with respect to one another. The angle pieces 6 are formed of a light and durable material, preferably of aluminium or an aluminium mixture (AlZn5Mg1).
[0063] Of the supporting ribbons 7 a - 7 c that are arranged through the angle pieces, the first ones 7 a are arranged to encompass both ends 2 of the container part 1 , encircling the edges of the end 2 via four angle pieces 6 in the transverse direction of the container; the second ones 7 b are arranged to encompass the bottom 4 and top part 5 of the container part 1 , encircling the edges of the bottom 4 /top part 5 via four angle pieces 6 in the longitudinal direction of the container; and the third ones 7 c are arranged to encompass the flanks 3 of the container part 1 , encircling the edges of the flank 3 via four angle pieces 6 . The supporting ribbons 7 a - c that pass through the angle pieces 6 are arranged to pass through the angle pieces 6 each along a passage of their own without contacting each other. Arranged inside the passages in the angle piece 6 are accurately dimensioned shields, which extend a little outside the inlet and outlet ports of the passages of the angle piece 6 , to protect the supporting ribbons 7 a - c from wear and breakage in conjunction with the angle piece 6 . The shields also seal up the supporting ribbons 7 a - c in place in the angle piece, preventing excessive movement of the ribbons, e.g. a lateral movement. The angle pieces 6 stay in place by means of the supporting ribbons 7 a - c , and vice versa the supporting ribbons 7 a - c can be firmly placed to support the container structure by means of the angle pieces 6 .
[0064] The advantage associated is that the supporting ribbon can be passed continuously through the angle pieces, with no breaks. In that case there is no need to arrange additional joints in the supporting ribbon.
[0065] The supporting ribbons 8 a , 8 b and 8 c , which do not pass through the angle pieces 6 , are each arranged to pass in parallel at a distance from another similar supporting ribbon. The supporting ribbons 8 a , i.e. the safety ribbons, are arranged to horizontally encompass the entire container. In this application, there are three pieces of supporting ribbons 8 a . The supporting ribbons 8 b , i.e. the longitudinal supporting ribbons of the bottom hatches, are arranged to pass vertically at the ends 2 and longitudinally in the bottom 4 . The supporting ribbons 8 b are fastened at their upper edges either to the supporting ribbon 7 a or 7 c . In this application, there are two pieces of supporting ribbons 8 b . The supporting ribbons 8 c , i.e. the so-called transverse supporting ribbons of the container part and bottom hatches, are arranged to pass in parallel to the cross section of the container part 1 about the flank 3 and bottom 4 of the container. An extension 8 d of the supporting ribbon 8 c extends over the top part 5 . Arranged at the top ends of the supporting ribbons 8 c are securing hoisting rings 11 , and the top ends of the supporting ribbons in question are attached to the supporting ribbon 7 b . There are six pieces of supporting ribbons 8 c in this application. The supporting ribbons 8 a - c are arranged to pass crosswise in such a manner that arranged to pass at the very bottom are supporting ribbons 8 b , on top of them are disposed supporting ribbons 8 a , and topmost are disposed supporting ribbons 8 c . Arranged at the crossing points of the supporting ribbons 8 a - 8 c are bonding locks 10 ( FIG. 5 ) for attaching the supporting ribbons 8 a - c to one another and for strengthening the supporting structure that consists of the supporting ribbons. In that case, the supporting ribbons are not slipping with respect to one another.
[0066] FIG. 5 represents one bonding lock in accordance with the invention. The bonding locks can be any bonding locks known per se in which two crossing supporting ribbons 8 a - c pass from different directions without contacting each other. The bonding locks are not described more fully herein.
[0067] The advantage associated with the use of angle pieces and bonding locks is that the supporting ribbons can be fastened or tied to each other without breaking the structure of the supporting ribbons and preventing the supporting ribbons from rubbing against each other. Thus, the supporting ribbons will withstand better without breaking in conjunction with a heavy load.
[0068] The container part 1 is formed mainly of a continuous casing 12 . The casing is formed mainly of a flexible polyester, which has been heat treated to be inelastic and which has a high breaking load. Unfolded, the casing is a carpet-like article which consists mainly of one material layer. Arranged in the casing are pockets, or the places for the angle pieces 6 are otherwise marked.
[0069] Arranged in conjunction with the casing 12 are a number of channels (not shown in the figures) inside which the supporting ribbons 7 b - c and 8 a - b can be placed either wholly or partially. In that case, the supporting ribbons can be made to more firmly bond with the casing 12 , and vice versa, the casing 12 can be made to bond with the supporting structure. Furthermore, the channels protect the supporting ribbons. Near the channels, the casing 12 is formed of two material layers between which the channels have been formed.
[0070] Arranged in the bottom part 4 of the casing 12 of the container part 1 are five openings 13 for the unloading hatches 14 ( FIG. 3 ). Attached to the bottom part 4 of the casing are hatches 14 made of the same material to cover the openings 13 of the hatches in the bottom 4 . The unloading hatches 13 , 14 are supported with supporting ribbons 8 b and 8 c , and the attachment of the unloading hatches 14 to the casing 12 is arranged between the casing 12 and the supporting ribbons 8 b - c . The hatches 14 are arranged to be openable and closable separately. Naturally, all the hatches 14 can be opened simultaneously. Conventionally, the hatches 14 are opened one by one, which enables one to control the emptying of the container.
[0071] The shape of the unloading hatch 13 , 14 can naturally vary, e.g. from a quadrangular one to a round one. In the embodiment as shown in FIG. 1 , the hatch 13 of the unloading opening and the hatch part 14 thereof are quadrangular. The hatches 14 are arranged such that whilst opened, in conjunction with the hatch 14 , a downwards tapering funnel-shaped structure 15 is formed for facilitating the unloading of the charcoal. Arranged in the lower edge of the funnel part 15 is a separate securing ribbon for preventing unscheduled opening of the hatch 14 . Thanks to the funnel part, the emptying of the container part is not performed with a terrible force.
[0072] Arranged in conjunction with the unloading hatches 13 , 14 are opening and locking means 16 ( FIGS. 1 and 3 ) for opening and closing each unloading hatch 14 , as well as for locking the hatch independent of each other. In this application, as the opening and locking means 16 , locking ribbons 16 are used, the first ends 17 a of them ( FIGS. 1 and 3 ) being attachable to the one flank 3 of the container part by means of locks 18 included in the opening and locking means whilst the unloading hatch is closed; and the second ends 17 b ( FIG. 4 ) are fixedly attached to the other flank 3 of the container part. The second ends 17 b of the locking ribbons 16 are attached to the lowermost supporting ribbon 8 a on the one flank of the container part; and the locks 18 are attached to the lowermost supporting ribbon 8 a on the other flank of the container part. For each unloading hatch 14 there are two locking ribbons 16 , which are arranged on both sides of the unloading hatch in the cross section of the unloading hatch and inside two adjacent supporting ribbons 8 c near them. Arranged at the first ends 17 a of the locking ribbons 16 are bolts 19 , which can be attached to the locks 18 .
[0073] In the embodiment of the container as shown in FIG. 1 , the unloading hatches always open from the side, in which case the person performing the opening does not need to go under the heavy container for opening purposes.
[0074] Furthermore, the transportation container as shown in FIG. 1 comprises a lid 20 ( FIGS. 1 and 4 ) for protecting the charcoal from humidity or dust etc. The lid 20 is formed by folding the upper edges of the casing 12 to form a lid on top of the top part 5 of the container part after filling the container. The upper edge of the casing 12 is preshaped so that by folding it in a predetermined manner a lid structure is achieved. The extensions 8 d of the supporting ribbons 8 c are arranged on top of the formed lid structure 20 for attaching and locking it. The locking mechanism of the lid 20 by means of the supporting ribbons 8 d is arranged in the same manner as the locking of the unloading hatches described above.
[0075] The transportation container as shown in FIG. 1 is elongated having a length of about 6 m and width of about 2 m. The load-carrying capacity of the transportation container is about 60 tonnes; as the filling, a load of 35 tonnes is usually used. The container is foldable whilst empty.
[0076] In one alternative embodiment, the container part can be open at the end or side, in which case the loading and unloading can be performed e.g. using a fork-lift truck. In that case, the structure of the supporting structure formed of the supporting ribbons and that of the loading/unloading hatches changes in a corresponding manner.
[0077] The transportation container of the invention is easily and advantageously suited for the transportation and/or long- or short-termed storage of various goods and raw materials in various embodiments.
[0078] The embodiments of the invention are not limited to the examples presented above, instead they can vary within the scope of the accompanying claims.
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A transportation container includes a container part ( 1 ), into which container part the goods to be transported and stored can be placed, the container part ( 1 ) including two ends ( 2 ) and two flanks ( 3 ) and a bottom ( 4 ) and a top ( 5 ) part. The transportation container is substantially foldable, and the container part ( 1 ) is made of a substantially shaping material, and the container part ( 1 ) includes at least one openable and closable hatch ( 13, 14 ) for unloading the goods; and arranged in conjunction with the container part ( 1 ), at its angles, are angle pieces ( 6 ); and arranged substantially about the container part ( 1 ) are supporting elements ( 7 a - c , 8 a - c ), at least part of the supporting elements ( 7 a - c ) being arranged to pass via the angle pieces ( 6 ) for arranging the shaping material and supporting thereof into the desired container form.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Divisional Application of co-pending application U.S. Ser. No. 10/788,083, filed Feb. 26, 2004, in the name of Jose F. Masello and Majo Cecur for a “Hydraulic Lash Adjuster And Improved Method Of Assembly Thereof”.
BACKGROUND OF THE DISCLOSURE
[0002] The present invention relates to hydraulic lash adjusters for internal combustion engines, and more particularly, to an improved check valve assembly for use in such lash adjusters, and to an improved method of assembling such lash adjusters.
[0003] In a conventional hydraulic lash adjuster (HLA) of the type to which the present invention relates, there is an outer body, which is typically disposed within a mating bore in the engine cylinder head, and disposed within the body is an output plunger assembly engaging a rocker arm. The output plunger assembly may be of either a one-piece or a two-piece construction, and typically, includes a ball plunger element which engages a socket formed in an “underside” surface of the rocker arm. A blind bore formed within the body cooperates with the plunger assembly to define a high pressure chamber, as is well known to those skilled in the art. There is normally a biasing spring seated within the high pressure chamber, biasing the plunger “outward” of the body bore (toward the rocker arm), as is also well known in the HLA art.
[0004] Most HLA's which are sold commercially are of the “conventional leakdown” type, in which the radial clearance space between the outer diameter of the plunger and the inner diameter of the body bore forms a leakdown path. This leakdown path (or clearance) permits communication of fluid from the high pressure chamber, through the leakdown clearance, and into the reservoir (or “low pressure” chamber) of the HLA whenever an axial force is transmitted from the rocker arm to the ball plunger.
[0005] As is well known to those skilled in the art, one of the key performance criteria of an HLA is the “leakdown” performance of the HLA, i.e., the leakdown flow and resulting plunger assembly travel, as a function of time, for a given force applied to the plunger assembly. For any given engine application, the HLA must provide a leakdown performance which is within a predetermined, specified tolerance range, in order for the HLA to be acceptable for assembly into the engine cylinder head, and in order for the engine valve gear train to operate in a manner which is satisfactory.
[0006] In a typical HLA, there is included a check valve assembly, disposed between the high pressure chamber and the low pressure (reservoir) chamber, and operable to control (either to block or to permit) fluid communication between those two chambers, in response to the instantaneous pressure differential between the chambers. Therefore, in the typical HLA, the lower end of the plunger assembly defines a check valve seat, and prior to insertion of the plunger assembly into the HLA body, the check valve assembly (typically consisting of a check ball, a spring, and some sort of retainer) is assembled to the lower end of the plunger assembly.
[0007] As is also well known to those skilled in the art, another of the key performance criteria for an HLA is the check valve assembly performance, in terms of the rate of fluid flow from the low pressure chamber into the high pressure chamber (or vice versa), in response to a particular pressure differential between the chambers. Again, for any given engine application, the HLA must provide a check valve assembly performance which is within a predetermined, specified tolerance range, in order for the HLA to be acceptable for assembly into the engine cylinder head, and in order for the engine valve gear train to operate in manner which is satisfactory.
[0008] Unfortunately, it occurs periodically that after the HLA is completely assembled, performance testing of the HLA shows that, either the leakdown performance or the check valve assembly performance is not within the specified, permissible limits. When such unacceptable performance occurs, the entire HLA is then either scrapped, (thus wasting several parts of the HLA which, individually, may have been acceptable parts, and therefore, wasting the material, labor and machining costs associated with those parts), or the HLA is sent through some sort of rework process, wherein parts are disassembled, re-inspected, re-sized, and re-assembled. Such a rework process is not only time-consuming, but is also quite expensive.
[0009] Although an HLA manufacturer normally produces several different, standard HLA models, each in relatively large volume, it is quite common for an engine manufacturer to request or need an HLA which is nearly identical to one of the standard models, but differs in respect to perhaps only one of the performance criteria, such as the leakdown performance, or the check valve performance, or the plunger travel. When the HLA manufacturer has the opportunity to make and sell such a non-standard HLA, it is then necessary for the HLA manufacturer to design (and provide tooling for) the non-standard part of the HLA, and design and test what then is effectively a whole new HLA design, and a different part number, even though the resulting HLA may have much commonality with an existing model. This approach to designing and manufacturing new HLA models adds substantially to the overall cost of manufacture of the HLA and the lead time to produce the required, non-standard HLA.
BRIEF SUMMARY OF THE INVENTION
[0010] Accordingly, it is an object of the present invention to provide an improved hydraulic lash adjuster, and an improved method for assembling such a lash adjuster, which makes it possible to verify the proper performance of the check valve assembly prior to assembly of the entire HLA.
[0011] It is another object of the present invention to provide an improved HLA, and an improved method of assembly thereof, in which the performance of the check valve assembly and the leakdown performance each may be changed, independently of the other, without designing and tooling an entirely new HLA.
[0012] It is another, related object of the present invention to provide an improved HLA, and a method of assembly thereof, which greatly facilitates the design and production of an HLA which varies, in perhaps only one aspect or performance criteria, from a standard HLA model already designed and tooled and, possibly in production.
[0013] The above and other objects of the invention are accomplished by an improved hydraulic lash adjuster for an internal combustion engine, the lash adjuster comprising a body defining a bore therein, a plunger slidingly received within the bore and defining a fluid chamber, the plunger and the bore cooperating to define a pressure chamber, and biasing means normally urging the plunger outward of the bore. The body and the plunger cooperate to define a leakdown clearance providing fluid communication between the pressure chamber and the fluid chamber. A check valve assembly is operably associated with the plunger for permitting or blocking fluid communication between the fluid chamber and the pressure chamber in response to changes in the pressure difference between the chambers. The check valve assembly has a predetermined relationship of permitted fluid communication versus pressure difference.
[0014] The improved hydraulic lash adjuster is characterized by the check valve assembly comprising a member, separate from the plunger, the member defining a valve seat. The check valve assembly further comprises a valve member, a spring disposed to bias the valve member toward its normal position, and a retaining member to retain the valve member. The check valve assembly is capable of being assembled and tested for compliance with the predetermined relationship of permitted fluid communication versus pressure difference, prior to installation of the check valve assembly within the plunger.
[0015] In accordance with another aspect of the invention, an improved method of assembling a hydraulic lash adjuster is provided, the lash adjuster comprising a body defining a bore therein, a plunger slidingly received within the bore, and defining a fluid chamber. The plunger and the bore cooperate to define a pressure chamber, and biasing means normally urges the plunger outward of the bore. The body and the plunger cooperate to define a leakdown clearance providing fluid communication between the pressure chamber and the fluid chamber. A check valve assembly is operably associated with the plunger for permitting or blocking fluid communication between the fluid chamber and the pressure chamber in response to changes in pressure difference between the chambers.
[0016] The improved method of assembly is characterized by (a) providing the body defining the bore; (b) providing a plurality of check valve assemblies, including a first check valve assembly and a second check valve assembly, the first and second check valve assemblies having substantially the same exterior configuration, but differing from each other in some performance criteria; (c) providing a plurality of plungers including a first plunger having a first characteristic and a second plunger having a second characteristic; (d) selecting one of the first and second check valve assemblies; (e) selecting one of the first and second plungers and installing therein the selected check valve assembly; and (f) inserting within the bore of the body the selected plunger and check valve assembly combination.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is an axial cross-section of one particular embodiment of hydraulic lash adjuster, made in accordance with the present invention.
[0018] FIG. 2A is an enlarged, axial cross-section of a check valve cartridge of the normally biased-open type, which comprises one aspect of the present invention.
[0019] FIG. 2B is an enlarged, axial cross-section of a check valve cartridge of the normally biased-closed type, and on the same scale as FIG. 1 .
[0020] FIG. 3 is an axial cross-section of a hydraulic lash adjuster body, on a substantially smaller scale than FIGS. 2A and 2B .
[0021] FIGS. 3A and 3B are axial cross-sections of lash adjuster plungers useable with the body of FIG. 3 , and on the same scale as FIG. 3 .
[0022] FIG. 4 is an axial cross-section of a hydraulic lash adjuster body which is different than that shown in FIG. 3 , but on the same scale.
[0023] FIGS. 4A and 4B are axial cross-sections of plungers useable with the body of FIG. 4 , and on the same scale as FIG. 4 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0024] Referring now to the drawings, which are not intended to limit the invention, FIG. 1 is an axial cross-section of one particular embodiment of HLA, by way of example only, made in accordance with the present invention. Therefore, FIG. 1 shows an hydraulic lash adjuster, generally designated 11 , which may be of the general type illustrated and described in U.S. Pat. No. 5,855,191, assigned to the assignee of the present invention and incorporated herein by reference. However, those skilled in the art will understand that the present invention, in each of its aspects, is not limited to the particular type of or configuration of HLA shown in FIG. 1 , as will be explained in greater detail subsequently.
[0025] The HLA 11 , as shown in FIG. 1 , may be of a general type and configuration well known to those skilled in the art (except where noted otherwise hereinafter), and will be described only briefly at this point. The HLA 11 includes a body 13 which, as noted previously, would typically be disposed within a mating bore in the engine cylinder head (not shown herein). Disposed within the body 13 is a plunger 15 , including a check valve assembly, generally designated 17 , with the combination of the plunger 15 and the check valve assembly 17 being biased in an “outward” direction (upward in FIG. 1 ), relative to the body 13 , by means of a plunger spring 19 . It should be noted that certain reference numerals 13 , 15 , 17 , 19 , and others to be introduced (with no “A” or “B”, etc., attached) will be used at various times hereinafter, and in the appended claims, to refer to the particular element, but in only a generic sense. For example, the generic body in FIG. 1 bears the reference numeral “ 13 ”, but in FIGS. 3 and 4 , there will be illustrated and described two specific bodies 13 A and 13 B, respectively.
[0026] Disposed within the plunger 15 is a fluid chamber 21 (also referred to hereinafter as a “reservoir” or a “low pressure chamber”). The body 13 and the lower end of the plunger 15 cooperate to define a high pressure chamber 23 (also referred to hereinafter, and in the appended claims, as simply the “pressure chamber”). As was mentioned previously, and as is well known to those skilled in the HLA art, the function of the check valve assembly 17 is either to permit fluid communication, or to block fluid communication, between the low pressure chamber 21 and the high pressure chamber 23 , in response to the pressure differential between the chambers 21 and 23 .
[0027] Disposed about the upper end of the body 13 is a cap member 25 , the function of which is to retain the plunger 15 , and limit outward movement thereof relative to the body 13 . It should be understood that the particular configuration of the cap member 25 , or even the presence of any cap member, is not an essential feature of the invention, and all that is essential to the invention (as is essential to any HLA) is that there be provided some suitable means for retaining the plunger 15 within the body 13 .
[0028] Referring now primarily to FIGS. 2A and 2B , and in accordance with one important aspect of the present invention, the check valve assembly 17 shown in FIG. 1 comprises a check valve cartridge. In accordance with a further aspect of the invention, there are multiple check valve cartridges provided, from among which one may be selected as part of the method of assembly of the HLA 11 . Therefore, but by way of example only, FIG. 2A illustrates a check valve cartridge 17 A, while FIG. 2B illustrates a check valve cartridge 17 B, it being understood that in accordance with one aspect of the invention, the check valve cartridges 17 A and 17 B are designed and produced to be “interchangeable” as that term will be explained in greater detail subsequently. One aspect of the check valve cartridges 17 A and 17 B being interchangeable is that they both have the same exterior configuration which, as may be seen by comparing FIGS. 2A and 2B , means that the cartridges 17 A and 17 B have the same outside diameters, but clearly not the same overall lengths, at least in the subject embodiment.
[0029] Referring now primarily to FIG. 2A , the check valve cartridge 17 A comprises a generally cylindrical seat member 27 , defining a check valve seat surface 27 S. Disposed about the seat member 27 , at the upper end thereof, is a seal member 29 which may comprise any of the materials now conventionally used for HLA seals. The seal member 29 is retained in place as shown in FIG. 2A by means of a retention and seat member 31 which, preferably, has an interference fit with the upper portion of the inside diameter of the seat member 27 .
[0030] Referring still to FIG. 2A , disposed at the lower end of the seat member 27 is a retainer 33 , which would normally be crimped in place, relative to the seat member 27 , as shown in FIG. 2A . As is well known to those skilled in the art, one function of the retainer 33 is to retain, and limit axial travel of, a check ball 35 which is biased toward an open position (away from the seat surface 27 S) by a compression spring 37 . Thus, the check valve cartridge 17 A is of the type referred to as “normally biased open”, in accordance with the teachings of U.S. Pat. No. 5,758,613, assigned to the assignee of the present invention and incorporated herein by reference.
[0031] Referring now primarily to FIG. 2B , the check valve cartridge 17 B includes a seat member 41 , defining a seat surface 41 S, and disposed around the seat member 41 is a seal member which, in the subject embodiment, and by way of example only, is (or at least, may be) the same seal member 29 used in the cartridge 17 A. The seal member 29 is retained in place by means of a retention member 43 which, on its inside diameter, has an interference fit with an adjacent outer surface of the seat member 41 .
[0032] A retainer 45 is in engagement, such as by crimping or any other suitable means, with a lower portion of the seat member 41 . Seated against the upper surface of the retainer 45 is a compression spring 47 which engages a check ball 49 and biases it toward the seat surface 41 S. Therefore, the check valve cartridge 17 B is of the type referred to as “normally biased closed”, as has been well known in the HLA art for many years.
[0033] In accordance with one important aspect of the present invention, as the check valve cartridges 17 A are produced, each one may be placed in an appropriate test fixture, and subjected to one or more predetermined pressure differentials, while the test fixture measures the permitted fluid flow past the check ball 35 to verify that, for any given pressure differential, the rate of fluid flow is within the predetermined tolerance range. Similarly, as each of the check valve cartridges 17 B is produced, it may be placed in its own test fixture, and subjected to one or more pressure differentials across the check ball 49 , while the fixture measures the rate of fluid flow, again to verify that for each pressure differential, the fluid flow is within the predetermined tolerance range.
[0034] After each check valve cartridge ( 17 A or 17 B) is tested, if it meets all of the check valve performance criteria specified for that particular cartridge, it then proceeds to the HLA assembly area. Those cartridges which do not meet all of the performance criteria are rejected (and possibly scrapped) at this stage of the process, rather than after the entire HLA is assembled and tested, as has been the case in connection with the prior art hydraulic lash adjusters and the prior art methods of assembly thereof.
[0035] Although the present invention is being illustrated and described in connection with an embodiment in which one of the available check valve assemblies is normally biased open, and the other is normally biased closed, those skilled in the HLA art will recognize that the invention is not so limited. In the broadest aspects of the method of assembling an HLA, all that is essential is that at least two different check valve assemblies be available, and that the two assemblies differ from each other in some performance criteria. For example, in the HLA assembly area, there could be provided two (or more) different types of check valve cartridge, wherein both are, for example, of the normally biased open type, but wherein the first cartridge ( 17 A) has one particular check ball size and/or travel, while the second cartridge (not shown herein) has a different check ball size and/or travel. Or, as another example, there could be provided two (or more) different types of check valve cartridge wherein both are of the normally biased-closed type, but wherein one ( 17 B) has one particular bias force for the spring 47 , while the other (not shown herein) has a different bias force for the spring 47 .
[0036] Referring now primarily to FIGS. 3 and 4 , there is shown in FIG. 3 a short HLA body 13 A and there is shown in FIG. 4 a long HLA body 13 B. By way of example only, the short body 13 A and the long body 13 B may be substantially identical, except for the overall length, and therefore each defines a body bore 51 , and in the subject embodiment, and by way of example only, the body bores 51 of both of the bodies 13 A and 13 B are identical in diameter, the significance of which will be described subsequently.
[0037] Referring now primarily to FIGS. 3A and 3B , there are illustrated short plungers 15 A and 15 B, respectively which, for purposes of the present invention, may be substantially identical in parameters such as overall length, outside diameter 55 , etc. However, in the subject embodiment, and by way of example only, the short plunger 15 A defines a cartridge recess 53 A which is adapted to receive therein the check valve cartridge 17 A, shown in FIG. 2 , while the short plunger 15 B defines a relatively shorter cartridge recess 53 B adapted to receive therein the relatively shorter check valve cartridge 17 B, shown in FIG. 2B . As noted above, the short plunger 15 A and the short plunger 15 B could have exactly the same outside diameters 55 , in which case, each would cooperate with the body bore 51 of the short body 13 A to provide the same leakdown clearance.
[0038] Referring now primarily to FIGS. 4A and 4B , there is shown a pair of long plungers 15 C and 15 D, respectively which, as was explained in connection with FIGS. 3A and 3B , may be substantially identical to each other in terms of overall length and outside diameter 55 , but in the subject embodiment, and by way of example only, differ from each other at least in regard to the fact that the long plunger 15 C defines a cartridge recess 53 C whereas the long plunger 15 D defines a relatively shorter cartridge recess 53 D. In the subject embodiment, and by way of example only, the cartridge recess 53 C is substantially identical to the cartridge recess 53 A, and therefore, is configured to receive therein the check valve cartridge 17 A, whereas, the cartridge recess 53 D is substantially identical to the cartridge recess 53 B, and therefore, is configured to receive therein the relatively shorter check valve cartridge 17 B.
[0039] It should be understood by those skilled in the art that, within the scope of the invention, the different check valve cartridges could all be configured to have the same axial length, thus eliminating the need to provide both of the short plungers 15 A and 15 B, or both of the long plungers 15 C and 15 D. However, the invention is being described in connection with an embodiment in which the check valve cartridges are different (and require different plungers) to help illustrate the flexibility in design afforded by the invention. Also, and as is now well known in the HLA art, the shorter plungers 15 A and 15 B would typically be utilized in markets which require relatively less plunger travel, as is now the case normally in the European market. On the other hand, the longer plungers 15 C and 15 D would typically be utilized in markets which require relatively greater plunger travel, as is now the case normally in the North American market.
[0040] In accordance with another important aspect of the present invention, there is provided the ability to assemble a number of different HLA models, each being different from the others in at least one aspect of its configuration or its performance criteria, but without the cost required for each different model of HLA to be comprised of parts and components which are completely unique to that particular model.
[0041] Therefore, and by way of example only, the short bodies 13 A and long bodies 13 B would be formed and machined, etc., and sent to the HLA assembly area, and the short plungers 15 A and 15 B and the long plungers 15 C and 15 D would also be formed and machined, etc. and also sent to the HLA assembly area. After the check valve cartridges 17 A and 17 B are assembled and tested, those which successfully pass the performance test would be sent to the HLA assembly area as was mentioned previously. In the HLA assembly area, it is then possible to assemble a number of different HLA models utilizing those opponents shown in FIGS. 2 through 4 .
[0042] For example, the assembly operator would select one of the long bodies 13 B, as shown in FIG. 4 . The assembly operator would then select one of the check valve cartridges 17 A, and one of the long plungers which is suitable for use with the cartridge 17 A, i.e., one of the long plungers 15 C. The assembly operator would then install the selected check valve cartridge 17 A within the selected long plunger 15 C, and then install within the body 13 B the assembled cartridge-plunger sub-assembly or combination. As is well known to those skilled in the art, just prior to installing the cartridge-plunger combination, it is necessary to put in place the plunger spring 19 (shown only in FIG. 1 ). In accordance with another aspect of this invention, there may be available to the assembly operator several different plunger springs ( 19 A and 19 B, not shown herein because both are represented generically by the spring 19 in FIG. 1 ), each having a different biasing characteristic (for example, a different “curve” of biasing force as a function of axial compression). Thus, two different HLA models could be provided simply by having available two different plunger springs 19 .
[0043] Although, for ease and simplicity of illustration, only two bodies ( 13 A and 13 B) have been shown and described herein, in which the only difference between them is the length, those skilled in the art will understand that other body configurations could be utilized. For example, a plurality of the normally-closed check valve cartridges 17 B could be assembled into a plurality of the short plungers 15 B, and then these cartridge-plungers combinations installed in the bodies of deactivating HLA's of the type which are now well know to those skilled in the HLA art.
[0044] For each different HLA assembly to be designed and assembled, it is necessary to start by specifying the check valve cartridge type (normally-biased open; normally-biased closed, or “free ball”, as that term is understood in the art) and check valve performance. Based upon that determination, the next step is to select the appropriate check valve cartridge (either 17 A or 17 B, etc.) from among the multiple cartridge models available. Next, the designer must specify the desired leakdown performance, and based upon that, select the appropriate plunger which “accepts” the selected check valve cartridge and at the same time, cooperates with the body to be used to provide the desired leakdown performance. The invention has been illustrated and described based upon the assumption that the different desired leakdown clearances may be achieved by selecting from among several different plungers, having slightly different diameters. However, it should be apparent that the same result could be achieved by having available several different bodies, each having a slightly different body bore diameter.
[0045] The invention has been described in great detail in the foregoing specification, and it is believed that various alterations and modifications of the invention will become apparent to those skilled in the art from a reading and understanding of the specification. It is intended that all such alterations and modifications are included in the invention, insofar as they come within the scope of the appended claims.
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A hydraulic lash adjuster ( 11 ) for an internal combustion engine, and an improved method of assembly of such a lash adjuster. The lash adjuster ( 11 ) is of the type having a body ( 13 ), a plunger ( 15 ), and a check valve assembly ( 17 ). In accordance with one aspect of the invention, the check valve assembly comprises a cartridge ( 17 A; 17 B) comprising a member ( 27;41 ) separate from the plunger ( 15 ) and defining a valve seat ( 27 S; 41 S). The check valve cartridge is capable of being assembled and tested for compliance with a predetermined relationship of flow versus pressure differential, prior to assembly into the plunger ( 15 ). In accordance with the improved method of assembly, a plurality of different bodies ( 13 A; 13 B) and plungers ( 15 A; 15 B; 15 C; 15 D) is provided, as well as a plurality of different, interchangeable check valve cartridges ( 17 A; 17 B), and the assembly operator selects a body, a plunger, and a cartridge to provide an assembled lash adjuster having the predetermined, desired operating parameters.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2004-040132, filed Feb. 17, 2004, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a nonvolatile semiconductor memory device, especially a NAND-structured flash memory, and in particular relates to a configuration of a core portion of the memory and its control circuit.
2. Description of the Related Art
Recently, an EEPROM (NAND-structured flash memory) having NAND-structured cells has often been used as an EEPROM having a larger capacity in digital devices such as digital cameras and mobile telephones.
Various improvements have been attempted in the NAND-structured flash memory with increasing use thereof. For example, in Jpn. Pat. Appln. KOKAI Publication No. 10-199280, driving is performed with a pair of adjacent bit lines in such a manner that when one of them is in a selected state, the other is in a non-selected state, in order to prevent erroneous operations due to noise or word line delay. In this case, the non-selected bit line is used as a dummy bit line, and data is sensed from the pair of bit lines by a differential amplifier. A dummy cell having a larger on-resistance than a memory cell is connected between the bit line and a source line, and in such a configuration, the dummy cell connected to the non-selected bit line is turned on. Further, the memory cell and the dummy cell are designed such that the dummy bit line indicates a midpoint potential in association with a voltage change of the selected bit line when data “0” and “1” are read.
Furthermore, Jpn. Pat. Appln. KOKAI Publication No. 2002-237194 provides a pre-charging method in which, in order to reduce time to pre-charge the bit lines, two pre-charge sections are provided, and one pre-charge section supplies a data line with a current that can be varied in accordance with voltage changes of the data line, while the other pre-charge section supplies the data line with a constant current irrespective of the voltage changes of the data line.
Incidentally, in a write operation of the NAND-structured flash memory, when the memory cell in the center of a NAND string is the selected cell, the memory cells on both sides thereof are also ordinary memory cells, so that a bias state of several cells around the selected cell is symmetrical. Conversely, when the memory cell at the end of the NAND string is the selected cell, the bias state around the selected cell is asymmetrical because one cell serves as a selection gate. As a result, the characteristics of writing into the memory cell are different in the memory cell next to the selection gate and the other memory cells.
In binary operation with little concern about increasing threshold distribution, the difference in characteristics is not a large problem. However, in the case of multi-level operation such as quaternary, octal and hexadecimal levels, the width of threshold distribution needs to be controlled to narrow the width, and it is therefore desired to have a uniform characteristic of memory cell writing.
If the writing characteristics are different in the memory cell at the end of the NAND string such as the memory cell next to the selection gate, and the memory cell in the center of the NAND string, it is necessary to individually control the voltage applied to a control gate of the memory cell, for example, depending on where the selected cell is located, and thus a complicated control circuit is needed to achieve this.
In addition, for example, step-up writing is utilized at present in which the writing voltage is stepped up to further reduce the width of threshold distribution. However, if the writing characteristics are significantly different in the memory cells, more time is spent in the step-up writing to reduce the width of threshold distribution, leading to lower performance.
Moreover, in writing, if the state of the selected cell should remain unchanged (electric charges should not be injected into a floating gate), a channel of the NAND string is previously charged before a word line is charged to a predetermined voltage.
At this moment, the gate potential of the source line side selection gate is VSS, and the selection gate is in a cut-off state. However, if a predetermined voltage is applied to the memory cell adjacent to the selection gate, the coupling capacitance of the selection gate and the control gate of the memory cell adjacent thereto causes the gate potential of the selection gate to float from VSS. This causes a phenomenon in which the selection gate conducts and the electric charges in the channel are discharged. In this way, “erroneous writing” occurs where a charge is injected into the floating gate of the selected cell whose state should not be changed.
On the other hand, in the NAND-structured flash memory, the size of one cell array tends to be increased directly with increasing capacity, and the length of the word line and bit line is only increasing. This is because array division is avoided as much as possible to reduce chip size to the minimum for cost reduction.
Furthermore, parasitic capacitance and resistance increase along with the increase in the length of the word line and bit line, which is a disadvantage to the performance of a chip, and therefore, some measures need to be taken. For example, the increased bit line length poses such problems that the pre-charge time is increased, that time is increased for a cell current to cause a small potential difference in the bit line, and that time is increased for the bit lines to recover their original state.
Moreover, the following problems are posed in a reading operation of the NAND-structured flash memory. In reading, the selected bit line is pre-charged to a predetermined voltage, and the potential of the non-selected bit line will be VSS which is a bit line shield potential. After the selected bit line has been pre-charged, a bit line side selection gate is opened to discharge the electric charges from the cell to the bit line in accordance with a threshold value (signal) written into the cell connected to the selected word line, and its small potential difference is amplified by a sense amplifier. After it is sensed, the bit line recovers its original potential.
On the other hand, the bit lines on both sides of the selected bit line are non-selected bit lines. Noise due to coupling is reduced in such a manner that the non-selected bit lines have a fixed potential (e.g., VSS) and are used as shielding lines. More specifically, the selected bit line and the non-selected bit lines are alternately arranged, and they are allocated in different pages. They are temporarily differentiated by parity, and respectively called an EVEN page and an ODD page.
In order to decrease the bit line pre-charge time, the non-selected bit line which is currently at VSS may be pre-charged to a pre-charge potential at the same time. The pre-charge time is reduced because the wiring capacitance between effective adjacent lines is eliminated and the wiring capacitance necessary to drive all the bit lines is reduced.
In this case, however, in the conventional structure of the NAND string, when the cell linked to the non-selected bit line serving as a shield has a negative threshold value (“1”), opening the selection gate will cause the current to flow from its bit line to the source line to lower the potential, resulting in a problem that it cannot serve as the shielding line.
Therefore, it has been desired to realize a NAND-structured flash memory capable of accomplishing a uniform writing characteristic of the memory cells by equalizing the writing characteristic of the memory cell at the end of the NAND string with that of the memory cell in the center.
Furthermore, there has also been a desire for a NAND-structured flash memory capable of reducing the pre-charge time in a bit line pre-charge operation when reading or verifying the NAND-structured flash memory.
BRIEF SUMMARY OF THE INVENTION
According to a first aspect of the invention, there is provided a NAND-structured flash memory, which comprises:
a memory cell array in which a plurality of memory strings are arranged in matrix form, each of the memory cell strings including a plurality of nonvolatile memory cells, the plurality of memory cells having first conducting paths and control gates, respectively, the first conducting paths of the plurality of memory cells being connected in series, at least one of the nonvolatile memory cells constituting each of the plurality of the memory strings having a function other than an external data storing function;
a plurality of first selection transistors having second conducting paths, and one end of the second conducting paths being connected to one end of the series of the first conducting paths, respectively;
a plurality of bit lines connected to the other end of the second conducting paths of the plurality of first selection transistors, respectively;
a plurality of second selection transistors having third conducting paths, and one end of the third conducting paths being connected to one end of the series of the first conducting paths, respectively; and
a source line connected to the other end of the third conducting paths of the plurality of second selection transistors.
According to a second aspect of the invention, there is provided a NAND-structured flash memory, which comprises:
a selection transistor having a first conducting path, one end of the first conducting path being connected to a bit line or a source line;
at least one dummy gate having a second conducting path and a control gate, one end of the second conducting path being connected to the other end of the first conducting path of the selection transistor;
a nonvolatile memory linked unit for storing external data, which includes a plurality of electrically erasable/writable nonvolatile memory cells having third conducting paths and control gates, the third conducting paths being connected in series, one end of the series of the third conducting paths being connected to the other end of the second conducting path of the dummy gate;
a dummy gate driving circuit controlling a potential of the control gate of the dummy gate; and
a memory cell driving circuit selectively driving the control gates of the plurality of nonvolatile memory cells to write, read or erase bit data for storing the external data.
According to a third aspect of the invention, there is provided a NAND-structured flash memory comprising:
a memory cell array in which a plurality of memory strings having a plurality of serially connected memory cells are arranged in matrix form;
first selection transistors having first conducting paths, one end of the first conducting paths being connected to an end of the plurality of memory strings, respectively;
second selection transistors having second conduction paths, one end of the second conducting paths being connected to the other end of the plurality of memory strings; and
a plurality of bit lines connected to the other end of the first conducting paths of the first selection transistors, wherein in at least one memory cell in each of the memory strings, information on whether one of the bit lines linked to the at least one memory cell is an even number column or an odd number column is written.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a diagram to explain a write operation of a nonvolatile memory;
FIG. 2 is a graph showing threshold distribution of a binary memory cell;
FIG. 3 is a graph showing threshold distribution of a quaternary memory cell;
FIG. 4 is a circuit diagram showing a structure of conventional one NAND string;
FIG. 5 is a diagram to explain a method of reading from a NAND-structured flash memory;
FIG. 6 is a diagram showing the state of cells adjacent to a selected cell in the center of the NAND string;
FIG. 7A is a diagram showing the state of cells adjacent to the selected cell at the end of the NAND string on a source line side;
FIG. 7B is a diagram showing the state of cells adjacent to the selected cell at the end of the NAND string on a bit line side;
FIG. 8 is a diagram to explain a problem caused in a selection gate at the end shown in FIG. 7A ;
FIG. 9 is a circuit diagram showing the structure of one NAND string in a first embodiment of the present invention;
FIG. 10 is a circuit diagram of a word line voltage control circuit in the first embodiment;
FIG. 11 is a circuit diagram showing the structure of the NAND string in second and third embodiments;
FIG. 12 is a circuit diagram of the word line voltage control circuit in the third embodiment;
FIG. 13 is a circuit diagram showing the structure of the NAND string in a fourth embodiment;
FIG. 14 is a graph explaining a bit line pre-charging method for a conventional NAND-structured flash memory;
FIG. 15 is a diagram explaining a bit line shielding method for the conventional NAND-structured flash memory;
FIG. 16 is a graph showing voltage changes at the start of a bit line selection gate voltage and a bit line pre-charge voltage of the conventional NAND-structured flash memory;
FIG. 17 is a circuit diagram explaining a bit line pre-charging method in a fifth embodiment;
FIG. 18 is a graph showing the voltage changes at the start of the bit line selection gate voltage and the bit line pre-charge voltage in the fifth embodiment;
FIG. 19 is a diagram explaining an operation during the pre-charge of bit line in the fifth embodiment;
FIG. 20 is a diagram showing a configuration of an electronic card according to a first application of a NAND-structured flash memory of the present invention;
FIG. 21 is a diagram showing the configuration of the electronic card according to a second application of the NAND-structured flash memory of the present invention;
FIG. 22 is a schematic diagram showing an appearance of a digital camera using the electronic card mentioned above; and
FIG. 23 is a schematic diagram showing an appearance of a mobile telephone using the electronic card mentioned above.
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will hereinafter be described referring to the drawings.
First Embodiment
Before describing the embodiments, a bias condition in writing into a NAND-structured flash memory is shown in FIG. 1 to reconfirm characteristics of the NAND-structured flash memory. In this method, a channel is fixed at ground potential, and a high potential (hereinafter referred to as VPGM) is applied to a control gate which is a word line, so as to pull electrons from the entire channel, and store the electrons in a floating gate. A threshold value of a memory cell transistor changes in accordance with the amount of electric charge stored in the floating gate.
As shown in FIG. 2 , in a NAND structure using a binary cell, a state in which electrons are stored in the floating gate and a state in which electrons are not stored are identified to store one bit. Further, as shown in FIG. 3 , in a NAND structure using a multi-level cell, the threshold value of the memory transistor which changes in accordance with the amount of electric charge stored in the floating gate is identified as several states. The amount of electric charge stored in the floating gate is controlled in accordance with, for example, a voltage applied to the control gate and time of applying the voltage in writing.
FIG. 4 shows a structure of a NAND string, which is a base unit of the NAND-structured flash memory. The NAND string has one end connected to a bit line and the other end connected to a source line. Further, both ends of the NAND string comprise selection gates (selection transistors) for selecting the NAND string. In a write operation, only one of a plurality of memory cells constituting the NAND string (memory cell linked unit) will be a memory cell targeted for writing, and the VPGM is applied to the control gate of this memory cell. This memory cell will hereinafter be called a selected cell.
On the other hand, a voltage to prevent erroneous writing (hereinafter referred to as VPASS) is applied to the control gates of the memory cells other than the selected cell (hereinafter referred to as non-selected cells), as shown in FIG. 5 .
When the memory cell in the center of the NAND string is the selected cell, the memory cells on both sides thereof are also ordinary memory cells, resulting in a symmetrical bias relationship as shown in FIG. 6 . Conversely, when the cell at the end of the NAND string is the selected cell, a bias is given in a special manner as shown in FIGS. 7A and 7B because one cell serves as the selection gate. As a result, the characteristics of writing into the memory cell are different in the memory cells next to the selection gate and the other memory cells.
In binary operation with little concern about increasing threshold distribution, this difference in characteristics is not a large problem. However, in the case of multi-level operation such as quaternary, octal and hexadecimal levels, the width of threshold distribution needs to be controlled to narrow the width, and it is therefore desired to have a uniform characteristic of memory cell writing.
Moreover, in writing, if the state of the selected cell should remain unchanged (electric charges should not be injected into the floating gate), the channel of the NAND string is previously charged before the word line is charged to VPGM or VPASS.
At this moment, the gate potential of the source line side selection gate is VSS, and the selection gate is in a cut-off state. However, if the VPGM or VPASS is applied to the memory cell adjacent to the selection gate, the coupling capacitance of the selection gate and the control gate of the memory cell adjacent thereto causes the gate potential of the selection gate to float from VSS. This causes a phenomenon in which the selection gate conducts and the electric charges in the channel are discharged. In this way, the “erroneous writing” occurs where a charge is injected into the floating gate of the selected cell whose state should not be changed.
Next, the NAND-structured flash memory according to a first embodiment of the present invention that can solve the problem described above will be described. The NAND-structured flash memory of the first embodiment is a quaternary NAND-structured flash memory, and as shown in FIG. 9 , one NAND string is composed of a bit line side selection gate (selection transistor), 34 memory cells, and a source line side selection gate, wherein the memory cell next to the bit line side selection gate and the memory cell next to the source line side selection gate are treated as dummy cells (dummy gates). The 32 memory cells between the two dummy cells are treated as quaternary cells.
As information is not stored in the dummy cells (dummy gates), the dummy cells are always treated as the non-selected cells in writing and reading. Insertion of the dummy cells will provide a structure in which the memory cell at the end is also placed between the cells on both sides, so that the writing operation can be performed on the uniform bias condition in the 32 memory cells placed between the dummy cells.
In FIG. 10 , only one block composed of 32 word lines and two dummy word lines is selected by a block selection circuit 4 in accordance with a block selection address BLK<0:9>. A high voltage (e.g., 27 V) is applied to a gate of a transfer gate 5 which is linked to the word line of the selected block, and 0 V is applied by the block selection circuit 4 to a gate of a transfer gate which is linked to the non-selected word line.
A selected word line voltage and a non-selected word line voltage are respectively generated by a selected word line voltage generator 2 and a non-selected word line voltage generator 1 , and a selected/non-selected word line selection circuit 3 selects the non-selected word line voltage or the selected word line voltage as a word line voltage. A word line selection address CGA< 0 : 4 > decides which word line will be the selected word line.
Furthermore, as the two dummy word lines are always treated as the non-selected word line, a non-selected word line voltage is directly applied to the dummy word lines, not via the selected/non-selected word line selection circuit 3 .
In such a configuration, the dummy word lines are always non-selected word lines, and the 32 memory cells put between the dummy word lines can perform an ordinary operation, and yet uniformity of memory cell writing characteristics can be enhanced.
It should be noted that the dummy cells are provided on both bit line and source line sides in FIG. 9 , but may be provided on one side. For example, when “1” is written, a pre-charge voltage is given to the bit line and the channel of the cell is charged. The selected/non-selected word line voltage is given to the selected/non-selected word line after the channel of the cell is sufficiently charged, thereby boosting a channel potential. In this case, it is desired that the bit line side selection gate and the source line side selection gate be in the cut-off state, but if the coupling noise subjected to the selection gates at the start of the word line is high, the selection gates will be turned on, and the electric charges will run from the channel to the bit line/source line. Regarding a potential relationship in this instance, generally, the bit line is pre-charged to 2.5 V, and 1.2 V is applied to the bit line side selection gate. On the other hand, the source line is charged to about 1.4 V, and 0 V is applied to the source line side selection gate.
As can be understood from the bias relationship described above, because the bit line side selection gate is more easily turned on than the source line side selection gate, the bit line side has lower coupling noise resistance properties. Therefore, even if the dummy cell is provided only next to the bit line side selection gate, the erroneous writing can be effectively prevented.
Furthermore, the source line is charged to about 1.4 V as described above, but this is done to completely cut off the source line side selection gate, and if the dummy gate is provided on the source line side and it can be cut off even with a source line voltage of 0 V, it is no longer necessary to charge the source line, and current consumption can be reduced. Therefore, a certain degree of effect is obtained if the dummy cell is provided only on the source side.
As described above, a distinctive effect can be achieved even if the dummy cell is provided on either bit line side or source line side. In the first embodiment, a non-selected gate voltage is given to the control gate of this dummy cell. Moreover, a quaternary memory cell is used for the dummy cell in the first embodiment, but a memory cell higher than the quaternary level such as the octal level may be used. Further, the dummy cell does not always need to be a memory cell, and may be a dummy gate in which conduction can be controlled by the control gate.
Second Embodiment
The NAND-structured flash memory in a second embodiment is a quaternary NAND-structured flash memory, and as shown in FIG. 11 , one NAND string is composed of the bit line side selection gate (selection transistor), 36 memory cells, and the source line side selection gate. The four memory cells including two next to the bit line side selection gate and two next to the source line side selection gate are treated as dummy cells (dummy gates), and the remaining 32 memory cells are treated as quaternary cells. As the two dummy cells are disposed next to the selection gate, it is possible to have a more uniform bias condition in the operation of writing into the quaternary cells than in the first embodiment.
The circuit in FIG. 10 of the first embodiment can be utilized directly as a word line voltage control circuit. In addition, a quaternary memory cell is also used for the dummy cell in the second embodiment, but a memory cell higher than the quaternary level such as the octal level may be used. Further, the dummy cell does not always need to be a memory cell, and may be a dummy gate in which conduction can be controlled by the control gate. Moreover, a certain degree of effect can be achieved if the dummy cell is provided only on the bit line or source line side. In this case, the non-selected gate voltage is given to the control gate of this dummy cell.
Third Embodiment
The NAND string in a third embodiment has the same configuration as that in the second embodiment, but a control gate charging voltage for the dummy cells adjacent to the selection gates is lower (e.g., 2.5 V) than the ordinary non-selected word line voltage (e.g., 14 V). This makes it possible to keep the effects of the coupling noise lower, which are caused to the selection gate when the control gate is charged.
FIG. 12 is a circuit diagram of the word line voltage control circuit (word line driving circuit) capable of the operation described above. The difference from the word line voltage control circuit in FIG. 10 is that a first dummy word line voltage generator 6 , a second dummy word line voltage generator 7 , a first dummy word line voltage selection circuit 8 and a second dummy word line voltage selection circuit 9 are added. As two dummy word line voltage generators are provided, the bit line side dummy gate and the source line side dummy gate can be driven at different voltages.
In addition, a memory cell higher than the quaternary level such as the octal level may be used instead of the quaternary memory cell in the third embodiment, and the dummy cell is not limited to a memory cell and may be a dummy gate in which conduction can be controlled by the control gate. Moreover, a certain degree of effect can be achieved if the dummy cell is provided only on the bit line or source line side.
Fourth Embodiment
The NAND-structured flash memory in a fourth embodiment is the quaternary NAND-structured flash memory, and as shown in FIG. 13 , one NAND string is composed of the bit line side selection gate (selection transistor), 34 memory cells, and the source line side selection gate. The four memory cells including two next to the bit line side selection gate and two next to the source line side selection gate are treated as binary cells, and the remaining 30 memory cells are treated as quaternary cells. In addition, the 30 memory cells may be memory cells higher than the quaternary level.
Bias uniformity in the operation of writing into the quaternary cell is equal to that in the second embodiment, and the two cells next to the selection gate are treated as binary cells with little concern about the increasing threshold distribution, thereby allowing the degree of integration to be higher than in the second embodiment.
The word line voltage control circuit in the above case can be easily achieved by modifying the circuit shown in FIG. 12 . In other words, the first dummy word line voltage generator 6 , the second dummy word line voltage generator 7 , the first dummy word line voltage selection circuit 8 and the second dummy word line voltage selection circuit 9 may be configured to enable the respective two dummy cells to be driven, and the dummy cells may perform the binary operation.
Fifth Embodiment
The NAND string in a fifth embodiment has the same configuration as that in the first embodiment. The dummy cells are treated as binary cells when data is written or read in a block unit, and when all data is written into the NAND string, its parity is written into the binary cell. The parity is written into the binary cell on either bit line side or source line side, and, for example, a flag that indicates whether the NAND string is in an erased state or written state is written into the other cell. The word line voltage control circuit in that case can be easily achieved by enabling the word line voltage control circuit shown in FIG. 12 to write the parity or flag mentioned above.
Also in the fifth embodiment, the bias uniformity in the operation of writing into the quaternary cell is equal to that in the first embodiment, and the two cells next to the selection gate are treated as binary cells with little concern about the increasing threshold distribution, thereby allowing the degree of integration to be higher than in the first embodiment.
Characteristics common to the first to fifth embodiments described above will be summed up here. Because of the selection gate placed next, the memory cells adjacent to the selection gate are generally different, in the relationship of bias subjected to the memory cells in the writing operation, from the other memory cells placed between the memory cells. Therefore, the memory cell writing characteristics are different in the memory cells next to the selection gate and the memory cells having the memory cells on both sides. Because higher values require strict control of the threshold distribution of the memory cells, a specific writing voltage control considering the writing characteristics is needed for the memory cells next to the selection gate, for example.
The control described above will be a factor of lowered performance and increased complexity of circuits, but according to the first to fifth embodiments, the dummy cells can be provided in the vicinity of the selection gates to achieve simple control of the writing voltage and the uniformity of writing characteristics of the main memory cell. As the wiring width and space of memory circuits are becoming smaller, benefits are provided particularly in the generation of 90 nm or less and multi-level memories.
Furthermore, when the control gate of the memory cell next to the selection gate is charged, the coupling capacitance of the control gate and the selection gate causes the voltage of the selection gate to float in some cases. For example, by providing the dummy gate and properly controlling the control gate voltage of the dummy gate, coupling effects on the selection gate can be minimized.
As described above, the dummy gate can be disposed to have a uniform characteristic of writing into the ordinary memory cells, to enhance its writing performance, and to simplify the control circuit. Moreover, in a multi-level NAND, the dummy gate can be used as the memory cell to record less information than the ordinary memory cell to retain additional information in addition to the effects described above.
Next, an embodiment to reduce pre-charge time will be described as a sixth embodiment.
Sixth Embodiment
Before describing the sixth embodiment, a reading operation of the NAND-structured flash memory will be more concretely described by use of FIGS. 14 to 16 . If a selected bit line 101 is BLE and a non-selected bit line 102 is BLO, the selected bit line BLE is pre-charged to a voltage VPRE from a VPRE transfer circuit because the gate voltage BLSE of a selection gate 103 is H. On the other hand, the non-selected line BLO will be VSS which is a bit line shield potential because the gate voltage BIASO of a selection gate 104 is H.
In the NAND-structured flash memory having the above configuration, the selected bit line 101 is first pre-charged to a pre-charge potential (VPRE) in reading. After the pre-charge, a bit line side selection gate SGD is opened to discharge the electric charges from the cell to the bit line 101 in accordance with a threshold value (signal) written into the cell connected to the selected word line, and its small potential difference is amplified by a sense amplifier. After it is sensed, the bit line 101 recovers its original potential.
On the other hand, the bit lines on both sides of the selected bit line 101 are the non-selected bit lines 102 . Noise due to coupling is reduced in such a method that the non-selected bit lines 102 have a fixed potential (e.g., VSS) and are used as shielding lines. More specifically, the selected bit line 101 and the non-selected bit lines 102 are alternately arranged, and they are allocated in different pages. They are temporarily differentiated by parity, and respectively called an EVEN page and an ODD page.
In order to decrease the bit line pre-charge time, the non-selected bit line 102 which is currently at VSS may be pre-charged to the pre-charge potential (VPRE) at the same time. The pre-charge time is reduced because the wiring capacitance between effective adjacent lines is eliminated and the wiring capacitance necessary to drive all the bit lines is reduced.
In this case, however, in the conventional NAND string structure, when the cell linked to the non-selected bit line 102 serving as a shield has a negative threshold value (“1” data), opening the selection gate 104 will cause the current to flow from the bit line 102 to a source line SRC to lower the potential, resulting in the problem that it cannot serve as the shielding line.
The sixth embodiment concerns the NAND-structured flash memory capable of solving the above problem. As shown in FIG. 17 , in the NAND-structured flash memory according to the sixth embodiment, two new cells are added next to the selection gate to the configuration of a conventional NAND string composed of 32 cells and two selection gates. Information is written into these cells in accordance with the parity of a bit line BL to which the NAND string is linked.
FIG. 17 is different from the prior art ( FIG. 15 ) in that a BL shield potential transfer circuit is eliminated, the selected bit line BLE 101 and the non-selected bit line BLO 102 are both charged to the pre-charge voltage by the VPRE transfer circuit via the selection gates 105 and 104 which have been turned on. The voltage changes at this moment in the gate control voltage BIASO, BIASE and the pre-charge potential VPRE are shown in FIG. 18 .
In an example shown in FIG. 19 , a cell 111 next to a drain side selection gate SGE of BL (EVEN) is written as “1”, a cell 112 next to a source side selection gate SGE is written as “0”, an SGD side cell 113 of BL (ODD) is written as “0”, and an SGS side cell 114 is written as “1”. In other words, information on whether the bit line to which the cell is linked is an even number sequence or odd number sequence is written into the cells 111 , 112 , 113 and 114 . Moreover, a word line WL_EVEN is connected to the control gates of the SDS side cells 111 and 113 , and a word line WL_ODD is connected to the SGS side cells 112 and 114 .
In other words, complementary data is written into the two memory cells 111 and 112 , or memory cells 113 and 114 within one memory cell. Further, the complementary data is also written into the memory cells 111 and 113 , or memory cells 112 and 114 which are connected to the same word line and included in the adjacent bit line.
In the reading operation, WL_EVEN has potential VSS, and WL_ODD has potential VREAD when the EVEN page is read. On the other hand, WL_ODD has potential VSS, and WL_EVEN has potential VREAD when the ODD page is read.
Directing attention to the non-selected ODD side bit line BL 102 , for example, when the EVEN page is read under the above configuration and setting of operating condition, WL_EVEN has VSS, and the cell 113 linked thereto is written as “0”. Accordingly, the cell 113 is cut off, and the current does not run from the bit line 102 pre-charged to VPRE to a source line CELSRC side.
Similarly, if attention is focused on the non-selected EVEN side BL 101 when the ODD page is read, WL_ODD has VSS, and the cell 112 linked thereto is written as “0”. Accordingly, the cell 112 is cut off, and the current does not run from the bit line BL 101 pre-charged to VPRE to the source line CELSRC side.
As described above, in the present embodiment, information on whether the bit line BL to which the NAND string is linked is the EVEN page or ODD page is previously written into the end cell next to the selection gate of the NAND string, so that the cell can be turned on and off by controlling the word line WL.
In this way, even when the non-selected bit line BL serving as the shield is charged to VPRE and the selection gate is opened, the current from the non-selected bit line BL to the source line CELSRC can be cut off, and noise due to the coupling is not caused to the selected bit line BL.
It should be noted that the embodiment has been described above on the presumption that the end cell next to the selection gate is the cell to be cut off, but actually, the cell to be cut off does not have to be the end cell and may be provided in the center of the NAND string. Moreover, the NAND string may have a length of 64 or 128 cells instead of 32 cells, in which case the effect of the added two new cells is small.
Furthermore, in the present invention, information on whether the bit line to which the NAND string is linked is, for example, the EVEN page or ODD page is previously written into the end cell next to the selection gate of the NAND string, so that the cell can be turned on and off by controlling the word line. In this way, even when the non-selected bit line serving as the shield is charged to VPRE and the selection gate is opened, the current cannot run from the bit line to the source line, and noise due to coupling caused to the selected bit line is reduced.
When the bit line is pre-charged in a reading or verifying operation, the selected bit line has conventionally been set to VPRE, and the non-selected bit line to VSS, but in the method described above, the selected bit line and the non-selected bit line are both pre-charged to VPRE at the same time. In other words, since the leakage current that passes when the non-selected bit line is pre-charged to VPRE can be cut off, adjacent coupling capacitance which is the major part of bit line capacitance is eliminated, and the pre-charge time and current consumption can be reduced.
Next, an electronic card will be described as an application of the NAND-structured flash memory of the present invention.
(First Application to Electronic Card)
FIG. 20 is a block diagram showing a first application of the NAND-structured flash memory of the present invention to an electronic card.
As shown in FIG. 20 , an electronic card, for example, a memory card 100 has a NAND-structured flash memory 110 according to the embodiment of this invention. The NAND-structured flash memory 110 receives a predetermined control signal and data from an unshown external device. Also, it outputs the predetermined control signal and data to the unshown external device. Therefore, connected to the NAND-structured flash memory 110 are a signal line (DAT) which transfers, for example, data, addresses or commands; a command line enable signal line (CLE) which indicates that a command is transferred to the signal line DAT; an address line enable signal line (ALE) which indicates that an address is transferred to the signal line DAT; and a ready/busy signal line (R/B) which indicates whether or not the nonvolatile semiconductor memory device 110 is operable.
In this way, the memory card 100 may be equipped only with the NAND-structured flash memory 110 .
(Second Application to Electronic Card)
FIG. 21 is a block diagram showing a second application of the NAND-structured flash memory of the present invention to an electronic card.
As shown in FIG. 21 , an electronic card, for example, a memory card 200 has a NAND-structured flash memory 210 and a controller 220 . The controller 220 controls, for example, the NAND-structured flash memory 210 , and exchanges predetermined signals with the unshown external device.
The controller 220 has interface (I/F) sections 221 and 222 which receive the predetermined signals from the NAND-structured flash memory 210 and the unshown external device, or which output the predetermined signal to the external device; a microprocessor (MPU) section 123 which performs predetermined calculations to convert a logical address input from the external device into a physical address; a buffer RAM 224 which temporarily stores data; and an error correction (ECC) section 225 which generates error correcting codes. A command signal line (CMD), a clock signal line (CLK) and a signal line (DAT) are connected to the controller 220 .
In this way, the memory card 200 may be equipped with the NAND-structured flash memory 210 , and the controller 220 which controls the NAND-structured flash memory 210 .
In addition, the controller 220 may be equipped only with the interface section with the external device and the nonvolatile semiconductor memory device 210 . In this case, the controller 220 is an integrated circuit device generally called a memory interface.
It should be noted that the controller 220 or the memory interface may be mounted on a different integrated circuit chip from, or the same integrated circuit chip as, that of the NAND-structured flash memory 210 .
FIG. 22 is a diagram showing the application of the electronic card to a digital camera, and the electronic card (memory card) 200 is used as a recording medium of the digital camera.
As shown in FIG. 22 , a case of a digital camera 271 has a card slot 272 that accommodates a circuit board (not shown) connected thereto. The memory card 200 is detachably installed in the card slot 272 of the digital camera 271 . The memory card 200 is installed in the card slot 272 to be electrically connected to an electronic circuit on the circuit board.
FIG. 23 is a diagram showing the application of the electronic card 200 to a mobile telephone 300 , and the electronic card (memory card) 200 is used as an external memory of the mobile telephone 300 . The memory card 200 is inserted into an external memory slot 310 . The external memory slot is connected to a CPU bus via an interface circuit. The provision of the external memory slot 310 in the mobile telephone 300 enables information stored in the external memory 200 to be read by the mobile telephone 300 and to be input to the mobile telephone 300 .
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
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A NAND-structured flash memory comprises a memory cell array wherein plural memory strings are arranged in matrix form, each of the memory cell strings including plural nonvolatile memory cells, the first conducting paths of the memory cells being connected in series, at least one of the memory cells having a function other than an external data storing function, plural first selection transistors having second conducting paths, and one end of the second conducting paths being connected to one end of the series of the first conducting paths, respectively, plural bit lines connected to the other end of the second conducting paths, plural second selection transistors having third conducting paths, and one end of the third conducting paths being connected to one end of the series of the first conducting paths, respectively, and a source line connected to the other end of the third conducting paths.
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TECHNICAL FIELD
[0001] The present invention relates to an apparatus for monitoring an oil and/or gas well. More specifically, the present invention relates to an apparatus for monitoring physical parameters in an oil and/or gas well, the apparatus being connectable to a wellhead of the oil and/or gas well, the apparatus comprising a flange assembly configured with a through bore and an end termination, in which through bore a sensor and associated electronics are arranged, and wherein the sensor is connected to the associated electronics.
BACKGROUND
[0002] During well completion of a fully drilled oil and/or gas well, a number of casings of different lengths and diameters will be cemented to the ground formation. Between the casings, which are disposed coaxially with each other, a so-called annulus will be formed. To prevent a leakage in the oil and/or gas well, a plurality of packer elements will suitably be arranged between the casings. The casings will be suitably suspended from a wellhead structure, where the wellhead structure is arranged at the top of the oil and/or gas well. During operation of the oil and/or gas well, the wellhead structure will conduct the well stream therethrough for further processing of the well stream. The wellhead structure will also be a safety mechanism against the well stream flowing uncontrolled to the surface.
[0003] A wellhead structure of this kind is subjected to large loads and stresses from the surrounding environment. Although these structures and installations are designed to be maintenance-free for a number of years, they must be inspected constantly for safety and financial reasons.
[0004] It is both desirable and necessary to carry out an inspection of such offshore installations, for example, various equipment, pipelines, wellheads etc., not only during production, but also during drilling, installation and maintenance and repair work, this inspection taking placed in the form of automated operations. This means that quite different demands are made on the equipment and monitoring, inspection and communication systems that are used offshore than what is normal for installations onshore.
[0005] In addition to the above, it will be extremely important to know how an oil and/or gas well is behaving, or what is happening in the oil and/or gas well, and this will be the case throughout the entire lifetime of the well, i.e., from when the actual drilling of the well starts until the well is finally shut down. This is done by monitoring a number of different parameters in the well, which parameters may for example be contamination, leaks, well pressure, the production itself, sand/erosion in the well, wellhead temperature, the state or condition of various equipment (for example, the position of a valve), corrosion etc.
[0006] In connection with, for example, production of oil and/or gas wells, it will be extremely important from a safety, reliability and cost aspect to prevent a so-called pressure leak from the well through the different annuli in the casings, and out to the surroundings. If an undesirable pressure leak of this kind nevertheless occurs, various safety systems are intended to be able to close the well even under pressure, so that well fluid which has flowed into the different annuli of the well can circulate out in a controlled manner.
[0007] By constantly or repeatingly carrying out measurements of, for example, the pressure in the well, where this can be done at a number of different points in the well, it will be possible to have at an earlier point in time an indication that a pressure increase is about to occur in the well, that a pressure leak in the well will or has already occurred, whereby various actions can be taken to ensure that the consequences of such a pressure build-up will be minimal or to prevent them altogether.
[0008] Various solutions have therefore been developed to monitor and/or control pressure in an oil or gas well, Reference can be made, for example, to U.S. Pat. No. 5,172,112, in which there is known that a pressure-measuring device measures pressure in a subsea pipe. The device includes a stationary unit mounted to the exterior of the subsea pipe and a movable unit that is lowered into position next to the stationary unit whenever the pressure is to be monitored or measured. The stationary unit, which is a strain gauge, will monitor the pressure in the pipe by measuring the “strain” in the pipe. The measurements will subsequently be transmitted from the stationary unit in the form of suitable signals, whereby the movable unit will then convert these signals to give a picture of the pressure that is within the subsea pipe.
[0009] A solution is known from GB 2 286 682 where an inductive pressure transducer is used to measure the pressure within a pipe. This is accomplished by passing an alternating current within an inductor coil to generate a magnetic field. The magnetic field passes through a gap formed between the pipe and the inductor coil, and then into the pipe. The fluid flowing in the pipe will, owing to its pressure, induce stress in the pipe, which stress will cause variations in the electromagnetic properties of the material from which the pipe is made, which variations can be sensed by the magnetic field that is formed. The sensed variations can then be converted to give a pressure measurement.
[0010] Another system for detecting a leakage in an oil and/or gas well is described in U.S. Pat. No. 4,116,044, where the system comprises a plurality of pressure-sensitive transducers that are arranged in a through hole in a wellhead. The pressure-sensitive transducers will be so arranged that they can detect a leakage in a plurality of annuli in the well. The transducers are connected through wires to a junction box which will be capable of carrying signals to a processing location. During replacement of the transducers, the well will have to be shut down as the replacement operation will involve the well being “opened”.
[0011] It is an object of the present invention to provide an improved apparatus for monitoring physical parameters in an oil and/or gas well, for instance with regard to safety, including fire safety, reliability and/or costs.
SUMMARY
[0012] The invention has been defined by the claims.
[0013] The apparatus disclosed herein may be used in a monitoring system which measures and monitors different parameters in an oil and/or gas well, for example, pressure and/or temperature, the monitoring system being designed so as to be capable of monitoring a number of different zones or areas in an oil and/or gas well. The purpose of the monitoring may be, through the measurements made, to see at an early stage that a pressure leak in the well is in the process of occurring, or already has occurred, thereby allowing various actions to be taken to prevent or even to limit the damage caused by the pressure leak. The apparatus can in a typical use be connected to a wellhead in the oil and/or gas well. However, it should be understood that the apparatus for monitoring physical parameters may also be used in other connections.
[0014] The disclosed apparatus comprises a flange assembly that is configured with a through bore and an end termination, which will seal or close an end of the apparatus. A sensor and associated electronics are arranged in the through bore. The sensor includes a first electronic circuitry. The sensor is connected to a second electronic circuitry via transmission devices, for example in the form of wires or the like, which are passed through a pressure-tight element arranged in the through bore. The pressure-tight element is arranged in the through bore in such a way that it separates two longitudinal portions of the through bore.
[0015] The pressure-tight element has, i.a., the effect of preventing a fluid leakage from occurring over the pressure-tight element. As a result, the apparatus will be provided with a double barrier arrangement for the passage leading into an annulus of the well head. This arrangement also provides a fire safe barrier between various parts of the apparatus, in particular between the sensor, including the first electronic cicuitry, and the second electronic circuitry.
[0016] In an embodiment, the pressure-tight element may be a ceramic element.
[0017] The pressure-tight element may alternatively be a glass element.
[0018] Alternatively, the pressure-tight element may include a metallic disc, and the transmission devices may include electrical conductors passed through bores in the metallic disc. Further, a glass, sapphire or a ceramic material may surround each conductor and fluidly seal the space between each conductor and the corresponding bore in the metallic disc.
[0019] In an embodiment, e.g. where the pressure-tight element is a ceramic element, the ceramic element may be so configured that it allows a current passage through the ceramic element. The ceramic element may in specific through-going lines or areas through the longitudinal direction thereof then be made of a mixture of a ceramic material and a conducting material (for example, platinum), so that current can be transferred across the ceramic element.
[0020] In this connection, it should also be understood that the ceramic element may be composed of several ceramic pieces along its longitudinal direction, which ceramic pieces, when assembled, will then form the ceramic element.
[0021] The current passage through the pressure-tight element may be obtained by using metallic or other electrically conducting materials. Wires or the like can then in a suitable manner be configured to be capable of being connected to each side of the pressure-tight element, so as to obtain a current passage through the pressure-tight element.
[0022] The sensor will be able to measure different parameters in the oil and/or gas well, after which these “measurements” in the form of suitable signals will be transmittable to the associated electronics. The associated electronics will then either be able to process the received signals themselves, or send these signals to another receiving and/or processing unit for further processing. This can be achieved in that the associated electronics can be connected to the receiving and/or processing unit via one or more electric wires, one or more signal cables etc., or even wirelessly.
[0023] The disclosed apparatus may be provided with one or more batteries or battery packs, which will supply the sensor, associated electronics etc. in the apparatus with necessary power as required. However, this can also be accomplished by connecting the apparatus to one or more power supplying wires.
[0024] To be able to connect the pressure-tight element, e.g. the ceramic element, in the apparatus, the pressure-tight element may be arranged in a sleeve, which sleeve is along a part of its length configured with a threaded portion. A corresponding threaded portion internally in the through bore in the apparatus will then be formed, so as to allow the sleeve containing the pressure-tight element to be connected to the apparatus.
[0025] In an embodiment of the present invention, the sensor is only designed to measure pressure and temperature, but it should be understood that the sensor may also be designed so as to be capable of measuring other parameters or additional parameters. It should also be appreciated that other devices may be used to carry out the desired measurements.
[0026] Furthermore, the sensor could be configured with a threaded portion along a part of its length, thereby enabling the sensor to be screwed to a tubular element, for example, a wellhead.
[0027] The flange assembly of the apparatus may be constituted of a front and a rear flange portion, where the rear flange portion overlaps a part of the front flange portion when they are assembled. The front and the rear flange portion will further be connected to each other by bolts, screws or the like, there additionally being provided one or more sealing devices, for example, O-rings or the like, between the overlapping parts of the front and rear flange portions, so as to provide a fluid-tight connection between them.
[0028] In order to be able to seal off one end of the apparatus when the apparatus is fixedly connected to a tubular element, for example, a wellhead, Christmas tree or the like, the end termination is configured with a projection, for example, in the form of a sleeve, at a distance from its outer periphery, which projection, when the end termination is connected to the rear flange portion, will extend a distance into the rear flange portion and essentially be in contact with the interior of the through bore in the rear flange portion. One or more sealing devices, for example, O-rings, are disposed between the overlapping portions of the end termination and the rear flange portion in order to provide a fluid-tight connection between them. The rear flange portion and the end termination are connected to each other by bolts, screws or the like.
[0029] It should be understood that the flange assembly may comprise more or fewer elements.
[0030] The flange assembly, the through bore therein and the end termination may have a circular shape, but it should also be understood that square, rectangular or other polygonal shapes may be used, both for the flange assembly and the through bore.
[0031] The apparatus may be arranged so as to be able to communicate with other similar apparatus. This may be done by connecting two or more apparatus together with the aid of at least one wire. The communication between the various units may also take place wirelessly.
[0032] The apparatus disclosed herein may be used in a temperature and pressure monitoring system for monitoring an oil and/or gas well.
[0033] Also disclosed is a wellhead for use with an oil and/or gas well, the well having a plurality of casings, the casings defining a plurality of annili. The wellhead is configured with a plurality of through-holes, each leading into a respective annulus of the well. Each through-hole is connected to an apparatus as has been disclosed in the present specification.
[0034] Thus, by means of the present invention an apparatus is provided that can be used in connection with a temperature and pressure monitoring system which allows the sensors in the system to be mounted or demounted under pressure, i.e., that the oil and/or gas well may be in production whilst the mounting/demounting is carried out; the system will further preserve the barriers in the safety system and any pressure leaks in the oil and/or gas well will to far greater extent be prevented in that an indication of “abnormal” conditions in the well is given at an earlier stage.
[0035] Other advantages and special features of the present subject invention will be made clear in the following detailed description, the attached drawings and the following patent claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0036] The present invention will now be described with reference to several embodiments of the invention as shown in the figures, wherein:
[0037] FIG. 1 is a schematic outline of a typical wellhead structure, comprising a temperature and pressure monitoring system;
[0038] FIG. 2 shows a first embodiment of an apparatus according to the present invention, seen in a partial side view and in a cross-section;
[0039] FIG. 3 shows a second embodiment of the apparatus according to the present invention, seen in a cross-section; and
[0040] FIG. 4 shows a third embodiment of the apparatus according to the present invention seen from the rear and in a cross-section.
DETAILED DESCRIPTION
[0041] FIG. 1 shows a typical wellhead structure that is used in connection with an oil and/or gas well, where a wellhead 1 , at its upper end, is connected to a riser 2 which extends between a floating structure (not shown), for example, a platform or the like, and the wellhead 1 . A first casing 3 extends a distance down into a surface formation and is cemented to the surface formation O.
[0042] The upper end of the first casing 3 is suitably suspended from the wellhead 1 , sealing devices 4 in the form of one or more packers being arranged between an exterior surface of the first casing 3 and an interior surface of the pressurised housing H of the wellhead 1 . Within the first casing 3 there is arranged another, second casing 5 , which will then extend through the first casing 3 and a longer distance down into the surface formation O than the first casing 3 .
[0043] The second casing 5 will, like the first casing 3 , be cemented to the surface formation O. The second casing 5 will in addition be partly supported by (suspended in) the first casing 3 . In order to obtain a tight connection between an interior surface of the first casing 3 and the exterior surface of the second casing 5 , sealing devices 4 are provided between the first and the second casing 3 , 5 .
[0044] As the second casing 5 has a smaller diameter than the first casing 3 , a space will be formed between the first and the second casing 3 , 5 , which space is called an annulus. The space that is delimited by the interior surface of the first casing 3 , the second casing 5 and the casing hanger in the first and the second casing 3 , 5 will define a first annulus A.
[0045] As described above for the first and the second casing 3 , 5 , a third casing 6 will run internally through the second casing 5 , and will be supported by (suspended in) the second casing 5 . The third casing 6 will have a diameter that is smaller than the diameter of the second casing 5 . Here, the second and the third casing 5 , 6 , together with the casing hanger in the second and the third casing 5 , 6 , will define a second annulus B. Within the third casing 6 there is arranged a last and fourth casing 7 , through which fourth casing 7 a production tubing (not shown) will run when the oil and/or gas well is in production. The fourth casing 7 will have a diameter that is smaller than the diameter of the third casing 6 . The space that is formed between the third and the fourth casing 6 , 7 and the casing hanger in the third and the fourth casing 6 , 7 will form a third annulus C. To obtain a tight connection between an interior surface of the second and the third casing 5 , 6 and the exterior surface of the third and the fourth casing 6 , 7 , sealing devices 4 are provided between the second and the third casing 5 , 6 and the third and the fourth casing 6 , 7 .
[0046] The wellhead 1 may furthermore be connected to a blow-out valve (not shown), a so-called BOP (Blow Out Preventer).
[0047] The above wellhead structure will provide a fluid and pressure-tight system, but conditions in the oil and/or gas well might mean that the sealing devices 4 , owing, for example, to large pressure build-ups in the well, temperature variations, or their service life, might begin to “leak”, such that a pressure leak occurs in the well, where this is not desirable.
[0048] In order to prevent such undesired pressure leaks, a plurality of apparatus for measuring different parameters 8 , which will be explained in more detail in connection with remaining FIGS. 2 to 4 , will be arranged along the length of the wellhead 1 , such that measurement and monitoring of different parameters, for example, pressure and/or temperature, can be carried out in each of the annuli A-C in the well. The wellhead 1 will then be configured with a plurality of through holes (not shown), to which holes the apparatus 8 can suitably be connected. The measurements made in each of the annuli A-C may be suitably transmitted to, for example, a floating structure for processing and monitoring.
[0049] FIG. 2 shows a first embodiment of a measuring or monitoring apparatus 8 according to the present invention, where the apparatus 8 is shown partly from the side and in a cross-section, when connected to the wellhead 1 . The wellhead 1 will then be configured with a plurality of through holes or passages, 9 , which passages 9 will then be so positioned as to lead in to each of the annuli A-C. The apparatus 8 comprises a sensor 10 and a flange assembly 11 , which are fixedly connected to each other. The flange assembly 11 is constituted of a front flange portion 12 and a rear flange portion 13 , which via a plurality of bolts 14 or the like are connected to each other. An end of the rear flange portion 13 will then be so configured that it overlaps an end of the front flange portion 12 when the front and the rear flange portion 12 , 13 are assembled. Both the front and the rear flange portion 12 , 13 will furthermore be configured with a groove or recess 16 , in which recess 16 an O-ring 17 is arranged when the front and the rear flange portion 12 , 13 are connected to each other, so as to provide a fluid-tight connection between them.
[0050] The flange assembly 11 is further configured with a through bore 14 , in which bore 14 the sensor 10 and the associated electronics 15 are arranged. A second end (opposite the end that is connected to the rear flange portion 13 ) of the front flange portion 12 will then be configured with a contact face 18 for the sensor 10 , the said contact face 18 forming a stop edge for the sensor 10 . The sensor 10 will then similarly be configured with a face 19 that will bear against the contact face 18 in the front flange portion 12 , such that the sensor 10 is positioned correctly in relation to the wellhead 1 . The sensor 10 will furthermore, along a part of its length, be configured with a threaded portion 20 , such that the sensor 10 can be screwed into the passage 9 in the wellhead 1 . The passage 9 in the wellhead 1 will then be configured with a complementarily threaded portion (not shown).
[0051] The sensor 10 comprises a first electronic circuitry, e.g. in the form of an electronic printed circuit board 21 , which via wires 22 is connected to a second electronic circuitry in the form of a separate main printed circuit board 23 arranged in the bore 14 in the front flange portion 12 . Through this configuration, the sensor 10 , comprising the electronic printed circuit board 21 , will be separated from the main printed circuit board 23 , the sensor 10 being arranged at the end of the front flange portion 12 which lies closest to the wellhead 1 , whilst the separate main printed circuit board 23 will be arranged at an opposite end of the front flange portion 12 , adjacent to the rear flange portion 13 .
[0052] Between the sensor 10 and the separate main printed circuit board 23 there is disposed a pressure-tight element 24 , for instance a ceramic element with wires 22 connecting the sensor 10 and the separate main printed circuit board 23 extending through the ceramic element.
[0053] In one embodiment, the wires 22 will, however, not run through the whole of the ceramic element 24 , only a certain length into the ceramic element 24 , such that wires 22 from sensor 10 and wires 22 to the main printed circuit board 23 , when arranged in the ceramic element 24 , will be located at a distance from each other. The ceramic element 24 is however so configured that through at least one through-going portion or area through the ceramic element 24 there is arranged a mixture of a ceramic material and an electrically conducting material (for example, platinum). This will mean that the ceramic element 24 will form a pressure-tight barrier in the apparatus 8 . The ceramic element 24 is in a fluid and/or pressure-tight way connected to a sleeve 25 . The sleeve 25 is further configured with a threaded portion (not shown) and a varying cross-section along its length. The current passage through the ceramic element 24 may however be achieved by, for example, using metallic or other electrically conducting materials.
[0054] The pressure-tight element 24 has been described above, by example, as a ceramic element. In this case the pressure-tight element 24 may be provided as a ceramic feedthrough disc, wherein wires or other electrical conductors may be embedded in the ceramic element. The ceramic material may be chrystalline or non-chrystalline. The ceramic material may, e.g., include aluminium oxide.
[0055] Alternatively, the pressure-tight element 24 may be a glass element, or as another alternative, the pressure-tight element 24 may include a metallic disc (e.g., made of steel or titanium), and the transmission devices may be electrical conductors (e.g., made of platinum) passed through bores in the metallic disc. Further, a glass, sapphire or a ceramic material may surround each conductor and fluidly seal the space between each conductor and the corresponding bore in the metallic disc.
[0056] The pressure-tight element 24 may be located in a portion of the bore 14 where the diameter is reduced. The pressure-tight element 24 is shown fitted into a portion of the bore having a diameter corresponding to the diameter of the pressure-tight element 24 . A sleeve 25 is located in the bore 14 in engagement with a first side of the pressure-tight element facing the passage 9 . The sleeve 25 in this position exerts pressure to the isolation element 24 . The sleeve may be configured with threads, provided for engagement with threads in the bore 14 , and may be provided with a diameter enlarged portion 25 b arranged to fit with a restriction of the bore 14 which may provide an end stop for the sleeve 25 . By engaging the threads of the sleeve 25 with the threads of the bore 14 , the sleeve may be screwed into a position exerting a pressure to the pressure-tight element 24 . A second side of the isolation element 24 , which faces away from the passage 9 , rests against a restriction in the diameter of the bore providing a contact portion 26 . In between the contact portion 26 and a portion of the second side of the isolation element a seal, for instance a metallic seal, may be provided. By moving the sleeve 25 relative to the bore 14 , for instance by screwing the sleeve 25 relatively to the bore 14 the isolation element 24 exerts a force to the seal of a size which provides an isolation engagement between the contact portion 26 , the seal and the isolation element 24 . This arrangement may enable or further improve the pressure tight properties of the apparatus.
[0057] The through bore 14 in the front flange portion 12 will along a part of its length be configured with a varying cross-section, which varying cross-section will be complementarily configured with the varying cross-section of the sleeve 25 . A rear edge 26 of the varying cross-section in the through bore 14 will, when the sleeve 25 with the pressure-tight element 24 , e.g. ceramic element, is arranged in the varying cross-section of the through bore 14 , together with an end of the sleeve 25 , form a tight connection between the front flange portion 12 and the sleeve 25 . This arrangement may form a fireproof connection in the apparatus 8 .
[0058] The rear flange portion 13 is configured with a through and threaded hole 27 , so as to enable a cable lead-in 28 , comprising a tensioning nut 29 , to be connected to the threaded hole 27 . Between the contact faces of the rear flange portion 13 and the cable lead-in 28 there is arranged a seal 30 in the form of an O-ring. An electric cable E is then passed through the cable lead-in 28 and connected to a connecting printed circuit board 31 in the though bore 14 in the flange assembly 11 .
[0059] The separate main printed circuit board 23 and connecting printed circuit board 31 are, by means of a securing device 32 , connected to a rear wall 33 of the front flange portion 12 . The securing device 32 will further ensure that the main printed circuit board 23 and the connecting printed circuit board 31 are arranged at a distance from each other. Signals received from the sensor 10 will then be wirelessly transmittable from the main printed circuit board 23 to the connecting printed circuit board 31 , in order thus, through the electric wire E, to be transmitted for processing on a floating structure (not shown).
[0060] The rear flange portion 13 , which is an “open” sleeve, is, at an end opposite the end overlappingly connected to the front flange portion 12 , configured for being connected to an end termination 34 , such that the apparatus 8 can be closed or sealed at the end opposite the connection to the wellhead 1 . The end termination 34 is then configured with a plurality of through openings 35 , which through openings 35 are used for passage of bolts 36 . An end termination in the rear flange portion 13 will then be configured with a plurality of threaded holes 37 for receipt and screw fastening of bolts 36 .
[0061] The end termination 34 will on one side be configured with a projection 38 , which projection 38 will be such that it essentially corresponds to the through bore 14 , such that the projection 38 will extend a certain distance into the rear flange portion 13 when the end termination 34 , via the bolts 36 , is connected to the rear flange portion 13 . A seal 39 in the form of an O-ring is arranged between the interior surface of the rear flange portion 13 and the exterior surface of the projection 38 , one or both of these surfaces then being configured with a groove for receiving the seal 39 .
[0062] Furthermore, the front flange portion 12 , in a face A which forms contact with the wellhead 1 , is configured with a plurality of holes 41 , such that bolts and nuts 42 can be used to fixedly connect the apparatus 8 to the wellhead 1 . Face A is further configured with a recess 43 for receiving a sealing element 44 such that a tight connection is provided between the apparatus 8 and the wellhead 1 when they are connected to each other.
[0063] FIG. 3 shows another embodiment of the apparatus 8 according to the present invention, where the apparatus 8 is now configured so as to be able to transmit signals from the sensor 10 wirelessly. With the exception of how the transmission of signals takes place according to this embodiment, the general component composition of the apparatus 8 and its operating principle are the same as described for the first embodiment of the invention as shown in FIG. 2 , and so for the sake of simplicity they are not described again.
[0064] The embodiment shown in FIG. 3 uses a wireless transmission of signals from the sensor 10 , where the rear flange portion 13 will be configured with a through and threaded hole 27 , so as to enable a wireless antenna 44 to be connected to the through and threaded hole 27 . A securing device 32 is also used in this embodiment to connect the separate main printed circuit board 23 and the connecting printed circuit board 31 to the rear wall 33 of the front flange portion 12 . However, the distance between the main printed circuit board 23 and the connecting printed circuit board 31 will now be greater than in the embodiment described with reference to FIG. 2 , seen in relation to the fact that a part of the wireless antenna 44 will extend a distance into the through bore 14 in the flange assembly 11 . Signals received from the sensor 10 will then be wirelessly transmittable from the main printed circuit board 23 to the connecting printed circuit board 31 , so as to be further transmittable wirelessly from the connecting printed circuit board 31 to the wireless antenna 44 , in order to be further transmitted wirelessly for processing on a floating structure (not shown). For signal amplification, a plurality of signal amplifying units (not shown) may be provided between the wellhead and the floating structure.
[0065] To operate the sensor 10 and/or the wireless antenna 44 in the apparatus 8 , a battery or a battery pack 45 is provided in the apparatus 8 when the apparatus 8 is assembled. This embodiment will mean that the battery or battery pack 45 can easily be replaced by unscrewing bolts 36 in the end termination 34 and removing the end termination 34 from the rear flange portion 13 . The battery or battery pack 45 can in a suitable manner, for example, by means of wires etc. (not shown), be connected to the connecting printed circuit board 31 .
[0066] The battery or battery pack 45 may also be connected to, or comprise a device (not shown) capable of ensuring that the battery or battery pack 45 is turned off and on at certain time intervals. The device can then turn the battery or battery pack 45 on for a pre-specified time unit (minutes, hours or days), so as to allow the desired number of measurements of, for example, pressure and temperature to be carried out, after which the device will turn the battery or battery pack 45 off. However, it should be understood that such a device must also comprise the possibility of being overridden, seen in relation to the fact that measurements with the apparatus 8 may also be carried out outside the pre-specified time units.
[0067] FIG. 4 shows an additional embodiment of the apparatus 8 according to the present invention, where the rear flange portion 13 in the apparatus 8 is configured with several through and threaded holes 27 . The general component composition of the apparatus 8 and its operating principle are the same as described for the first embodiment of the invention as shown in FIG. 2 , and so for the sake of simplicity they are not described again.
[0068] Configuring the rear flange portion 13 with several through and threaded holes 27 , will enable the apparatus 8 to be connected to two electric cables E, an electric cable E and a wireless antenna 44 , or even two wireless antennas 44 . Alternatively, one of the through and threaded holes 27 can initially be closed by a stop plug 46 . If, for example, the electric wire E or the wireless antenna 44 for some reason is knocked off or damaged there will be the possibility of connecting to the apparatus 8 by removing the stop plug 46 and, for example, coupling a wireless antenna 44 to the other through and threaded hole 27 .
[0069] In addition, this embodiment will also permit several similar apparatus to be connected on the same line, where the apparatus will then be able to communicate with each other digitally.
[0070] The invention has now been explained by referring to some non-limiting examples. A person of skill in the art will understand that it will be possible to make a number of variations and modifications to the temperature and pressure monitoring system as described within the scope of the invention as defined in the attached claims.
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The present invention relates to an apparatus for monitoring physical parameters in an oil and/or gas well, the apparatus being connectable to a wellhead of the oil and/or gas well. The apparatus comprises a flange assembly configured with a through bore and an end termination, in which through bore a sensor and associated electronics are arranged. The sensor, including a first electronic circuitry, is connected to a second electronic circuitry via transmission devices that are passed through a pressure-tight element arranged in the through bore. The invention also relates to a wellhead for use with an oil and/or gas well with a plurality of casings defining a plurality of annili. The wellhead is configured with a plurality of through-holes, each leading into a respective annulus of the well, and each through-hole is connected to an apparatus as mentioned above.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
BACKGROUND OF THE INVENTION
[0003] This invention relates to papermaking and particularly to the treatment of cellulosic material preparatory to use of the treated material to manufacture paper web material.
[0004] As is well known in the art, paper is commonly formed from wood. Generally, the industry divides wood used in papermaking into two categories; namely hardwoods and softwoods. Softwood fibers (tracheids) come from needle-bearing conifer trees such as pine, spruce, alpine fir, and Douglas fir. Hardwood fibers are derived from deciduous trees of various varieties.
[0005] Among the distinguishing differences between hardwood (HW) fibers and softwood (SW) fibers are(a) the length of the individual cellulosic fibers of the wood, (b) the coarseness of the fibers, and (c) the stiffness or collapsibility of the fibers.
[0006] The morphology of softwood fibers, tends to limit the potential uses of the papers producible from such fibers. “Paper” as used herein includes webs or sheets without limitation as to the size or basis weight of the web or sheet. For example, either HW or SW paper may be employed as “bleached board” (useful in containers for consumer products, for example) or as “container board” or “liner board” (useful in corrugated boxes, for example). Printability of a paper is a major consideration with respect to the end use of the paper. SW fibers are notoriously problematic as respects the printability of the paper produced from these fibers in that SW fiber papers tend to be inordinately porous, stiff, and must be treated specially to obtain a paper surface which is suitably printable.
[0007] It is well known in the art that HW and SW must be subjected to specific treatments for converting the wood into a fibrous slurry employed in the formation of a paper web. Softwoods are more plentiful and are more readily replaceable, as by tree farming. Softwoods in general are less costly. Thus, it is desirable that SW fibers be substituted for HW fibers wherever possible in papermaking. Southern pine, or mixtures of hardwoods and softwoods, are commonly examined as possible substitutes for end products which have heretofore been manufactured using hardwoods.
[0008] Heretofore, in attempts to utilize SW fibers in printable paper, it has been proposed to treat the pulped fibers with hydrolytic enzymes. Refining of the enzyme-treated fibers to alter their size, shape, degree of fibrillation, etc., have been employed. Enzyme treatments suffer from sensitivities of the enzyme to process conditions, and a tendency to become inactivated and/or to be carried forward into the papermaking equipment. The lack of cost-effectiveness has also been a long-standing issue.
[0009] Chemical treatments, such as hydrogen peroxide treatment, are commonly carried out under alkaline conditions for bleaching or brightening of wood pulps. This condition that is maximized for bleaching, usually does not correlate with the best conditions for maximum oxidation.
[0010] Smoothness and Formation are measures of, among other things, the printability of the paper. “Formation”, as used as a paper characteristic usually, and herein, is a synonym for relative uniformity over a scale of some distance, e.g., 5 to 20 mm. Formation may be judged by viewing it with light from the back and other means. Both smoothness and formation are affected, among other things, fiber length, morphology and collapsibility.
BRIEF SUMMARY OF THE INVENTION
[0011] In accordance with one aspect of the present invention, it has been found that alteration of the morphology of cellulose fibers, particularly softwood fibers, by (a) subjecting the fibers to a metal ion-activated peroxide treatment carried out at a pH of between about 1 and about 9, preferably between 3 and 7, and (b) subjecting the treated fibers to a refining treatment converts SW fibers to HW-like fibers in many respects. The metal ion-activated peroxide treatment has been noted to act on pulp cellulose and hemi-cellulose, causing oxidation and oxidative degradation of cellulose fibers. The chemical treatment of the pulp, taken alone, is not sufficient to attain the desired modification of the morphology of the fibers, however, subsequent refining or like mechanical treatment of the chemically-treated fibers to achieve a given degree of refinement of the fibers requires dramatically less refining energy, e.g., between about 30 and 50% less energy to achieve a desired end point of refinement. The pulp treated in accordance with the present invention demonstrates substantially reduced fiber length or fiber length distribution, thereby enabling better uniformity of paper sheet (web) structure as measured by formation or texture. Moreover, the treated fibers are more collapsible during sheet consolidation and result in significantly improved paper surface properties such as smoothness. In these respects, SW fibers treated in accordance with the present invention are substantially functionally equivalent to HW fibers in regards to their usefulness in papermaking. The treatment of the present invention may be applied to wood chemical pulps (or pulp mixtures) having various processing histories such as pulping, bleaching or acid hydrolysis, or other combinations of processing of wood into pulp suitable for infeed to a papermaking machine.
[0012] In one embodiment, the present invention may be applied to pulp which has already been subjected to refining, chemical treatment, enzyme treatment, microfibrilltion, and/or acid hydrolysis, for example, to increase the pulp freeness or improve drainage during the papermaking process and/or to reduce the cellulose particles suspension viscosity and improving flow characteristic.
[0013] In a further embodiment, the advantages of the present invention may be achieved employing a hypochlorite treatment at pH 3-9, preferably, pH 3-8 and employing hypochlorous acid as the dominate active agent, followed by subsequent refining of the treated pulp.
[0014] Moreover, either the metal ion-activated peroxide or the hypochlorous acid treatment may be applied alone to refined fibers for increased freeness/drainage, or on micro-fibrillated cellulose materials for reduced suspension viscosity. Further, either embodiment may be employed as a means for controlling the viscosity of a pulp suspension at any of various locations between the initial digestion of the cellulose material to and including the feeding of the pulp suspension into a papermaking machine. This latter aspect of the present invention is applicable in the dissolution of pulp for viscose production, for example. In certain stances, the beneficial effects of the present invention are exhibited in the calendaring of a paper web or sheet formed from treated SW fibers or combinations of HW fibers and treated SW fibers.
[0015] In a still further embodiment, the present invention may be combined with a fiber fractionation process for the treatment of specific fiber fractions.
[0016] Paper produced employing pulp treated in accordance with the present invention exhibits tear strengths at HW levels, with little material deterioration of tensile strength. Improved bonding of the fibers within the sheet is also provided due to enhanced freeness.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0017] The above-mentioned features of the invention will become more clearly understood from the following detailed description of the invention read together with the drawings in which:
[0018] FIG. 1 is a graph depicting the energy savings attributable to the present invention when refining Southern Pine pulp;
[0019] FIG. 2 is a graph depicting fiber length reduction achieved when treating Southern Pine pulp in accordance with the present invention;
[0020] FIG. 3 is a graph depicting the shifting of fiber length distribution between treated and untreated softwood pulp in accordance with the present invention;
[0021] FIG. 4 is a microphotograph depicting untreated pine fibers;
[0022] FIG. 5 , is a microphotograph depicting pine fibers treated in accordance with the present invention;
[0023] FIG. 6 is a graph depicting the relationship of bulk vs. smoothness of hardwood pulp, untreated pine pulp and treated pine pulp;
[0024] FIG. 7 is a graph depicting the relationship of bulk vs. freeness of the pulps depicted in FIG. 6 ;
[0025] FIG. 8 is a graph depicting the relationship of tear vs. freeness of the pulps depicted in FIG. 6 ;
[0026] FIG. 9 is a graph depicting bulk and smoothness relationship of untreated hardwood pulp, untreated pine pulp, and various mixtures of hardwood and softwood pulps;
[0027] FIG. 10 is a graph depicting the fiber length reduction of untreated pine pulp and pulp treated in accordance with the present invention, employing low intensity disc refining;
[0028] FIG. 11 is a graph depicting the energy savings associated with disc refining employed as a component of the present invention when processing treated and untreated pine pulp; and
[0029] FIG. 12 is a graph depicting the relationship between fiber length reduction and the energy employed in refining untreated pulp and pulp treated in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0030] In accordance with one aspect of the present invention, there is provided a method for the transformation of softwood fibers, particularly Southern pine fibers, into hardwood-like fibers. The method employs the steps of (a) subjecting a SW pulp containing cellulose and hemicellulose, to a solution containing a transitional metal ion and a peroxide at a pH of between about 1 and 9 for a time sufficient to oxidize a substantial portion of the cellulose/hemi-cellulose and to oxidatively degrade the cellulose fibers, and (b) subjecting the treated pulp to a refining operation. The pulp thus treated, when formed into a web on a papermaking machine exhibits many hardwood-like properties such as overall formability into a web having surface properties like webs formed from hardwood fibers employing conventional papermaking techniques.
[0031] In one embodiment of the present invention, softwood fibers obtained from coniferous trees, and particularly Southern pine trees, are converted into a pulp employing the kraft process in which the fibers are treated in a heated alkaline solution to substantially separate the fibers from their lignin binder, as is well known in the art. Whereas Southern pine fibers are particularly suitable for treatment employing the present invention, it is recognized that fibers from other coniferous trees may be employed. Further, the present invention may be advantageously employed with mixtures of SW and HW fibers, for example mixtures containing between about 50% and 90% by weight of SW pulp and between about 10% and 50% HW pulp.
[0032] The SW pulp or mixture of SW and HW pulps, prior to treatment thereof employing the present invention, may comprise pulp which has not undergone any conventional treatment of the pulp subsequent to the digestion step. However, the present invention is useful in treating pulps which, subsequent to digestion, have undergone substantially any of the commonly employed treatments of pulp such as an acid hydrolysis for removal of hexauronic acid, oxidation/bleaching employing oxygen and/or peroxide, or ozone, on the pulp and/or mechanical treatment of the pulp, ie., refining. In the most commonly contemplated process, the pulp or mixture of pulps, to be subjected to the method of the present invention will be a pulp(s) which has been digested and at least washed to remove black liquor.
[0033] In accordance with one aspect of the present invention, the pulp solution, at a temperature of between about 40 and 120 degrees C., is subjected to a solution of a transitional metal-activated peroxide for between about 10 and 600 minutes. In general, a higher treatment temperature will require less residence time, and vice versa. It is preferable that the treatment be done at 70-79 degrees C., with a residence time between 30-180 minutes. The treatment (either continuous or batch) can be carried out in a bleach tower, high-density tower, re-pulper tanks, or any suitable vessel with sufficient mixing and residence time.
[0034] In a preferred embodiment, and contrary to the conventional peroxide treatment of pulp wherein transitional metal ions are avoided or eliminated to avoid pulp damage or degradation by hydroxyl radicals, the treatment solution of the present invention, includes between about 0.2% and about 5% by wt. hydrogen peroxide and between about 0.002% and about 0.1% of a transitional metal ions, based on pulp. Iron (III) salts such as ferric chloride, or iron (II) salts such as ferrous sulfate and ferrous chloride, are especially useful as a source of the metal ions. Other metal ions, such as copper (II), cobalt (II) may be employed. In any event, as noted, only a trace of the transitional metal ions is required to achieve the advantageous results of the present invention, preferably between about 0.002% and about 0.01% of the metal ion.
[0035] Further contrary to conventional peroxide treatment of pulp wherein the peroxide treatment is carried out with the pulp at a very high pH for bleaching, in the present invention, the pulp treatment is carried out at a pH of between about 1 and about 9, preferably a pH between about 2 and 7.
[0036] Subjection of softwood pulp to the solution of the present invention at a temperature between about 40 C and about 120 C and at a pH between about 1 and about 9, has been found to cause oxidation and oxidative pulp degradation of the long, stiff and coarse kraft fibers. This chemical treatment of the fibers is followed by a mechanical treatment of the treated pulp, e.g., refining employing a conventional disc refiner, to cause fiber morphology change and paper property enhancement with respect to hardwood pulps. It will be understood by one skilled in the art that other mechanical treatment devices which provide equivalent refining of the pulp fibers may be employed.
[0037] Bleached southern pine Kraft pulp from International Paper-Augusta mill was treated at pH 4 with 1% hydrogen peroxide as based on pulp, with 0.01% Fe added as with ferric chloride. The treatment was conducted at the temperature of 80° C. for 1 hour. Both the treated and the control (untreated) pine pulps were refined with a PFI refiner. The data on PFI freeness and average fiber length are shown in Table I
TABLE I PFI Revolutions 0 Rev. 2000 Revs. 4000 Revs. 6000 Revs Control Freeness 739 CSF 675 CSF 522 CSF 481 CSF Southern Average Fiber 2.50 mm 2.47 mm 2.47 mm 2.42 mm Pine Length, L(L) Treated Freeness 746 CSF 524 CSF 364 CSF — Southern Average Fiber 2.37 mm 1.84 mm 1.64 mm — Pine Length, L(L)
[0038] As shown in FIG. 1 , the results of refining revolution (indication of refining energy) vs. freeness development show that iron catalyzed hydrogen peroxide treatment of pulp enhances pulp refining considerably, resulting in substantial energy savings for reading the same freeness level.
[0039] FIG. 2 shows the fiber length reduction (length-weighted average) by refining and indicates that, with catalyzed hydrogen peroxide treatment before refining, the fiber length is substantially reduced after being subsequently refined. While for comparison, the untreated pulp (control) showed little fiber length reduction by PFI refining.
[0040] FIG. 3 further illustrates the fiber length reduction as shown in FIG. 2 . In FIG. 3 , there is demonstrated the fiber length distribution curves, with the treated vs. the untreated (control) southern pine, at the same refining. As seen, the treatment caused a significant shift of fiber length to shorter range than the control.
EXAMPLE 2
[0041] Bleached southern pine as employed in Example 1 was treated with 1% hydrogen peroxide based on pulp at pH 4, with 0.006% FE (II) as from ferrous sulfate. The treatment was carried out at the temperature of 70° C. for 1 hour. The treated pulp and control were PFI refined as in Example 1. TAPPI hand sheets were then made from these pulps.
[0042] To illustrate fiber morphology (beyond fiber length distributions) and fiber collapsibility, SEM (scanning electron microscopy) images were made of the hand sheet surface of treated vs. the control (untreated) softwood pulps, compared at 4000 Revs of PFI refining. These microphotographs are depicted in FIGS. 4 (untreated) (control) and 5 (treated) and demonstrate that the treated pine fibers are much more collapsed, or flattened, as compared to the fiber of the control. The collapsed and flattened fibers are desirable for making paper or paperboard with superior surface and printing properties. Some broken or cut fibers (fiber ends) can also be seen from the SEM of treated hand sheet, indicating fiber shortening.
EXAMPLE 3
[0043] Bleached southern pine pulp was treated with 1% hydrogen peroxide catalyzed by 0.006% Fe(II) at pH 4 as in the Example 2 above. The treated pulps were PFI refined, and made into hand sheets for paper physical property evaluations. Results are shown in Table II.
TABLE II Basis Tear Extensional Weight, Bulk, Sheffield Factor Stiffness, g/m2 cc/g Smoothness 100*gf/g/m2 lbs/in. Treated Pine Pulp 730 CSF 151.9 1.90 375.6 190.9 2960 (Unrefined) 556 CSF 155.2 1.34 165.3 111.9 4780 421 CSF 154.4 1.36 127.2 103.4 5050 304 CSF 155.2 1.26 129.7 98.1 5210 Control Pine Pulp 740 CSF 162.4 1.91 380 270.9 3490 (Unrefined) 661 CSF 155.6 1.40 249.6 193.6 4020 625 CSF 159.9 1.35 185.3 188.7 4340 569 CSF 158.5 1.31 191.6 167.4 4540 443 CSF 155.9 1.27 157.8 170.2 4340 Bleached Hardwood Pulp 615 CSF 166 1.88 333 52.3 2040 584 CSF 163.1 1.64 268.6 87.9 2520 544 CSF 164.9 1.53 224.4 100 2840 507 CSF 161.0 1.40 175.2 112.6 3030 462 CSF 160.5 1.36 142.2 126.9 3010 427 CSF 162.8 1.31 127.8 107.8 3480 362 CSF 163.9 1.273 89 123.6 3320
[0044] From this table, it is noted that the treated pine, after refined to ˜560 CSF or lower freeness (to shorten the fibers also), show improved bulk-smoothness. This is also shown in FIG. 6 . FIG. 7 depicts the bulk at given freeness, which suggests the advantage of refining the treated pine to lower freeness, such as 400 CSF (depending on drainage or furnish mix requirements on paper machines).
[0045] In terms of mechanical properties, the treatment impacted significantly the Tear strength, reducing it to the level of hardwood ( FIG. 8 ). This is acceptable when using the treated pine fibers to replace hardwood fibers in a paper furnish. The reduction in Tear results from significant fiber length reduction, and the effect of chemistry.
[0046] Other mechanical properties were only slightly affected, and remain substantially higher than hardwood furnish. Interestingly, as shown in Table II, the elastic stiffness of treated pine can even be higher than that of the control pine.
EXAMPLE 4
[0047] The treated pine as in Example 3 above, refined to 560 CSF, was also mixed with hardwood pulp of a range of freeness, to investigate the mixed furnish paper properties such as bulk and smoothness. The results are listed in Table III.
TABLE III Sheffield Smoothness Bulk, cc/g 10% Treated Pine (560 CSF) + 323 1.83 90% Hardwood 308 1.83 171.2 1.37 137.8 1.33 20% Treated Pine (560 CSF) + 302 1.75 80% Hardwood 231.8 1.5 182.8 1.43 136.6 1.32 50% Treated Pine (560 CSF) + 318 1.79 50% Hardwood 182.4 1.41 163.4 1.38 147.6 1.29
[0048] FIG. 9 plots the bulk-smoothness curve of the mixed pulp furnish (data from Table III), along with 100% pine and hardwood curves (data from Table II). It is obvious that the treated pine can be used to replace substantial amounts of hardwood pulp. The exact amount of hardwood replacement in the paper mill, however, may also be affected somewhat by the nature, type and optimization of commercial refiners.
EXAMPLE 5
[0049] A Voith LR1 Disc Refiner was used to refine bleached southern pine which had been treated with 1% hydrogen peroxide, as catalyzed by Fe(III) at pH4. The refiner specific edge load was set at 0.8 Ws/m. As seen from Table IV, FIG. 10 , energy saving and fiber length reduction were confirmed.
TABLE IV Refining Treated Southern Pine Control Southern Pine Energy, Kajaani average Kajaani average kW · h/ fiber length, fiber length, ton pulp Freeness L(L) Freeness L(L) 0 750 CSF 2.07 mm 750 CSF 2.11 mm 46 677 CSF 2.05 mm 722 CSF 2.12 mm 78 610 CSF 1.98 mm 677 CSF 2.12 mm 118 455 CSF 1.84 mm 633 CSF 2.14 mm 158 317 CSF 1.66 mm 579 CSF 2.09 mm 198 197 CSF 1.48 mm 538 CSF 2.10 mm
EXAMPLE 6
[0050] A Voith LR1 Disc Refiner was used to refine bleached southern pine, which had been treated with 1% hydrogen peroxide, as catalyzed by Fe(II) at pH4. The refiner specific edge load was set at 4 km.
[0051] From Table V, FIGS. 11, 12 , it is seen that energy saving and fiber length reduction were confirmed.
TABLE V Treated Southern Pine RefiningEnergy, 25 46 99 119 — kW · h/ton Freeness 590 CSF 442 CSF 185 CSF 115 CSF — Kajaani average 1.9 mm 1.72 mm 1.4 mm 1.2 mm — length L(L) Untreated Pine - Control Refining Energy, 0 29 40 75 90 KW · h/ton Freeness 730 CSF 671 CSF 657 CSF — 522 CSF Kajaani average 2.14 mm — — 2.12 1.93 length L(L)
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A method for alteration of the morphology of cellulose fibers, particularly softwood fibers, by (a) subjecting the fibers to a metal ion-activated peroxide treatment carried out at a pH of between about 1 and about 9, preferably between 3 and 7, and (b) subjecting the treated fibers to a refining treatment thereby converts SW fibers to HW-like fibers in many respects. The metal ion-activated peroxide treatment has been noted to act on pulp cellulose and hemi-cellulose, causing oxidation and oxidative degradation of cellulose fibers. The chemical treatment of the pulp, taken alone, is not sufficient to attain the desired modification of the morphology of the fibers, however, subsequent refining or like mechanical treatment of the chemically-treated fibers to achieve a given degree of refinement of the fibers requires dramatically less refining energy to achieve a desired end point of refinement and to impart other desirable properties to the pulp. A pulp of modified SW fibers and a mixture of HW fibers and modified HW fibers are disclosed.
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CROSS REFERENCES TO A RELATED PATENT APPLICATION
This application is a continuation in part of my copending application, Ser. No. 788,588, filed on Apr. 18, 1977, for WATER SAMPLE COLLECTING DEVICE now U.S. Pat. No. 4,09l,676 which in turn is a continuation in part of my copending application Ser. No. 691,905, filed on June 1, 1976, for WATER SAMPLER DEVICE and issued as U.S. Pat. No. 4,037,477, on July 26, 1977.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to rotatable valve structures but is more particularly directed to a floating valve assembly for ball valves responsive to variations in pressures of fluids being controlled by the valve assembly.
2. Description of the Prior Art
All rotatable valve assemblies utilizing ball or spherical surfaced valves consist of a pair of valve seats engaging the valve on opposite sides thereof with seals interposed between the valve and valve seats. The amount of pressure or force being imposed at the seals by the valve seats against the ball valve determines the effectiveness of the seal against leakage. However, the greater this pressure is, the more difficult it will be to actuate or rotate the valve from one position to the other.
The conventional rotatable valve devices provide valve seats that are fixed in relation to the ball valve. Consequently, in order to prevent the possibility of leakage of fluids past rotatable valves when in a closed position, the valve seats are secured tightly against the valve. In so doing, the ball valve becomes difficult to rotate to its various positions especially if the valve is manually actuated. Therefore, it is important that the valve seats be tightened against the valve only to the degree that the seals therebetween prevent any leakage when the valve is in a closed position. In addition if there is an increase in fluid pressure after the valve seats had been adjusted for a lesser pressure, a leakage would possibly occur. Other conditions that may cause rotatable valves to leak occur after a considerable passage of time or use of the valve when the seals become worn, misshapen or lose their resiliency so that the valve seats are no longer sufficiently tightened against the valve to render the seals effective to prevent leakage therealong. By the use of a floating valve seat, the present invention contemplates avoiding the above objections to the conventional fixed valve seals for ball valves.
SUMMARY OF THE INVENTION
Therefore, a principal object of the present invention is to provide a rotatable valve assembly for fluids under pressure having a ball valve secured in position by a fixed valve seat on one side and a floating valve seat on the other side which is responsive to the fluid under pressure.
Another object of the present invention is to provide a rotatable valve assembly for fluids under pressure having a ball valve secured in position by valve seats engaging the ball valve with a force that varies with variation of the fluids under pressure whereby the force exerted by the valve seats is no greater than that required to render the valve leaktight.
A further object of the present invention is to provide a rotatable valve assembly having a ball valve secured in position by valve seats on either side thereof with seals interposed between the ball valve and the seats whereby the seals remain effective after passage of considerable time and use.
With these and other objects in view, the invention will be best understood from a consideration of the following detailed description taken in connection with the accompanying drawings forming a part of this specification, with the understanding, however, that the invention is not confined to any strict conformity with the showing of the drawings but may be changed or modified so long as such changes or modifications mark no material departure from the salient features of the invention as expressed in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a perspective view of a water sampler having a rotatable valve assembly constructed in accordance with my invention.
FIG. 2 is a fragmentary longitudinal cross sectional view taken along the line 2--2 of FIG. 1 showing the ball valve in an open position.
FIG. 3 is a similar view with the ball valve rotated to its closed position.
FIG. 4 is an exploded view of either end of the water sampler showing the valve assembly.
FIG. 5 is a perspective view of an alternate construction of the flexible diaphragm.
FIG. 6 is a fragmentary view of the tubular housing.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings wherein like numerals are used to designate similar parts throughout the several views the numeral 10 refers to my water sampler consisting of a tubular member 11 at each end of which there is a chamber 13 mounting a spherical or ball valve assembly A, the subject matter of the present application.
Each of the ball valve assemblies A is identical in construction and operation so that a detailed description of either ball valve assembly applies to the other. Within the valve chambers 13 are identical ball or spherical valves 14 rotatably mounted therein. Each of the valve chambers 13 is provided with a peripheral groove 12 forming a ledge or shoulder 15 by reason of the wall thickness of the tubular member 11 being thinner at the valve chamber 13 than that portion of the tubular member 11 extending between the valve chambers 13. The ledge 15 supports a floating valve seat 16 at its periphery 17 with a flexible diaphragm 18 interposed between the shoulder 17 and the ledge 15. The flexible diaphragm 18 is locked in position in the slot 12 by means of an O-ring 19 positioned in the peripheral slot 12 and wedged between the periphery of the flexible diaphragm 18 and the upper surface 120 of the slot 12. The O-ring 19 also acts as a seal to prevent the leakage of fluid at the periphery of the valve seat 16. The ball valve 14 is provided with an axially disposed opening 20 forming a fluid passageway while the valve seat 16 and flexible diaphragm 18 have openings 21 and 22 respectively in alignment with the opening 20 whereby fluid may flow into and out of the sampler 10 when the valve 14 is in an open position, as shown by FIG. 2. The ball valve 14 engages an O-ring 23 mounted on a slot 24 formed on the valve seat 16 to form a seal between the ball valve 14 and the valve seat 16 and thereby prevent the leakage of fluid therealong when the valve 14 is in a closed position.
A fixed ring-shaped valve seat 25 is mounted at each of the free ends of the tubular member 11 engaging the ball valves 14 to maintain the ball valves 14 in a firm but rotatable condition within the chambers 13. The outer valve seats 25 are each provided with a centrally disposed opening 26 and an inner peripheral groove 27 adjacent the opening 26 for receiving a hollow O-ring 28 that engages the ball valve 14, for sealing same. The outer valve seat 25 are non-movable being secured to the bottle 11 by peripheral matching grooves 29 and 30 formed on the inner surface of the bottle 11 and outer surface of the outer valve seat 22 respectively with a pliable locking rod 31 received therein, as shown and described in detail in my U.S. Pat. No. 3,986,635, for Closure Locking And Orienting Device. Bores 32 formed in the wall of the bottle 11 in alignment with the grooves 29 and 30 permit the threading of the pliable rod 31 into position in the matching grooves 29 and 30 to secure the valve seat 25 against movement. Openings 3 formed in the side walls of the bottle 11 prevent water from being trapped in the valve chamber 13 when the valves 14 are in an open position.
The ball valve 14 is provided with a slot 34 on its outer surface for receiving a plug 35 mounted on the end of a stub shaft 36. The latter extends through an opening in the tubular member 11, in alignment with a bore 35 in a collar 38 mounted on the tubular member 11. A pulley 39 is rotatably mounted on the stub shaft 38 and provided with a radially disposed bore 40 for receiving a pin 41 which extends into an 180° peripheral groove 42 formed on the periphery of the collar 38. The pin 41 is secured to an elongated elastic member 43 on one side and a lanyard 44 on the other side thereof. The elastic member 43 extends between the pulleys 39 as shown by FIG. 1 while the lanyards 44 extend to a release device R whose function is explained in detail in my aforesaid copening application and form no part of this invention.
In the normal use of my water sampler bottle 10 after the container 11 has reached the depth in a body of water at which a sample of water is to be contained within the container 10, the valves 14 are rotated to their closed positions as shown by FIG. 3 and described in detail in my copending application. The O-ring 19 forms a fluid tight juncture between the floating valve seat 16 and the inner surface of the tubular member 11 as well as securing the flexible diaphragm 18 against its outer periphery from slipping out of the groove 17. The O-rings 23 and 28 prevent any leakage of fluid between the ball valve 14 and valve seats 16 and 25. As the water sampler 10 filled with the desired sample of water is brought up to the surface of the body of water, the pressure of water within the bottle 11 will be greater than that in the surrounding body of water. Consequently, the flexible diaphragm 18 and the seat 16 will slide in the direction of the fixed valve seat 25 causing the O-ring 23 to bear more tightly against the ball valve 14 which in turn causes the hollow O-ring 28 to become more tightly compressed against the ball valve 14 so that the probability of leakages at the O-rings 23 and 28 is greatly reduced and the valve seats 16 and 25 are tightened against the ball valve 14 at no greater pressure than that required by the increased pressure of fluid within the container 11 since the floating valve seat 16 moves in response to the fluid pressure within the container 11. On the other hand, if the floating valve seat were fixed and not floating as described herein, it is obvious leakages along the seals 23 and 28 may occur upon the increase of fluid pressure thereon. To avoid possibility of leakage in this instance of increase fluid pressure, the valve seats 16 and 25 would have to be tightened against ball valve 14 in the conventional ball valve devices at a maximum pressure that would insure no leakage at the time the pressures within and without the bottle 10 are at their highest differential. Operation of the ball valve 14 now becomes difficult. In fact, if the ball valve is too tightly held between the fixed valve seats, the valve may become stuck and not be capable of rotating to its closed position.
The floating valve 16 permits the ready and easy actuation of the valve 14 when there is no necessity for the seals 23 and 27 to be tightly compressed against the ball valve 14 until there is a higher pressure of water within the bottle 11 than outside of the bottle. Then after the valve 14 is actuated to its closed position, in response to the higher internal fluid pressure the floating valve seat 14 will then slide outwardly against the ball valve 14 to more tightly compress the seals 23 and 28 against the valve seats 16 and 25 and render them more effectively leakproof.
In my copending application wherein a floating valve seat is provided, the O-ring is positioned between the floating valve seat and the tubular member. It has been found that after a passage of time, this O-ring which must be capable of rolling as the floating valve seat moves toward and away from the ball valve, loses its ability to roll as it either becomes fused to the container or loses its flexibility, and thereby becomes non-circular in cross section. The comparable O-ring 19 of the present invention remains secured in the slot 12 at all times to seal against leakage as well as secure the preiphery of the flexible diaphragm 18 in the slot 12 to permit the flexible diaphragm 18 to move with the floating valve seat 16.
In the alternate construction of my flexible diaphragm 50 shown in FIG. 5, the flexible diaphragm 50 is provided with an O-ring 51 at its periphery molded as a single unit, otherwise the latter is identical in construction and function as the previously described flexible diaphragm 18 and O-ring 19.
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A rotatable valve assembly for controlling the flow of fluids under pressure having a ball valve, a valve seat engaging the valve on opposite sides thereof, one of the valve seats being fixed and the other being movable; with fluid tight seals mounted on the valve seats and engaging the ball valve, the movable valve seat being responsive to the fluid under pressure whereby variation of fluid pressures will compel the movement of the ball valve toward and away from the fixed valve seat to provide a fluid tight seal therealong.
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This is a division of application Ser. No. 923,549 filed Oct. 27, 1986 and now U.S. Pat. No. 4,729,976.
FIELD OF THE INVENTION
The invention is a process for the bulk polymerization of dicyclopentadiene, the dicyclopentadiene polymer prepared by this process and the catalyst used in the process.
BACKGROUND OF THE INVENTION
It is known from U.S. Pat. No. 3,627,739 to polymerize dicyclopentadiene (abbreviated DCPD) to polydicyclopentadiene (poly DCPD) with the aid of a tungsten catalyst. The obtained poly DCPD is rather brittle and has a low Izod impact strength. Efforts have been made to improve this product and European Patent Application No. 84,888 discloses a method to prepare poly DCPD with improved properties. Application 84,888 also discloses a process for the polymerization in bulk of DCPD with the aid of a metathesis catalyst system, comprising e.g. phenol substituted tungsten hexachloride together with an activator, e.g. ethyl aluminum dichloride, and diethyl aluminum chloride or tetrabutyl tin. The application further discloses that the DCPD used should be purified in order to prevent impurities from inhibiting the polymerization. It is stressed that it is often desirable to purify the starting materials even further by treatment with silica.
Applicant has now found a versatile metathesis catalyst system for the polymerization of DCPD in bulk, which is more stable, less sensitive to oxygen and moreover can polymerize DCPD of impure quality.
SUMMARY OF THE INVENTION
The invention is a process for preparing a polymer which comprises contacting dicyclopentadiene with a catalyst comprising (a) a tungsten compound having the formula ##STR1## wherein R 2 is an alkyl group having at least 3 carbon atoms and R 3 is selected from the group consisting of an hydrogen atom and a bulky alkyl group having at least 3 carbon atoms, R 1 is selected from the group consisting of an hydrogen atom and an alkyl group of 1 to 10 carbon atoms, (m+n) is equal to 6 and n is 1 or 2, and
(b) a tin compound having the formula ##STR2## wherein r 4 is selected from the group consisting of a phenyl group, and an alkyl group having 1 to 10 carbon atoms, under conditions effective to prepare a polymer of dicyclopentadiene and recovering said polymer. The invention is also said polymer of dicyclopentadiene as prepared in the process of the invention and the invention is a catalyst used in the process of the invention to prepare said polymer.
DETAILED DESCRIPTION OF THE INVENTION
It has been found that the tin compound of the present invention process, in contrast with aluminum compounds used in other processes, are much less sensitive to oxygen, and consequently nitrogen atmospheres do not need to be used in the process according to the invention.
It has also been found that the use of tetrabutyl tin, together with the above-defined tungsten compound did not polymerize DCPD. Tetramethyl tin and tetraethyl tin did not work either, when used together with bis(2,6-diisopropylphenoxy) tungsten tetrachloride.
The above-mentioned European Patent Application No. 84,888 discloses that an unmodified tungsten compound, such as phenol substituted tungsten hexachloride, will rapidly polymerize DCPD. To prevent premature polymerization of the tungsten compound/DCPD solution a Lewis base or a chelating agent can be added. The use of WCl 6 , often mentioned in the general prior art as one of the components of a metathesis catalyst, is not desirable in the process according to the present invention.
The tungsten compounds used as catalyst component in the process according to the invention contain in the phenyl nucleus a bulky alkyl group, preferably an isopropyl group, a tertiarybutyl group or a neo-pentyl group.
Suitable tungsten compounds may be represented by the following chemical formulas ##STR3## wherein R is isopropyl, and ##STR4## wherein R' is tert-butyl
The tungsten compounds may be prepared by reacting tungsten hexachloride with an appropriate amount of 2,6-diisopropyl phenol and 2,4-di-tert-butyl-4-methylphenol respectively.
Of the trialkyl tin hydrides, suitable for use in the process of the invention, those in which the alkyl group contains 1 to 6 carbon atoms are preferred, the tributyl tin hydride being most preferred. Triphenyl tin hydride may also be used.
As stated already hereinbefore the DCPD may be of an impure grade, such as commercially available endo-DCPD. A technical grade of DCPD contains about 5 to 6 percent by weight of codimers.
The amount of the tungsten compound catalyst component used in the process according to the invention may range from 0.01 to 1 mol %, preferably from 0.02 to 0.1 mol%, calculated on the amount of DCPD.
The mol ratio of the tin compound versus the tungsten compound ranges from 15:1 to 1:1, preferably from 12:1 to 3:1.
It is observed, that anti-oxidants (such as Ionol), moisture and oxygen do not disturb the polymerization.
Generally the polymerization takes place in bulk, but the catalyst components, viz. the above-defined tungsten compound and the tin compound, may be dissolved in a small amount of solvent, such as toluene. It is preferred however, to use, DCPD as a solvent. In case of the tin compound no solvent at all may also suffice, since the tin compound is a liquid.
A preferred method of the polymerization of DCPD is to contact a tungsten compound catalyst component stream with a tin compound catalyst component stream whereby at least one of the streams contains the DCPD, and to polymerize the DCPD. For example it is possible to dissolve the tungsten catalyst in DCPD and either to dissolve the tin catalyst in DCPD or in another solvent or to use the tin catalyst without any solvent.
After both streams have contacted with each other, the resulting mixture may be injected or poured into a mold, where the polymerization takes place. The polymerization is exothermic, but heating the mold from about 50 to 100° C. is preferred.
The tin catalyst as well-as the tungsten catalyst may be stored in DCPD for some time, provided that the DCPD contains only a few ppms of water or less. The tin catalyst is storable in DCPD during one or two months without loosing its activity. Even the tungsten catalyst and the catalyst prepared in Example 2 hereinafter admixed with each other in dry DCPD under nitrogen may be stored for one day, without losing activity.
The properties of the poly DCPD, obtained by the process according to the invention are:
______________________________________Hardness shore D 65-80Compressive strength MPa 30-50Compressive modulus GPa 0.8-1.2Vicat soft. temp. °C. 165-170(1 kg load)Izod impact strength kJ/m.sup.2 6.0-9.5(British Standard notched)Flexural strength MPa 70-75Glass transition temp. °C. 95Flexural modulus GPa 1.7-1.8______________________________________
During the polymerization of DCPD, fillers, anti-oxidants, stabilizers, pigments, plasticizers may be present in the reaction mixture.
The catalyst system used is specifically of interest for reaction injection molding or casting. Because of the low viscosity of the DCPD/catalyst system, the polymerization is very suitable for large castings with intricate molds.
Polymerization temperatures of up to 200° C. are reached in exothermic reactions.
The poly DCPD obtained by the process according to the invention may be subjected to a heat-treatment of 200° C. to 300° C. for about 1 hour or longer. After this heat-treatment the glass transition temperature of the polymer has been increased to about 160° C.
This post-curing treatment may be beneficial to certain uses of the poly DCPD.
The invention further relates to a two components catalyst system, comprising
(a) a tungsten compound of the formula ##STR5##
wherein R 2 is a bulky alkyl group having at least 3 carbon atoms and R 3 is selected from the group consisting of a hydrogen atom and a bulky alkyl group having at least 3 carbon atoms, and n is 1 or 2,
(b) a tin compound of the formula ##STR6##
wherein r 4 is selected from the group consisting of a phenyl group, and an alkyl group having 1 to 10 carbon atoms.
The two component catalyst system may form part of a package wherein at least one of the components is dissolved in dicyclopentadiene.
It is possible to manufacture drums containing DCPD together with a pre-determined amount of one of the components, e.g. the tungsten catalyst and drums containing DCPD with the tin catalyst in an amount adapted to the desired mol ratio of components to be used in the polymerization of DCPD.
The invention will be illustrated with the following examples. The examples are given for the purpose of illustration only and the invention is not to be regarded as limited to any of the specific materials or conditions used in the examples.
EXAMPLE 1
CATALYST PREPARATION
2 g of WCl 6 was weighed in a 100 ml dried serum cap bottle and dissolved in 40 ml of dried toluene under a dry nitrogen blanket. 1.73 ml of dried 2,6-diisopropylphenol was added slowly at 100° C. The evolved HC1 was collected in an excess of aqueous sodium hydroxide solution. The reaction mixture was kept for 4 h at 100° C. The catalyst was isolated by evaporation of the solvent. Analysis showed that two chlorine atoms of the tungsten hexachloride were replaced by the bulky phenoxy groups.
product: Bis(2,6-isopropylphenoxy) tungsten tetrachloride=catalyst 1.
EXAMPLE 2
CATALYST PREPARATION
4 g of WCl 6 was weighed in a 10 ml dried serum cap bottle and dissolved in 20 ml of dried toluene under a dry nitrogen blanket. A solution of 6.6 g dried 2,6-di-tert-butyl-4-methylphenol (Ionol) in 20 ml of dried toluene was added slowly at 90° C. The evolved HC1 was collected in an excess of aqueous sodium hydroxide solution. The reaction mixture was kept for 4 h at 95° C. The catalyst was isolated by evaporation of the solvent.
Analysis showed that one chlorine atom of the tungsten hexachloride was replaced by the bulky phenoxy group.
Product: 2, 6-di-tert-butyl-4-methylphenoxy tungsten pentachloride=catalyst 2.
In the polymerization experiments a technical grade of DCPD was used, which contained:
3.5% isopropenyl-2-norbornene
1.1% 5-cis and trans-1-propenyl-2-norbornene
0.7% 5-methyltetrahydroindene
70 ppm water
If dry DCPD was used, it contained less than 1 ppm of water.
Example 3
0.08 g of catalyst 1 was dissolved in 40 g of DCPD in a 100 ml serum cap bottle. 3 ml of a 0.2 mol/1 solution of tributyl tin hydride in toluene was added at ambient temperature by means of a hypodermic syringe. The bottle was shaken thoroughly and placed in an oil-bath of 90° C. The reactive mix gelled very rapidly and an exothermic polymerization was observed. A maximum temperature of 200° C. after 4,5 minutes from initiation was observed.
EXAMPLE 4
0.09 g of catalyst 1 was dissolved in 40 g of DCPD in a 100 ml serum cap bottle. 2.5 ml of a 0.3 mol/1 solution of triphenyl tin hydride in toluene was added at ambient temperature by means of a hypodermic syringe. The bottle was shaken thoroughly and placed in an oil-bath of 90° C. An exothermic polymerization was observed for which a maximum temperature of 160° C. after 4,5 minutes from initiation was recorded.
EXAMPLE 5
0.07 g of catalyst 2 was dissolved in 40 g of DCPD in a 100 ml serum cap bottle. 2.5 ml of a 0.25 mol/1 tributyl tin hydride solution in toluene was added at ambient temperature by means of a hypodermic syringe. The bottle was shaken thoroughly and placed in an oil-bath of 90° C. An exothermic polymerization was observed for which a maximum temperature of 150° C. after 11 minutes from initiation was recorded.
EXAMPLE 6
COMPARATIVE EXPERIMENT
0.08 g of catalyst 1 was dissolved in 40 g of DCPD in a 100 ml serum cap bottle. 2 ml of a 0.3 mol/1 tetramethyl tin solution in toluene was added at ambient temperature by means of a hypodermic syringe. The bottle was shaken thoroughly and placed in an oil-bath of 90° C. No polymerization at all was observed.
EXAMPLE 7
0.08 g of catalyst 1 together with 0.08 g of Ionol were dissolved in 40 g dried DCPD and stored at room temperature. After six days 2 ml of a 0.3 mol/1 solution of tributyl tin hydride in toluene was added. The bottle was shaken thoroughly and placed in an oil-bath of 90° C. An exothermic polymerization was observed for which a maximum temperature of 195° C. after 3 minutes from initiation was recorded.
EXAMPLE 8
0.07 g of catalyst 2 was dissolved in 40 g of dried DCPD and stored at room temperature. After 7 days 2 ml of a 0.3 mol/1 solution of tributyl tin hydride in toluene was added. The bottle was shaken thoroughly and placed in an oil-bath of 90° C. An exothermic polymerization was observed with a T max of 200° C. after 14 minutes from initiation.
EXAMPLE 9
0.022 g of tributyl tin hydride was dissolved in 10 g of dried DCPD and stored at room temperature. After 31 days this solution was added to a freshly prepared solution of 0.02 g of catalyst 1 in 10 ml of dried CDPD. The reactive mix was homogenized and heated in an oil-bath of 90° C. An exothermic polymerization was observed with a T max of 170° C.
EXAMPLE 10
0.25 g of catalyst 2 was dissolved in 105 g of dried DCPD. 5.8 ml of a 0.3 mol/1 solution of tributyl tin hydride in toluene was added. The mixture was homogenized and stored in contact with the atmosphere. After 1 day 40 ml of the mixture, which was still a thin liquid, was heated till 90° C. in an oil-bath. An exothermic polymerization was still observed with a T max of 170° C.
EXAMPLE 11
0.5 g of catalyst 2 was dissolved in 350 g of technical DCPD in contact with the atmosphere. 1.4 ml of tributyl tin hydride was added whereafter the solution was thoroughly homogenized in contact with the atmosphere.
The reactive mix was poured in a preheated (110° C.) aluminum mold of 35×10×1 cm. The mold was kept at 110° C. for 45 minutes whereafter the temperature was raised to 200° C. at which temperature the mold was kept for another 45 minutes. After cooling a polymer sheet was extracted from the mold which was free from any DCPD odor.
EXAMPLE 12
COMPARATIVE EXPERIMENT
0.086 g of catalyst 2 was dissolved in 20 g dry DCPD in a 100 ml serum cap bottle. 0.257 g tetrabutyl tin in 20 g dry DCPD was added at room temperature by means of a hypodermic syringe. The bottle was shaken thoroughly and placed in an oil-bath of 90° C. No polymerization at all was observed.
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The invention is a process for preparing a polymer which comprises contacting dicyclopentadiene with a catalyst comprising a phenolic substituted tungsten halide and a trialkyltin hydride or triphenyltin hydride and recovering said polymer. The invention is also a polymer of dicyclopentadiene as prepared in the process of the invention and a catalyst used in the process of the invention to prepare said polymer.
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TECHNICAL FIELD
[0001] This invention relates to a cylinder block assembly for an engine having an increased lubricant capacity and in particular to a cylinder block assembly in which the volume and flow rate of lubricant within the engine is controlled. The invention also relates to a method of lubricating an engine.
BACKGROUND
[0002] During operation of an engine, a lubricant such as engine oil is pumped from a sump into the working portions of an engine in order to lubricate, clean and cool the engine's moving parts. Excess oil supplied to the moving parts is drained back to the sump along various paths defined in the engine cylinder block and cylinder head.
[0003] A large volume of lubricating oil is desirable in an engine. For example, where the volume of engine oil is increased, service intervals can be increased thereby minimizing maintenance costs. However, the volume of oil that can be employed in an engine is limited by engine size as, in general, it is desirable to maintain engine size at a minimum while large volumes of oil require large storage reservoirs in an engine.
[0004] UK Patent specification No 100,345 describes a lubricating system for a car engine comprising a circulating oil tank located beneath a cylinder block of the engine, and a fresh oil tank formed in the side of the block. Filling of the fresh oil tank results in overflow oil passing through a weir to the circulating oil tank. The system includes a first pump to pump oil from the circulating oil tank to the oil circulation system and a second pump which supplies oil from the fresh oil tank to the oil circulation system. While the fresh oil tank provides an extra volume of oil for the engine, the means for supplying the fresh oil to the circulation system necessitates the use of a pump in the supply line as the disposition of the line is such that oil will not flow to the circulating system when the line is open. Moreover, in order for fresh oil to be supplied to the oil circulation system, both pumps need to operate at the same time. These shortcomings result in a lubricating system which is more expensive to manufacture and operate. The present invention sets out to overcome one or more of the disadvantages of the prior art.
SUMMARY OF THE INVENTION
[0005] According to the invention there is provided a cylinder block assembly comprising a cylinder block, a primary lubricant reservoir below the cylinder block, a secondary lubricant reservoir at a side of the cylinder block, a fluid passage extending between the primary and secondary lubricant reservoirs, and a valve which can be actuated to open and close the fluid passage, wherein the fluid passage is adapted to permit gravitational flow of the lubricant from the secondary lubricant reservoir to the primary lubricant reservoir when open, wherein actuation of the valve is controlled by a level of lubricant in the primary lubricant reservoir.
[0006] The invention also extends to an engine having such a cylinder block assembly.
[0007] The invention also extends to a method for lubricating an engine comprising the steps of:
[0008] pumping lubricant around the engine from the primary lubricant reservoir;
[0009] collecting a proportion of returned lubricant in the secondary lubricant reservoir; and
[0010] controlling the return of lubricant from the secondary lubricant reservoir through the fluid passage to the primary lubricant reservoir by means of the valve.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Various embodiments of the invention will now be described, by way of example only, having regard to the accompanying diagrammatic drawings in which:
[0012] [0012]FIG. 1 a is a partial transverse cross section through a cylinder block assembly according to one embodiment of the invention, including a cylinder block provided with a secondary lubricant reservoir at a side wall thereof, the cylinder block also being provided with a primary lubricant reservoir and a cylinder head; and
[0013] [0013]FIG. 1 b is a partial transverse cross section through a cylinder block assembly according to another embodiment of the invention, including a cylinder block provided with a secondary lubricant reservoir at a side wall thereof in which the pannier oil tank is defined by the cylinder block and a cylinder block apron.
DETAILED DESCRIPTION
[0014] A cylinder block 1 is provided with at least one secondary lubricant reservoir which acts as an engine oil capacitor to increase engine lubricating oil capacity. In the present example, the secondary lubricant reservoir takes the form of a pannier oil tank 11 ; however the secondary lubricant reservoir can be of any construction that may be adapted by a skilled person in accordance with the present invention.
[0015] In FIG. 1 a , the pannier oil tank 11 is integrally formed in the cylinder block 1 while in FIG. 1 b the pannier oil tank 11 is defined between the cylinder block 1 and a cylinder block apron 2 . The illustrated embodiments are described in more detail below, but it is to be understood that the form and construction of the pannier oil tank may be varied in accordance with the present invention.
[0016] As shown in FIG. 1 a , the cylinder block 1 is a casting made up of a cylinder block body 4 and a cylinder block base 5 . Two cylinder block side walls 35 and two cylinder block end walls 36 upstand from the cylinder block base 5 (only one side wall 35 and end wall 36 is shown). The cylinder block 1 is provided with a primary oil reservoir in the form of a sump 37 attached to the cylinder block base 5 . The cylinder block 1 has a cylinder head 8 fitted with a cylinder head cover 9 .
[0017] The side walls 35 are shaped to define a crankcase housing 7 of a crankcase 6 adjacent the cylinder block base 5 . A crankshaft 10 is contained within the crankcase 6 .
[0018] The side wall 35 of the cylinder block 1 is formed to define the pannier oil tank 11 between a side wall outer wall 12 and a side wall inner wall 13 adjacent the cylinder block base 5 . The pannier oil tank 11 is further defined by a bottom wall 14 at the cylinder block base 5 . A bottom wall valve opening 15 in the bottom wall 14 provides a fluid passage 38 between the pannier oil tank 11 and the sump 37 . The pannier oil tank 11 is open at a top end 34 . The bottom wall 14 may be formed as a separate plate to facilitate core sand removal from the pannier oil tank 11 where the pannier oil tank 11 is cast integrally with the cylinder block 1 .
[0019] The pannier oil tank 11 is adapted to store lubricating oil 16 or other lubricant. The bottom wall valve opening 15 is openable and closeable by a float valve 17 located in the sump 37 . The float valve 17 is of substantially conventional construction and is provided with a valve head 18 moveable between an open position to allow drainage of oil 16 from the pannier oil tank 11 through the fluid passage 38 and into the sump 37 , and a closed position to allow filling of the pannier oil tank 11 in accordance with oil levels in the sump 37 . The bottom wall valve opening 15 is dimensioned to allow relatively brisk oil flow in the open position. As the lubricant level in the sump 37 increases, the valve 17 closes the aperture 15 when the level of the lubricant 16 reaches a predetermined level.
[0020] At its open top end 34 , the pannier oil tank 11 is adapted to receive lubricating oil 16 through a filler tube 19 defined in the side wall outer wall 12 . Whilst the float valve 17 is in the open position, oil received via the filler tube 19 will pass through the pannier oil tank 11 and through the valve opening 15 into the sump 37 . When the oil level in the sump 37 has reached a predetermined design level, the float valve 17 will close the valve opening 15 and the pannier oil tank 11 will commence to fill.
[0021] A conventional dipstick (not shown) or sight glass 40 is used in conjunction with the pannier oil tank 11 to determine when the design quantity of oil has been reached. It is envisaged that the maximum oil level of the engine will be at or just below the open top end 34 of the filler tube 19 .
[0022] When the engine is in operation, oil is received in the pannier oil tank 11 from a cylinder block duct 21 which extends between the cylinder head 8 and the pannier oil tank 11 via a cavity 20 . The cylinder block duct 21 is located in the cylinder block side wall 35 .
[0023] The apparatus may be configured such that the pannier oil tank 11 is the prime recipient of oil from the various oil return sources in an engine. Those sources may include, for example, a pressure relief valve 24 , shown in FIG. 1 b , that may be required to relieve oil pressure in the lubricating oil circuit of the engine, particularly at low engine speeds.
[0024] It may be found desirable to include, in an engine, more than one float valve 17 or even a series of float valves 17 , to cater for the variable engine inclinations that the engine may experience in use. The speed of oil drain from the pannier oil tank 11 into the sump 37 that may be required in use or in service may also influence the number and location of float valves 17 .
[0025] The side wall inner wall 13 is provided with an aperture 32 located at the top end 34 of the pannier oil tank 11 . The aperture 32 serves as an overflow for the pannier oil tank 11 so that oil can flow from the pannier oil tank 11 , through the aperture 32 , into the sump 37 when the capacity of the pannier oil tank 11 is exceeded.
[0026] [0026]FIG. 1 b shows an engine including a cylinder block 1 with a pannier oil tank 11 in accordance with a second embodiment of the invention. The cylinder block 1 of FIG. 1 b is broadly similar to the cylinder block 1 of FIG. 1 a . Accordingly, like numerals indicate like parts. However, in the present embodiment, the pannier oil tank 11 is defined by an apron 2 and the cylinder block side wall 35 . More particularly, the pannier oil tank 11 is defined between the crankcase housing 7 and the apron 2 .
[0027] The apron 2 is sealably adhered to the side wall 35 to define the pannier oil tank 11 . Briefly, the apron 2 is made up of an apron bottom portion 26 , an apron cylinder block portion 27 and an apron cylinder head portion 28 attachable to the cylinder head 8 . The apron 2 is formed from a metal sheet or other suitable material and is shaped and contoured to complement the side wall 35 of the cylinder block 1 . Advantage is thus taken of a natural cavity that exists in the necked region of a conventional crankcase to define, with apron 2 , a pannier oil tank 11 .
[0028] The apron 2 is folded at the bottom portion 26 to define an elongate box-like beam 30 for reinforcing the apron 2 and the cylinder block 1 to which the apron 2 is adhered. The beam 30 is secured to a cylinder block flange 31 defined at the cylinder block base 5 .
[0029] The apron 2 may be provided with cooling elements 33 on its outer surface in the region of the pannier oil tank 11 to facilitate cooling of oil 16 contained within the pannier oil tank 11 . The pannier oil tank 11 of FIG. 1 b is also provided with a bottom wall 14 . However, in the present embodiment, the bottom wall 14 is formed by the cylinder block base 5 .
[0030] Accordingly, the bottom wall valve opening 15 of the pannier oil tank 11 and the fluid passage 38 of FIG. 1 b are defined in the cylinder block base 5 . The bottom wall valve opening 15 is also openable and closeable by a float valve 17 in the sump 37 .
[0031] The pannier oil tank 11 of FIG. 1 b , like pannier oil tank 11 of FIG. 1 a is adapted to receive oil from a filler tube (not shown) and the cylinder block duct 21 in communication with the cylinder head 8 via the cavity 20 defined between the apron 2 and the cylinder block 1 . In the embodiments of both FIGS. 1 a and 1 b the cylinder block duct 21 is in communication with the interior of the cylinder head cover 9 via cylinder head ducts 29 provided in the cylinder head 8 itself. The pannier oil tank 11 can also receive oil from miscellaneous sources as described in relation to FIG. 1 a.
[0032] The aperture 32 in the crankcase housing 7 also functions to receive crankcase gases from the crankcase 6 .
[0033] Both embodiments of the invention are provided with a sump oil pick up 22 located in the sump 37 and an oil pump 23 , also housed in the sump 37 , for pumping oil from the sump 37 to the crankshaft 10 . Oil is directed to the crankshaft 10 by a crankshaft oil feed 25 in communication with the oil pump 23 while the pressure relief oil valve 24 is disposed between the pannier oil tank 11 and the crankshaft oil feed 25 . An oil spray (not shown) in communication with the oil pump 23 can also be provided to assist in piston cooling and lubrication of piston pins and rings and the cylinder block side and end walls 35 , 36 respectively.
[0034] The lubricating oil is filtered by an oil filter (not shown) to clean the oil and remove debris therefrom in conventional manner.
INDUSTRIAL APPLICABILITY
[0035] The pannier oil tanks 11 of FIGS. 1 a and 1 b operate in a similar manner and operation and use of the invention will now be described in relation to a typical six cylinder 6.0 liter engine having a pannier oil tank 11 on each cylinder block side wall 35 . However, it will be appreciated by those skilled in the art that the invention finds application in engines having different numbers of cylinders and different capacities while engines can be provided with one, two or more pannier oil tanks 11 as required.
[0036] Lubrication oil 16 from engine main and big end bearings and from piston cooling jets and the like is returned to the sump 37 in a substantially conventional manner.
[0037] Other oil flow from the cylinder head 8 , pressure relief valves 24 and engine components including turbo-chargers, camshafts, idler shaft bearings and the like may be returned first to the pannier oil tanks 11 via the cylinder block ducts 21 and the cylinder head ducts 29 .
[0038] In the 6.0 liter engine of the present example, the sump 37 is adapted to receive ten liters of oil while the pannier oil tanks 11 are dimensioned to receive six liters of oil before overflowing into the sump 37 through the aperture 32 . Maximum oil flow from the pannier oil tanks 11 via bottom wall valve openings 15 is restricted to six or less liters per minute.
[0039] The fluid passage 38 is disposed such that, when open, oil flows under the force of gravity from the pannier oil tank 11 to the sump 37 without the need for an additional pump.
[0040] The float valve 17 is set at a level such that the bottom wall valve opening 15 is open under least favorable operating conditions when oil levels in the sump 37 are at their lowest levels, due to the high volume of oil 16 in circulation in an engine. Accordingly, the float valve 17 is closed under most operating conditions.
[0041] As indicated above, the initial volume of oil is fed, prior to engine start-up, into the pannier oil tank 11 via the filler tube 19 . When the oil level in the pannier oil tank reaches the aperture 32 the additional fed oil overflows through the aperture into the sump 37 .
[0042] At engine start-up, the pannier oil tanks 11 are full under normal conditions. The float valves 17 are closed due to the high oil level in the sump 37 .
[0043] Accordingly, upon engine start up, oil levels in the sump 37 are lowered as oil is pumped around the engine components, enabling the float valve 17 to open to a limited extent.
[0044] At idle speed oil will circulate at a rate which returns 18 liters of oil per minute to the sump 37 and 6.5 liters of oil per minute to the pannier oil tanks 11 . If the float valves 17 are closed, and the pannier oil tanks are full, then the 6.5 liters of oil per minute returned to the pannier oil tanks will overflow through the aperture 32 and return to the sump 37 . However, under abnormal conditions where the float valves 17 are open, then assuming the float valves 17 are fully opened and sized to permit a flow of 6 liters of oil per minute, the pannier oil tanks 11 are filled approximately 12 minutes after start up, based on a net flow of 0.5 liters of oil per minute into the pannier oil tanks.
[0045] In practice, the float valves 17 are generally completely shut due to high oil levels 16 in the sump 37 so that the pannier oil tanks 11 fill at a faster rate.
[0046] At most engine operating regimes, flow rate of oil returned to the pannier oil tanks 11 greatly exceeds flow rate from the pannier oil tanks 11 . Flow rates are calibrated such that, at idle speeds, oil in circulation is insufficient to allow oil levels in the sump 37 to depress to the point where the valves 17 will open. As previously described, any overflow from the pannier oil tanks 11 through the apertures 32 simply enters circulation in the engine. At running speeds, oil levels in the sump 37 are further depressed due to the increased volume of oil in circulation whereby the float valves 17 may open. Opening of the float valves 17 in such a manner therefore results in a stabilization of oil levels in the pannier oil tanks 11 at a level proportionate to return flow of the oil 16 .
[0047] Oil within the pannier oil tanks 11 is also cooled in the embodiment described in FIG. 1 b due to the cooling elements 33 .
[0048] In short, oil level within the sump 37 is regulated to be at a correct level in accordance with engine requirements at all times due to the presence of the pannier oil tanks 11 and the co-operation of the bottom wall valve openings 15 and float valves 17 .
[0049] Table 1 below summarizes the above described oil flows in an engine:
TABLE 1 Typical Oil Flows Peak Torque/ Idle Cruise Rated Speed Litre/min % Litre/min % Litre/min % Speed - rpm 700 1500 2200 Bearings 17 32 47 Cooling Jet 1 8 13 Return to sump 18 73% 40 44.1% 60 47.3% Turbo 3 4.2 4.5 Relief valve 0 30 40 Head/valve gear 1 2 2 Bypass filter 1 8 11.5 Miscellaneous 1.5 6.4 8.7 Return to pannier 6.5 27% 50.6 55.9% 66.7 52.7% oil tanks (11) Total flow 24.5 100% 90.6 100% 126.7 100%
[0050] As indicated above, where the engine is running the volume of oil 16 in circulation results in oil levels in the sump 37 being lowered so that the float valves 17 are partially opened. However, when the engine is stopped, oil in circulation within the engine is returned to the sump 37 and the pannier oil tanks 11 in proportions relative to the engine operating speed immediately prior to shut down. The float valves 17 remain open until the sump 37 is at least partially filed with oil 16 . In practice, return of oil 16 to the sump 37 occurs in advance of return of oil 16 to the pannier oil tanks 11 due to longer return paths from pannier oil tank filling sources, such as the cylinder head 8 . When the float valves 17 are closed, the oil level in the sump 37 continues to rise to a normal level due to the large volume of sump return oil 16 in circulation.
[0051] When servicing the engine, oil drain may be achieved through a sump plug or a suction tube into the sump 37 . At a critical drainage level, the float valves 17 are opened thereby permitting the pannier oil tanks 11 also to drain.
[0052] On refilling, the pannier oil tanks 11 are filled through the filler tube 19 and hence the sump 37 becomes filled via the bottom wall valve opening 15 . If an excessive filling rate is used, the oil tank panniers 11 simply overflow into the sump 37 via the apertures 32 as previously described.
[0053] The invention finds application in engines where it is desired to incorporate an oil capacitor to supplement the oil sump without detriment to engine servicing efficiency and without compromising oil cleanliness and durability within the engine during operation.
[0054] The invention is not limited to the embodiments herein before described which may be varied in both construction and detail.
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In an internal combustion engine, a large volume of lubricant is desirable to increase service intervals and thus reduce maintenance costs. Large lubricant volumes typically require an undesirable increase in engine size. A cylinder block assembly for an internal combustion engine in accordance with this invention comprises a cylinder block, a primary lubricant reservoir or sump below the cylinder block, and a secondary lubricant reservoir at a side of the cylinder block. The secondary lubricant reservoir may be formed as a pannier oil tank by sealably attaching an apron to a side of the cylinder block. A fluid passage extending between the secondary lubricant reservoir and the primary lubricant reservoir is closeable by a valve and is adapted to permit lubricant flow from the secondary lubricant reservoir to the primary lubricant reservoir when open. The secondary lubricant reservoir increases the oil capacity of the cylinder block.
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TECHNICAL FIELD
[0001] The present invention relates to a hot-dip Zn alloy-plated steel sheet excellent in blackening resistance.
BACKGROUND ART
[0002] As plated steel sheet excellent in corrosion resistance, a hot-dip Zn alloy-plated steel sheet having a base steel sheet with a surface coated with a hot-dip Zn alloy plating layer including Al and Mg is known. The composition of the plating layer of a hot-dip Zn alloy-plated steel sheet includes, for example, 4.0 to 15.0% by mass of Al, 1.0 to 4.0% by mass of Mg, 0.002 to 0.1% by mass of Ti, 0.001 to 0.045% by mass of B, and the balance of Zn and unavoidable impurities. The hot-dip Zn alloy-plated steel sheet includes a plating layer of mixed metal structure of [primary crystal Al] and [single phase Zn] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic structure], having sufficient corrosion resistance and surface appearance as an industrial product.
[0003] The hot-dip Zn alloy-plated steel sheet described above can be continuously produced by the following steps. First, a base steel sheet (steel strip) is passed through a furnace, dipped in a hot-dip Zn alloy plating bath, and then passed through, for example, a gas wiping apparatus, such that the amount of the molten metal adhered to the surface of the base steel sheet is adjusted to a specified amount. Subsequently, the steel strip with the specified amount of molten metal adhered thereto is passed through an air jet cooler and a mist cooling zone, so that the molten metal is cooled to form a hot-dip Zn alloy plating layer. Further, the steel strip with the hot-dip Zn alloy plating layer is passed through a water quenching zone, so as to come in contact with cooling water. A hot-dip Zn alloy-plated steel sheet is thus obtained.
[0004] The hot-dip Zn alloy-plated steel sheet thus produced, however, allows the surface of the plating layer to be blackened over time in some cases. Since the progress of blackening of a hot-dip Zn alloy-plated steel sheet spoils the appearance with a dark gray color without metallic luster, a method for suppressing the blackening has been needed.
[0005] As a method for preventing the blackening, adjusting of the temperature of the surface of a plating layer in the water quenching zone has been proposed (e.g. refer to PTL 1). In the invention described in PTL 1, the temperature of the surface of a plating layer is adjusted at lower than 105° C. when contacted with cooling water in the water quenching zone so that blackening of the surface of a plating layer is prevented. Alternatively, instead of the temperature control of the surface of a plating layer at lower than 105° C., readily oxidizable elements (rare earth elements, Y, Zr or Si) are added into a plating bath and the temperature of the surface of a plating layer is adjusted at 105 to 300° C. so that blackening of the surface of the plating layer is prevented.
CITATION LIST
Patent Literature
PTL 1
Japanese Patent Application Laid-Open No. 2002-226958
SUMMARY OF INVENTION
Technical Problem
[0006] In the invention described in PTL 1, since the surface of a plating layer is required to be cooled to a specified temperature before passed through a water quenching zone, the production of a hot-dip Zn alloy-plated steel sheet is restricted in some cases. For example, the feed rate of a plated steel sheet having a large thickness is required to be slow so that the plated steel sheet is cooled to a specified temperature, resulting in reduced productivity. In addition, in the case of adding readily oxidizable elements into a plating bath, the readily oxidizable elements tend to form a dross. Consequently, complicated concentration control of the readily oxidizable elements is required, resulting in a complicated production process, which has been a problem.
[0007] An object of the present invention is to provide a hot-dip Zn alloy-plated steel sheet excellent in blackening resistance which can be produced without reduction in productivity and without complicated control of the components of a plating bath.
Solution to Problem
[0008] The present inventors have found that the problem can be solved by forming a composite oxide film containing the constituent components of a plating layer and vanadium on the surface of the plating layer and reducing the ratio of Zn hydroxide contained in the composite oxide film, and accomplished the present invention through further study.
[0009] The present invention relates to the following hot-dip Zn alloy-plated steel sheet.
[0010] [1] A hot-dip Zn alloy-plated steel sheet comprising: a steel sheet; a hot-dip Zn alloy plating layer disposed on a surface of the steel sheet; and a composite oxide film disposed on a surface of the hot-dip Zn alloy plating layer; wherein the composite oxide film comprises constituent components of the hot-dip Zn alloy plating layer and vanadium, and the composite oxide film satisfies, at the whole of a surface of the composite oxide film, following Equation 1:
[0000]
S
[
Hydroxide
]
S
[
Hydroxide
]
+
S
[
Oxide
]
×
100
≤
40
(
Equation
1
)
[0011] S[Oxide] is a peak area derived from Zn oxide and centered at approximately 1022 eV in an intensity profile of the XPS analysis of the surface of the composite oxide film; and S[Hydroxide] is a peak area derived from Zn hydroxide and centered at approximately 1023 eV in the intensity profile of the XPS analysis of the surface of the composite oxide film.
[0012] [2] The hot-dip Zn alloy-plated steel sheet according to claim 1 , wherein: the hot-dip Zn alloy plating layer comprises 1.0 to 22.0% by mass of Al, 0.1 to 10.0% by mass of Mg, and the balance of the hot-dip Zn alloy plating layer being Zn and unavoidable impurities.
[0013] [3] The hot-dip Zn alloy-plated steel sheet according to claim 2 , wherein: the hot-dip Zn alloy plating layer further comprises at least one selected from the group consisting of 0.001 to 2.0% by mass of Si, 0.001 to 0.1% by mass of Ti, and 0.001 to 0.045% by mass of B.
[0014] [4] The hot-dip Zn alloy-plated steel sheet according to any one of claims 1 to 3 , wherein the adhering amount of the vanadium contained in the composite oxide film is in the range of 0.01 to 10.0 mg/m 2 .
Advantageous Effects of Invention
[0015] According to the present invention, a hot-dip Zn alloy-plated steel sheet excellent in blackening resistance can be easily produced at high productivity.
BRIEF DESCRIPTION OF DRAWINGS
[0016] FIGS. 1A to 1D illustrate the intensity profiles of the chemical binding energy corresponding to the 2p orbitals of Zn at the surface of a composite oxide film.
[0017] FIG. 2A illustrates an exemplary method for contacting a cooling aqueous solution with the surface of a hot-dip Zn alloy plating layer by a spraying process;
[0018] FIG. 2B illustrates an exemplary method for contacting a cooling aqueous solution with the surface of a hot-dip Zn alloy plating layer by a dipping process; and
[0019] FIG. 3 is a schematic diagram illustrating the configuration of a part of the production line of a hot-dip Zn alloy-plated steel sheet.
DESCRIPTION OF EMBODIMENTS
[0020] (Hot-Dip Zn Alloy-Plated Steel Sheet of the Present Invention)
[0021] The hot-dip Zn alloy-plated steel sheet of the present invention includes a base steel sheet, a hot-dip Zn alloy plating layer, and a composite oxide film. The hot-dip Zn alloy-plated steel sheet of the present invention is excellent in blackening resistance, by virtue of a specified composite oxide film.
[0022] The type of the base steel sheet is not particularly limited. For example, a steel sheet made of low-carbon steel, medium-carbon steel, high-carbon steel, alloy steel or the like may be used as the base steel sheet. When excellent press formability is required, a steel sheet for deep drawing made of low-carbon Ti-alloyed steel, low-carbon Nb-alloyed steel or the like is preferably used as the base steel sheet. Alternatively, a high-strength steel sheet containing P, Si, Mn and the like may be used.
[0023] The hot-dip Zn alloy plating layer is disposed on the surface of a base steel sheet. The composition of the hot-dip Zn alloy plating layer may be appropriately selected depending on the purpose. For example, the plating layer includes 1.0 to 22.0% by mass of Al, 0.1 to 10.0% by mass of Mg, and the balance of Zn and unavoidable impurities. The plating layer may further include at least one selected from the group consisting of 0.001 to 2.0% by mass of Si, 0.001 to 0.1% by mass of Ti, and 0.001 to 0.045% by mass of B. Examples of the hot-dip Zn alloy plating include a molten Zn—0.18% by mass of Al—0.09% by mass of Sb alloy plating, a molten Zn—0.18% by mass of Al—0.06% by mass of Sb alloy plating, a molten Zn—0.18% by mass Al alloy plating, a molten Zn—1% by mass of Al—1% by mass of Mg alloy plating, a molten Zn—1.5% by mass of Al—1.5% by mass of Mg alloy plating, a molten Zn—2.5% by mass of Al—3% by mass of Mg alloy plating, a molten Zn—2.5% by mass of Al—3% by mass of Mg—0.4% by mass of Si alloy plating, a molten Zn—3.5% by mass of Al—3% by mass of Mg alloy plating, a molten Zn—4% by mass of Al—0.75% by mass of Mg alloy plating, a molten Zn—6% by mass of Al—3% by mass of Mg—0.05% by mass of Ti—0.003% by mass of B alloy plating, a molten Zn—6% by mass of Al—3% by mass of Mg—0.02% by mass of Si—0.05% by mass of Ti—0.003% by mass of B alloy plating, a molten Zn—11% by mass of Al—3% by mass of Mg alloy plating, a molten Zn—11% by mass of Al—3% by mass of Mg—0.2% by mass of Si alloy plating, and a molten Zn—55% by mass of Al—1.6% by mass of Si alloy plating. Although blackening of a plating layer can be suppressed by addition of Si as described in PTL 1, in the case of the hot-dip Zn alloy-plated steel sheet of the present invention, blackening of a plating layer can be suppressed without addition of Si to the plating layer.
[0024] The amount of the hot-dip Zn alloy plating layer adhered is not specifically limited. The amount of the plating layer adhered may be, for example, approximately 60 to 500 g/m 2 .
[0025] The composite oxide film is disposed on the surface of a hot-dip Zn alloy plating layer, preferably on the entire surface. The composite oxide film mainly contains constituent components of the hot-dip Zn alloy plating layer (e.g. Zn, Al and Mg) and vanadium. The composite oxide film satisfies, at the entire surface, the following equation 2.
[0000]
S
[
Hydroxide
]
S
[
Hydroxide
]
+
S
[
Oxide
]
×
100
≤
40
(
Equation
2
)
[0026] wherein S[Oxide] is a peak area derived from the Zn oxide and centered at approximately 1022 eV in the intensity profile of the XPS analysis of the surface of a composite oxide film; and S[Hydroxide] is a peak area derived from the Zn hydroxide and centered at approximately 1023 eV in the intensity profile of the XPS analysis of the surface of a composite oxide film.
[0027] The equation 2 indicates that the ratio of the peak area derived from the Zn hydroxide and centered at approximately 1023 eV (hereinafter referred to as “hydroxide ratio”) is 40% or less relative to the total of the peak area derived from the Zn oxide and centered at approximately 1022 eV and a peak area derived from the Zn hydroxide and centered at approximately 1023 eV in the intensity profile measured in the XPS analysis.
[0028] FIGS. 1A to 1D illustrate the intensity profiles of the chemical bonding energy corresponding to the 2p orbitals of Zn at the surface of the composite oxide film of a hot-dip Zn alloy-plated steel sheet. FIG. 1A illustrates the intensity profile with a Zn hydroxide ratio of approximately 80%, FIG. 1B illustrates the intensity profile with a Zn hydroxide ratio of approximately 40%, FIG. 1C illustrates the intensity profile with a Zn hydroxide ratio of approximately 15%, and FIG. 1D illustrates the intensity profile with a Zn hydroxide ratio of approximately 10%. A dotted line is the base line, a broken line is the intensity profile derived from Zn oxide (a peak centered at approximately 1022 eV), and a dashed dotted line is the intensity profile derived from Zn hydroxide (a peak centered at approximately 1023 eV). In the hot-dip Zn alloy-plated steel sheet of the present invention, the Zn hydroxide ratio is 40% or less over the entire surface of the plating layer as shown in FIGS. 1B to 1D .
[0029] The XPS analysis of the surface of the composite oxide film of a hot-dip Zn alloy-plated steel sheet of the present invention is performed using an XPS analyzer (AXIS Nova, produced by Kratos Group PLC.). The peak area derived from Zn oxide and centered at approximately 1022 eV and the peak area derived from Zn hydroxide and centered at approximately 1023 eV are calculated using software (Vision 2) attached to the XPS analyzer.
[0030] The position of the peak derived from Zn oxide is precisely at 1021.6 eV, and the position of the peak derived from Zn hydroxide is precisely at 1023.3 eV. These values may change in some cases due to characteristics of XPS analysis, contamination of a sample, and charging of a sample. Those skilled in the art, however, are capable of distinguishing the peak derived from Zn oxide from the peak derived from Zn hydroxide.
[0031] The adhering amount of the vanadium in the composite oxide film is not specifically limited, but preferably in the range of 0.01 to 10.0 mg/m 2 . With an adhering amount of the vanadium of 0.01 mg/m 2 or more, the blackening resistance can be further improved. With an adhering amount of the vanadium of 10.0 mg/m 2 or less, the reactivity with a chemical conversion liquid for chemical conversion treatment can be improved. The adhering amount of vanadium in a composite oxide film can be measured using an ICP emission analyzer.
[0032] (Producing Method of Hot-Dip Zn Alloy-Plated Steel Sheet of the Present Invention)
[0033] The producing method of a hot-dip Zn alloy-plated steel sheet of the present invention is not specifically limited. For example, the hot-dip Zn alloy-plated steel sheet of the present invention may be produced by: (1) a first step of forming a hot-dip Zn alloy plating layer (hereinafter, also referred to as “plating layer”) on the surface of a base steel sheet; and (2) a second step of contacting a specified aqueous solution with the surface of the plating layer for cooling of the base steel sheet and the plating layer at a raised temperature through formation of the plating layer, and for forming a composite oxide film. Each of the steps is described as follows.
[0034] (1) First Step
[0035] In the first step, a base steel sheet is dipped in a hot-dip Zn alloy plating bath, so that a hot-dip Zn alloy plating layer is formed on the surface of the base steel sheet.
[0036] First, a base steel sheet is dipped in a hot-dip Zn alloy plating bath, and a specified amount of molten metal is allowed to adhere to the surface of the base steel sheet by gas wiping or the like. As described above, the type of the base steel sheet is not specifically limited. The composition of the plating bath is appropriately selected depending on the composition of the hot-dip Zn alloy plating layer to be formed.
[0037] Subsequently, the molten metal adhered to the surface of a base steel sheet is cooled to a temperature equal to or more than 100° C. and equal to or less than the solidifying point of the plating layer so as to be solidified. A plated steel sheet is thus formed, having a plating layer with a composition approximately the same as the composition of the plating bath, on the surface of the base steel sheet.
[0038] (2) Second Step
[0039] In the second step, a specified cooling aqueous solution is contacted with the surface of the hot-dip Zn alloy plating layer, so that the base steel sheet and the plating layer at a raised temperature through formation of the hot-dip Zn alloy plating layer are cooled. In this step, a composite oxide film is formed on the surface of the plating layer. From the viewpoint of productivity, the second step is performed preferably by water quenching (water cooling). In this case, the temperature of the surface of the hot-dip Zn alloy plating layer when the cooling aqueous solution is to be contacted with the surface of the hot-dip Zn alloy plating layer is equal to or more than 100° C. and approximately equal to or less than the solidifying point of the plating layer.
[0040] The cooling aqueous solution is formed of an aqueous solution containing a vanadium compound. The concentration of the vanadium compound in the cooling aqueous solution is preferably 0.01 g/L or more in terms of V element. When a concentration of the vanadium compound is less than 0.01 g/L in terms of V element, blackening of the surface of a composite oxide film may not be sufficiently prevented.
[0041] The method for preparing the aqueous solution (cooling aqueous solution) containing a vanadium compound is not specifically limited. For example, a vanadium compound and a dissolution promoter on an as needed basis, may be dissolved in water (solvent). Preferable examples of the vanadium compound include acetylacetone vanadyl, vanadium acetylacetonate, vanadium oxysulfate, vanadium pentoxide, and ammonium vanadate. These vanadium compounds may be used singly or in combination.
[0042] In the case of adding a dissolution promoter, the amount of the dissolution promoter added is not specifically limited. For example, 90 to 130 parts by mass of the dissolution promoter may be added to 100 parts by mass of the vanadium compound. With an excessively small amount of the dissolution promoter added, the vanadium compound cannot be sufficiently dissolved in some cases. On the other hand, with an excessively large amount of the dissolution promoter added, the effect is saturated, resulting in a cost disadvantage.
[0043] Examples of the dissolution promoter include 2-aminoethanol, tetraethylammonium hydroxide, ethylene diamine, 2,2′-iminodiethanol, and 1-amino-2-propanol.
[0044] The method for contacting the cooling aqueous solution with the surface of a hot-dip Zn alloy plating layer is not specifically limited. Examples of the method for contacting the cooling aqueous solution with the surface of a hot-dip Zn alloy plating layer include a spraying process and a dipping process.
[0045] FIGS. 2A and 2B illustrate exemplary methods for contacting a cooling aqueous solution with the surface of a hot-dip Zn alloy plating layer. FIG. 2A illustrates an exemplary method for contacting a cooling aqueous solution with the surface of a hot-dip Zn alloy plating layer by a spraying process. FIG. 2B illustrates an exemplary method for contacting a cooling aqueous solution with the surface of a hot-dip Zn alloy plating layer by a dipping process.
[0046] As shown in FIG. 2A , cooling for spraying process includes a plurality of spray nozzles 110 , squeeze rollers 120 disposed downstream of spray nozzles 110 in the feed direction of a steel strip S, and housing 130 which covers the nozzles and the rollers. Spray nozzles 110 are disposed on both sides of the steel strip S. The steel strip S is cooled by a cooling aqueous solution supplied from spray nozzles 110 such that a water film is temporarily formed on the surface of the plating layer, inside housing 130 .
[0047] The cooling aqueous solution is then removed with squeeze roller 120 . The adhering amount of vanadium in the composite oxide film can be adjusted by controlling the opening of squeeze rollers 120 .
[0048] As shown in FIG. 2B , cooling apparatus 200 for dipping process includes dip tank 210 in which a cooling aqueous solution is stored, dip roller 220 disposed inside dip tank 210 , and squeeze rollers 230 disposed downstream of dip roller 220 in the feed direction of the steel strip S so as to remove the extra cooling aqueous solution adhered to the steel strip S. The steel strip S fed into dip tank 210 is then contacted with the cooling aqueous solution so as to be cooled. The steel strip S is then subjected to a turn of direction by the rotating dip roller 220 , and pulled upward. The cooling aqueous solution is removed with squeeze roller 230 . The adhering amount of vanadium in the composite oxide film can be adjusted by controlling the opening of squeeze rollers 230 .
[0049] According to the procedure described above, a hot-dip Zn alloy-plated steel sheet of the present invention can be produced.
[0050] Although the composite oxide film was formed through contact with an aqueous solution containing a vanadium compound in the water quenching step, it is conceivable that a composite oxide film can be also formed by applying an aqueous solution containing a vanadium compound to a cooled hot-dip Zn alloy-plated steel sheet and drying the applied aqueous solution (post-treatment method). Accordingly, the present inventors tried to form a composite oxide film by applying an aqueous solution containing a vanadium compound (the same aqueous solution as that used in the producing method described above) to a hot-dip Zn alloy-plated steel sheet cooled to normal temperature with a general industrial water, and drying the applied aqueous solution. Although a composite oxide film containing constituent components of a plating layer and vanadium was also formed on the surface of the plating layer through such a post-treatment method, the composite oxide film had a Zn hydroxide ratio of more than 40%. The hot-dip Zn alloy-plated steel sheet thus produced had no outstanding difference in blackening resistance compared with a hot-dip Zn alloy-plated steel plate having no composite oxide film.
[0051] The reason is not clear why the hot-dip Zn alloy-plated steel sheet of the present invention has higher blackening resistance than a hot-dip Zn alloy-plated steel sheet having no composite oxide film. As described above, the hot-dip Zn alloy-plated steel sheet produced by the post-treatment method has a Zn hydroxide ratio of more than 40% in the composite oxide film, which is different from that of the hot-dip Zn alloy-plated steel sheet of the present invention. Furthermore, the blackening resistance is notably different between the hot-dip Zn alloy-plated steel sheet of the present invention and the hot-dip Zn alloy-plated steel sheet produced by the post-treatment method. It is therefore conceivable that the stability of Zn contained in the composite oxide film is different between the hot-dip Zn alloy-plated steel sheet of the present invention and the hot-dip Zn alloy-plated steel sheet produced by the post-treatment method, and the Zn contained in the composite oxide film of the hot-dip Zn alloy-plated steel sheet of the present invention is more difficult to transform into an oxygen-deficient zinc oxide as the source of blackening. This may be the reason why the hot-dip Zn alloy-plated steel sheet of the present invention has higher blackening resistance.
[0052] (Production Line)
[0053] The hot-dip Zn alloy-plated steel sheet of the present invention may be produced, for example, in the following production line.
[0054] FIG. 3 is a schematic diagram illustrating a part of production line 300 of a hot-dip Zn alloy-plated steel sheet. Production line 300 forms a plating layer and a composite oxide film on the surface of a base steel sheet (steel strip), and can continuously produce hot-dip Zn alloy-plated steel sheets of the present invention. Production line 300 may further form a chemical conversion coating on the surface of the composite oxide film on an as needed basis, and can continuously produce plated steel sheets with chemical conversion treatment.
[0055] As shown in FIG. 3 , production line 300 includes furnace 310 , plating bath 320 , air jet cooler 340 , mist cooling zone 350 , water quenching zone 360 , skin pass mill 370 , and tension leveler 380 .
[0056] The steel strip S fed from a feeding reel not shown in drawing through a predetermined step is heated in furnace 310 . The heated steel strip S is dipped in plating bath 320 , so that molten metal is adhered to both sides of the steel strip S. An excess amount of molten metal is then removed with a wiping apparatus having wiping nozzle 330 , allowing a specified amount of molten metal to be adhered to the surface of the steel strip S.
[0057] The steel strip S with a specified amount of molten metal adhered thereto is cooled to the solidifying point of the molten metal or lower by air jet cooler 340 or in mist cooling zone 350 . Air jet cooler 340 is a facility for cooling the steel strip S by spraying a gas. Mist cooling zone 350 is a facility for cooling the steel strip S by spraying atomized fluid (e.g. cooling water) and a gas. The molten metal is thereby solidified, so that a hot-dip Zn alloy plating layer is formed on the surface of the steel strip S. When the steel strip s is cooled in mist cooling zone 350 , no water film is formed on the surface of the plating layer. The temperature after cooling is not specifically limited, and may be, for example, 100 to 250° C.
[0058] The hot-dip Zn alloy-plated steel sheet cooled to a specified temperature is further cooled in water quenching zone 360 . Water quenching zone 360 is a facility for cooling the steel strip S through contact with a large amount of cooling water in comparison with mist cooling zone 350 , supplying an amount of water to form a temporary water film on the surface of the plating layer. For example, water quenching zone 360 includes headers having 10 flat spray nozzles disposed at intervals of 150 mm in the width direction of the steel strip S, which are disposed in 7 rows in the feeding direction of the base steel sheet S. In water quenching zone 360 , an aqueous solution containing a vanadium compound is used as cooling aqueous solution. The steel strip S is cooled in water quenching zone 360 , with the cooling aqueous solution in an amount to temporarily form a water film on the surface of the plating layer being supplied. For example, the cooling aqueous solution has a water temperature of approximately 20° C., a water pressure of approximately 2.5 kgf/cm 2 , and a water quantity of approximately 150 m 3 /h. The phrase “a water film is temporarily formed” means a state allowing a water film in contact with a hot-dip Zn alloy-plated steel sheet to be visually observed for approximately one second or more. Through cooling using an aqueous solution of a vanadium compound in water quenching zone 360 , a composite oxide film containing the constituent components of a plating layer and vanadium with a Zn hydroxide of 40% or more is formed on the surface of the plating layer.
[0059] The water-cooled hot-dip Zn alloy-plated steel sheet is rolled for thermal refining by skin pass mill 370 , corrected to flat by tension leveler 380 , and then wound onto tension reel 390 .
[0060] When a chemical conversion coating is further formed on the surface of a plating layer, a specified chemical conversion treatment liquid is applied to the surface of the hot-dip Zn alloy-plated steel sheet corrected by tension leveler 380 , with roll coater 400 . The hot-dip Zn alloy-plated steel sheet through the chemical conversion treatment is dried and cooled in drying zone 410 and air cooling zone 420 , and then wound onto tension reel 390 .
[0061] As described above, the hot-dip Zn alloy-plated steel sheet of the present invention has excellent blackening resistance and can be easily produced at high productivity.
[0062] The present invention is described in detail with reference to Examples as follows. The present invention is, however, not limited to the Examples.
Examples
Experiment 1
[0063] In Experiment 1, the blackening resistance of a hot-dip Zn alloy-plated steel sheet was examined for the hot-dip Zn alloy-plated steel sheet cooled using a cooling water containing a metal compound after plating.
[0064] 1. Production of Hot-Dip Zn Alloy-Plated Steel Sheet
[0065] Using production line 300 shown in FIG. 3 , hot-dip Zn alloy-plated steel sheets were produced. A hot-rolled steel strip with a sheet thickness of 2.3 mm was prepared as base steel sheet (steel strip) S. Plating was applied to the base steel sheet using the plating bath compositions and conditions described in Table 1, so that 14 types of hot-dip Zn alloy-plated steel sheets having different plating layer compositions from each other were produced. The composition of the plating bath and the composition of the plating layer are approximately the same.
[0000]
TABLE 1
Plating conditions
Sheet
Bath
Adhering
passing
Plating
Plating bath composition (balance: Zn) (% by mass)
temperature
amount
speed
No.
Al
Mg
Si
Ti
B
Sb
(° C.)
(g/m 2 )
(m/min)
1
0.18
—
—
—
—
0.09
430
90
80
2
0.18
—
—
—
—
0.06
430
90
80
3
0.18
—
—
—
—
—
430
90
80
4
1
1
—
—
—
—
430
90
80
5
1.5
1.5
—
—
—
—
430
90
80
6
2.5
3
—
—
—
—
430
90
80
7
2.5
3
0.4
—
—
—
430
90
80
8
3.5
3
—
—
—
—
430
90
80
9
4
0.75
—
—
—
—
430
90
80
10
6
3
—
0.05
0.003
—
430
90
80
11
6
3
0.02
0.05
0.003
—
430
90
80
12
11
3
—
—
—
—
450
90
80
13
11
3
0.2
—
—
—
450
90
80
14
55
—
1.6
—
—
—
600
90
80
[0066] In production of a hot-dip Zn alloy-plated steel sheet, the cooling conditions in air jet cooler 340 were changed, such that the temperature of the steel sheet (the surface of plating layer) is adjusted at 200° C. immediately before passing through water quenching zone 360 . In water quenching zone 360 , any one of the aqueous solution described in Table 2 was used as cooling aqueous solution for formation of the composite oxide film. Each of the cooing aqueous solutions was prepared by dissolving the metal compound described in Table 2 and a dissolution promotor on an as needed basis at a specified ratio in a water having a pH of 7.6, and adjusting the water temperature to 20° C. The concentration of the metal compound in each of the cooling aqueous solutions was 250 mg/L in terms of metal element in any case. The spray apparatus in water quenching zone 360 for use includes headers having 10 flat spray nozzles disposed at intervals of 150 mm in the width direction, which are disposed in 7 rows in the feeding direction of the base steel sheet S. Each of the cooling aqueous solutions supplied from water quenching zone 360 was under conditions with a water pressure of 2.5 kgf/cm 2 and a water quantity of 150 m 3 /h.
[0067] As Comparative Example, a composite oxide film was formed by using a water containing no metal compound instead of using any one of the aqueous solutions described in Table 2 in water quenching zone 360 , then applying any of the aqueous solutions described in Table 2 by a roll coat method or a spray ringer roll method, and drying the applied aqueous solution (post-treatment method).
[0000]
TABLE 2
Metal compound (A)
Dissolution promoter (B)
Cooling
Amount
Ratio of
water
added
amount
Category
No.
Name
(mg/L)
Name
added (B/A)
Example
1
Vanadium
1709
Tetraethylammonium
1.1
acetylacetonate
hydroxide
2
Acetylacetonate vanadyl
1301
Ethylene diamine
1.3
3
Ammonium metavanadate
574
—
—
4
Sodium metavanadate
598
—
—
5
Divanadium tetroxide
407
2,2′-Iminodiethanol
0.9
6
Vanadium pentoxide
446
1-Amino-2-propanol
1.1
Comparative
7
Ammonium chromate
606
—
—
Example
8
Potassium chromate
467
—
—
9
Sodium silicate
1087
—
—
[0068] 2. Evaluation of Hot-Dip Zn Alloy-Plated Steel Sheet
[0069] (1) Measurement of Zn(OH) 2 Ratio on Surface of Composite Oxide Film
[0070] For each of the hot-dip Zn alloy-plated steel sheets, the Zn hydroxide ratio on the surface of the composite oxide film was measured using an XPS analyzer (AXIS Nova, produced by Kratos Group PLC.). The Zn hydroxide ratio was calculated using software (Vision 2) attached to the XPS analyzer.
[0071] (2) Measurement of Adhering Amount of V on Surface of Composite Oxide Film
[0072] For each of the hot-dip Zn alloy-plated steel sheets, the adhering amount of vanadium on the surface of the composite oxide film was measured using an ICP emission analyzer (ICPS-8100, produced by Shimadzu Corporation).
[0073] (3) Treatment for Accelerating Deterioration of Gloss
[0074] A test piece was cut out from each of the produced hot-dip Zn alloy-plated steel sheets. Each of the test pieces was placed in a thermo-hygrostat (LHU-113, produced by Espec Corp.), and subjected to a treatment for accelerating deterioration of the gloss at a temperature 70° C., with a relative humidity of 90%, for 72 hours.
[0075] (4) Measurement of Degree of Blackening
[0076] The brightness (L* value) at the surface of the plating layer for each of the hot-dip Zn alloy-plated steel sheets was measured before and after the treatment for accelerating deterioration of the gloss. The brightness (L* value) at the surface of the plating layer was measured using a spectroscopic color difference meter (TC-1800, produced by Tokyo Denshoku Co., Ltd), by spectral reflectance measurement in accordance with JIS K 5600. The measurement conditions are as follows:
[0077] Optical condition: d/8° method (double beam optical system)
[0078] Field of view: 2-degree field of view
[0079] Measurement method: reflectometry
[0080] Standard illuminant: C
[0081] Color system: CIELAB
[0082] Measurement wavelength: 380 to 780 nm
[0083] Measurement wavelength interval: 5 nm
[0084] Spectroscope: 1,200/mm diffraction grating
[0085] Lighting: halogen lamp (voltage: 12 V, power: 50 W, rating life: 2,000 hours)
[0086] Measurement area: 7.25 mm diameter
[0087] Detection element: photomultiplier tube (R928 produced by Hamamatsu Photonics K.K.)
[0088] Reflectance: 0 to 150%
[0089] Measurement temperature: 23° C.
[0090] Standard plate: white
[0091] For each of the plated steel sheets, the evaluation was ranked as “A” for a difference in L* values (ΔL*) between before and after the treatment for accelerating deterioration of the gloss of less than 1, “B” for a difference of 1 or more and less than 3, “C” for a difference of 3 or more and less than 7, and “D” for a difference of 7 or more. It can be determined that a plated steel sheet evaluated as “A” or “B” has blackening resistance.
[0092] (4) Evaluation Results
[0093] For each of the plated steel sheets, the relation between the type of the cooling aqueous solution for use and the method for forming the composite oxide film (a water quenching method (WQ), a roll coat method (RC), or a spray ringer roll method (SP)), and the Zn hydroxide ratio, the adhering amount of V and the evaluation results of the degree of blackening is described in Table 3 to Table 6.
[0000]
TABLE 3
Cool-
Adhering
Black-
Test
Plat-
ing
Treat-
Amount
ening
Cate-
piece
ing
water
ment
Hydroxide
of V
test
gory
No.
No.
No.
method
Ratio (%)
(mg/m 2 )
result
Ex.
1
11
1
WQ
7
0.004
B
Ex.
2
11
2
WQ
11
0.004
B
Ex.
3
11
3
WQ
7
0.005
B
Ex.
4
11
4
WQ
13
0.004
B
Ex.
5
11
5
WQ
7
0.005
B
Ex.
6
11
6
WQ
25
0.005
B
Ex.
7
11
1
WQ
6
0.01
A
Ex.
8
11
2
WQ
11
0.017
A
Ex.
9
11
3
WQ
16
0.013
A
Ex.
10
11
4
WQ
19
0.022
A
Ex.
11
11
5
WQ
23
0.029
A
Ex.
12
11
6
WQ
24
0.027
A
Ex.
13
11
1
WQ
8
0.13
A
Ex.
14
11
2
WQ
18
0.18
A
Ex.
15
11
3
WQ
21
0.17
A
Ex.
16
11
4
WQ
14
0.12
A
Ex.
17
11
5
WQ
25
0.16
A
Ex.
18
11
6
WQ
18
0.18
A
Ex.
19
11
1
WQ
22
1.02
A
Ex.
20
11
2
WQ
7
1.01
A
Ex.
21
11
3
WQ
23
0.96
A
Ex.
22
11
4
WQ
7
0.96
A
Ex.
23
11
5
WQ
5
0.98
A
Ex.
24
11
6
WQ
19
1.01
A
Ex.
25
11
1
WQ
20
7.95
A
Ex.
26
11
2
WQ
16
7.98
A
Ex.
27
11
3
WQ
6
8.02
A
Ex.
28
11
4
WQ
21
8.05
A
Ex.
29
11
5
WQ
6
8.01
A
Ex.
30
11
6
WQ
18
8.04
A
[0000]
TABLE 4
Cool-
Adhering
Black-
Test
Plat-
ing
Treat-
Amount
ening
piece
ing
water
ment
Hydroxide
of V
test
Category
No.
No.
No.
method
Ratio (%)
(mg/m 2 )
result
Ex.
31
11
1
WQ
13
15.04
A
Ex.
32
11
2
WQ
8
14.97
A
Ex.
33
11
3
WQ
17
14.98
A
Ex.
34
11
4
WQ
5
14.99
A
Ex.
35
11
5
WQ
14
14.97
A
Ex.
36
11
6
WQ
17
14.96
A
Comp. Ex.
37
11
7
WQ
19
0
C
Comp. Ex.
38
11
8
WQ
9
0
C
Comp. Ex.
39
11
9
WQ
24
0
D
Comp. Ex.
40
11
1
RC
76
1.03
D
Comp. Ex.
41
11
2
RC
76
0.96
D
Comp. Ex.
42
11
3
RC
65
0.99
D
Comp. Ex.
43
11
4
RC
71
7.96
D
Comp. Ex.
44
11
5
RC
83
7.96
D
Comp. Ex.
45
11
6
RC
76
8.01
D
Comp. Ex.
46
11
1
SP
76
1.06
D
Comp. Ex.
47
11
2
SP
76
1.05
D
Comp. Ex.
48
11
3
SP
65
1.01
D
Comp. Ex.
49
11
4
SP
71
8.03
D
Comp. Ex.
50
11
5
SP
83
8.03
D
Comp. Ex.
51
11
6
SP
76
8.03
D
[0000]
TABLE 5
Cool-
Adhering
Black-
Test
Plat-
ing
Treat-
Amount
ening
Cate-
piece
ing
water
ment
Hydroxide
of V
test
gory
No.
No.
No.
method
Ratio (%)
(mg/m 2 )
result
Ex.
52
9
1
WQ
11
0.005
B
Ex.
53
14
2
WQ
12
0.004
B
Ex.
54
2
3
WQ
7
0.007
B
Ex.
55
10
4
WQ
12
0.005
B
Ex.
56
1
5
WQ
15
0.003
B
Ex.
57
12
6
WQ
22
0.005
B
Ex.
58
5
1
WQ
14
0.024
A
Ex.
59
8
2
WQ
8
0.019
A
Ex.
60
13
3
WQ
11
0.022
A
Ex.
61
3
4
WQ
14
0.017
A
Ex.
62
10
5
WQ
8
0.021
A
Ex.
63
4
6
WQ
24
0.023
A
Ex.
64
13
1
WQ
20
0.221
A
Ex.
65
7
2
WQ
21
0.239
A
Ex.
66
12
3
WQ
6
0.217
A
Ex.
67
9
4
WQ
5
0.224
A
Ex.
68
7
5
WQ
16
0.189
A
Ex.
69
5
6
WQ
12
0.24
A
Ex.
70
12
1
WQ
15
1.08
A
Ex.
71
9
2
WQ
6
1.05
A
Ex.
72
4
3
WQ
9
0.98
A
Ex.
73
1
4
WQ
14
0.97
A
Ex.
74
14
5
WQ
8
0.95
A
Ex.
75
3
6
WQ
10
1.04
A
Ex.
76
10
1
WQ
10
7.85
A
Ex.
77
8
2
WQ
6
7.81
A
Ex.
78
13
3
WQ
19
8.19
A
Ex.
79
10
4
WQ
22
7.81
A
Ex.
80
6
5
WQ
8
8.12
A
Ex.
81
12
6
WQ
15
8.09
A
[0000]
TABLE 6
Cool-
Adhering
Black-
Test
Plat-
ing
Treat-
Amount
ening
piece
ing
water
ment
Hydroxide
of V
test
Category
No.
No.
No.
method
Ratio (%)
(mg/m2)
result
Ex.
82
5
1
WQ
24
15.16
A
Ex.
83
9
2
WQ
24
15.01
A
Ex.
84
1
3
WQ
18
15.08
A
Ex.
85
2
4
WQ
6
14.96
A
Ex.
86
13
5
WQ
12
15.05
A
Ex.
87
6
6
WQ
11
15.04
A
Comp. Ex.
88
13
7
WQ
20
0
C
Comp. Ex.
89
12
8
WQ
5
0
C
Comp. Ex.
90
10
9
WQ
12
0
D
Comp. Ex.
91
9
1
RC
72
1.02
D
Comp. Ex.
92
14
2
RC
70
0.96
D
Comp. Ex.
93
12
3
RC
88
0.91
D
Comp. Ex.
94
8
4
RC
74
0.97
D
Comp. Ex.
95
9
5
RC
67
0.91
D
Comp. Ex.
96
5
6
RC
65
1.08
D
Comp. Ex.
97
9
1
SP
72
0.99
D
Comp. Ex.
98
14
2
SP
70
0.96
D
Comp. Ex.
99
12
3
SP
88
0.83
D
Comp. Ex.
100
8
4
SP
74
0.88
D
Comp. Ex.
101
9
5
SP
67
0.81
D
Comp. Ex.
102
5
6
SP
65
1.07
D
[0094] As shown in Table 3 to Table 6, in the case of cooling using an aqueous solution containing vanadium in water quenching zone 360 , a composite oxide film containing vanadium was formed having the surface with a Zn hydroxide ratio of 40% or less, and excellent blackening resistance. In contrast, in the case of cooling using an aqueous solution containing no vanadium in water quenching zone 360 , a composite oxide film containing no vanadium was formed, and blackening was insufficiently suppressed. In the case of application of an aqueous solution containing vanadium by a roll coat method or a spray ringer roll method, a composite oxide film was formed, having the surface with a Zn hydroxide ratio of more than 40%, and blackening was insufficiently suppressed.
[0095] From the comparison of the blackening resistance of the test pieces Nos. 1 to 6 and Nos. 52 to 57 with the blackening resistance of the test pieces Nos. 7 to 36 and Nos. 58 to 87, it is found that the blackening resistance is particularly excellent in the case of an adhering amount of vanadium in the composite oxide film of 0.01 mg/m 2 or more.
[0096] From the results described above, it is found that the cooling using an aqueous solution containing vanadium in water quenching zone 360 allows a composite oxide film to be formed, which contains vanadium and has the surface with a Zn hydroxide ratio of 40% or less. The plated steel sheet having such a composite oxide film is excellent in blackening resistance.
Experiment 2
[0097] In Experiment 2, the 102 types of hot-dip Zn alloy-plated steel sheets produced in Experiment 1 were subjected to a chemical conversion treatment under the following chemical conversion treatment conditions A to C. Blackening resistance was measured when the treatment for accelerating deterioration of the gloss was carried out in the same manner as in Experiment 1. The appearance after the chemical conversion treatment was also evaluated.
[0098] In chemical conversion treatment conditions A, ZINCHROME 3387N (chrome concentration: 10 g/L, produced by Nihon Parkerizing Co., Ltd.) was used as chemical conversion treatment liquid. The chemical conversion treatment liquid was applied to have an adhering amount of chromium of 10 mg/m 2 by a spray ringer roll method.
[0099] In chemical conversion treatment conditions B, an aqueous solution containing 50 g/L of magnesium phosphate, 10 g/L of potassium fluorotitanate, and 3 g/L of an organic acid was used as chemical conversion treatment liquid. The chemical conversion treatment liquid was applied to have an adhering amount of metal components of 50 mg/m 2 by a roll coat method.
[0100] In chemical conversion treatment conditions C, an aqueous solution containing 20 g/L of a urethane resin, 3 g/L of ammonium dihydrogen phosphate, and 1 g/L of vanadium pentoxide was used as chemical conversion treatment liquid. The chemical conversion treatment liquid was applied to have a dried film thickness of 2 μm by a roll coat method.
[0101] In the evaluation of the appearance for each of the plated steel sheets after the chemical conversion treatment, the evaluation was ranked as “B” for the chemical conversion treatment coating having no white turbidity, and “D” for the chemical conversion treatment coating having white turbidity.
[0102] For each of the plated steel sheets, the relation between the type of the original sheet for the chemical conversion treatment and the type of chemical conversion treatment, and the evaluation results of the degree of blackening and the appearance is described in Table 7 to Table 10.
[0000]
TABLE 7
Original
sheet for
conversion
Black-
Test
Chemical
treatment
ening
piece
conversion
(test piece
test
Appear-
Category
No.
treatment
No.)
result
ance
Ex.
103
A
1
B
B
Ex.
104
B
2
B
B
Ex.
105
C
3
B
B
Ex.
106
A
4
B
B
Ex.
107
B
5
B
B
Ex.
108
C
6
B
B
Ex.
109
A
7
A
B
Ex.
110
B
8
A
B
Ex.
111
C
9
A
B
Ex.
112
A
10
A
B
Ex.
113
B
11
A
B
Ex.
114
C
12
A
B
Ex.
115
A
13
A
B
Ex.
116
B
14
A
B
Ex.
117
C
15
A
B
Ex.
118
A
16
A
B
Ex.
119
B
17
A
B
Ex.
120
C
18
A
B
Ex.
121
A
19
A
B
Ex.
122
B
20
A
B
Ex.
123
C
21
A
B
Ex.
124
A
22
A
B
Ex.
125
B
23
A
B
Ex.
126
C
24
A
B
Ex.
127
A
25
A
B
Ex.
128
B
26
A
B
Ex.
129
C
27
A
B
Ex.
130
A
28
A
B
Ex.
131
B
29
A
B
Ex.
132
C
30
A
B
[0000]
TABLE 8
Original
sheet for
chemical
conversion
Black-
Test
Chemical
treatment
ening
piece
conversion
(test
test
Appear-
Category
No.
treatment
piece No.)
result
ance
Ex.
133
A
31
A
D
Ex.
134
B
32
A
D
Ex.
135
C
33
A
D
Ex.
136
A
34
A
D
Ex.
137
B
35
A
D
Ex.
138
C
36
A
D
Comp. Ex.
139
A
37
D
B
Comp. Ex.
140
B
38
D
B
Comp. Ex.
141
C
39
D
B
Comp. Ex.
142
A
40
D
B
Comp. Ex.
143
B
41
D
B
Comp. Ex.
144
C
42
D
B
Comp. Ex.
145
A
43
D
B
Comp. Ex.
146
B
44
D
B
Comp. Ex.
147
C
45
D
B
Comp. Ex.
148
A
46
D
B
Comp. Ex.
149
B
47
D
B
Comp. Ex.
150
C
48
D
B
Comp. Ex.
151
A
49
D
B
Comp. Ex.
152
B
50
D
B
Comp. Ex.
153
C
51
D
B
[0000]
TABLE 9
Original
sheet for
chemical
conversion
Black-
Test
Chemical
treatment
ening
piece
conversion
(test
test
Appear-
Category
No.
treatment
piece No.)
result
ance
Ex.
154
A
52
B
B
Ex.
155
B
53
B
B
Ex.
156
C
54
B
B
Ex.
157
A
55
B
B
Ex.
158
B
56
B
B
Ex.
159
C
57
B
B
Ex.
160
A
58
A
B
Ex.
161
B
59
A
B
Ex.
162
C
60
A
B
Ex.
163
A
61
A
B
Ex.
164
B
62
A
B
Ex.
165
C
63
A
B
Ex.
166
A
64
A
B
Ex.
167
B
65
A
B
Ex.
168
C
66
A
B
Ex.
169
A
67
A
B
Ex.
170
B
68
A
B
Ex.
171
C
69
A
B
Ex.
172
A
70
A
B
Ex.
173
B
71
A
B
Ex.
174
C
72
A
B
Ex.
175
A
73
A
B
Ex.
176
B
74
A
B
Ex.
177
C
75
A
B
Ex.
178
A
76
A
B
Ex.
179
B
77
A
B
Ex.
180
C
78
A
B
Ex.
181
A
79
A
B
Ex.
182
B
80
A
B
Ex.
183
C
81
A
B
[0000]
TABLE 10
Original
sheet for
chemical
conversion
Black-
Test
Chemical
treatment
ening
piece
conversion
(test
test
Appear-
Category
No.
treatment
piece No.)
result
ance
Ex.
184
A
82
A
D
Ex.
185
B
83
A
D
Ex.
186
C
84
A
D
Ex.
187
A
85
A
D
Ex.
188
B
86
A
D
Ex.
189
C
87
A
D
Ex.
190
A
88
D
B
Ex.
191
B
89
D
B
Comp. Ex.
192
C
90
D
B
Comp. Ex.
193
A
91
D
B
Comp. Ex.
194
B
92
D
B
Comp. Ex.
195
C
93
D
B
Comp. Ex.
196
A
94
D
B
Comp. Ex.
197
B
95
D
B
Comp. Ex.
198
C
96
D
B
Comp. Ex.
199
A
97
D
B
Comp. Ex.
200
B
98
D
B
Comp. Ex.
201
C
99
D
B
Comp. Ex.
202
A
100
D
B
Comp. Ex.
203
B
101
D
B
Comp. Ex.
204
C
102
D
B
[0103] As shown in Table 7 to Table 10, the plated steel sheets having a composite oxide film including vanadium, with the surface having a Zn hydroxide ratio of 40% or less, had excellent blackening resistance even when a chemical conversion coating is formed. In contrast, in the case of an adhering amount of vanadium in the composite oxide film of more than 10.0 mg/m 2 (test piece Nos. 31 to 36 and Nos. 82 to 87), the reactivity between the chemical conversion treatment liquid and the surface of the plating layer (composite oxide film) was decreased, and the chemical conversion treatment coating had white turbidity.
[0104] From the results, it is found that in the case of chemical conversion treatment, the adhering amount of vanadium in the composite oxide film is preferably adjusted to 10.0 mg/m 2 or less.
[0105] This application claims priority based on Japanese patent Application No. 2013-250139, filed on Dec. 3, 2013, the entire contents of which including the specification and the drawings are incorporated herein by reference.
INDUSTRIAL APPLICABILITY
[0106] The hot-dip Zn alloy-plated steel sheet obtained by the production method of the present invention is excellent in blackening resistance, and useful as plated steel sheet for use in, for example, roof materials and exterior materials for buildings, home appliances, and automobiles.
REFERENCE SIGNS LIST
[0000]
100 , 200 Cooling apparatus
110 Spray nozzle
120 , 230 Squeeze roll
130 Housing
210 Dip tank
220 Dip roller
300 Production line
310 Furnace
320 Plating bath
330 Wiping nozzle
340 Air jet cooler
350 Mist cooling zone
360 Water quenching zone
370 Skin pass mill
380 Tension leveler
390 Tension reel
400 Roll coater
410 Drying zone
420 Air cooling zone
S: Steel strip
|
This hot-dip Zn-alloy-plated steel sheet comprises: a steel sheet; a hot-dip Zn-alloy-plated layer arranged on a surface of the steel sheet; and a complex oxide coating film arranged on a surface of the hot-dip Zn-alloy-plated layer. The complex oxide coating film includes vanadium and a constituent component of the hot-dip Zn-alloy-plated layer, and the entire surface of the coating film satisfies the following formula (1): S[Hydroxide]/(S[Hydroxide]+S[Oxide])×100≦40. In formula (1): S[Oxide] is the area exhibited by a peak having a center at approximately 1022 eV ascribable to a Zn oxide in an intensity profile in XPS analysis of the surface of the complex oxide coating film; and S[Hydroxide] is the area exhibited by a peak having a center at approximately 1023 eV ascribable to a Zn hydroxide in an intensity profile in XPS analysis of the surface of the complex oxide coating film.
| 2
|
FIELD OF INVENTION
The present invention relates to improvement of traditional sleeping pillows.
BACKGROUND OF THE INVENTION
A traditional sleeping pillow having a rectangular sealed bag with loose filling basically has only one height. The height may vary from pillow to pillow. The pillows are used in hotel and at home. Hotel pillows have been a problem for travelers. The pillows may be either too high or too low, and a traveler just cannot do anything if his pillow is too high. The pillows at home are not ideal either. They may be a little bit too high for shoulder horizontal sleeping posture and a little bit too low for shoulder vertical posture. It is also known that some people need neck support and some don't. A traditional pillow is simply not very flexible in satisfying the different needs. There are special pillows. However, they have different configurations, are not as acceptable as the traditional pillows, and some do not fit in the traditional pillowcase. With minimum change from traditional pillow, this invention is to solve all these problems.
OBJECTIVES OF THE INVENTION
The primary objective of this invention is to improve traditional pillows such that they allow the user to easily choose, during sleep or not during sleep, to rest his head on a more comfortable height.
Another objective of this invention is to improve traditional pillows such that they allow the user to have the choice of various neck supports.
Yet another objective of this invention is to provide improved traditional pillows which can use traditional pillowcase in the market.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1.1 shows the front perspective view of a configuration of this invention.
FIG. 1.2 is the top view of the configuration shown in FIG. 1.1.
FIG. 2.1 is the front view of a variation of the configuration shown in FIG. 1 .
FIG. 2.2 is the top view of the configuration shown in FIG. 2.1.
FIG. 3.1 is the front view of another variation of the configuration shown in FIG. 1 .
FIG. 3.2 is the top view of the configuration shown in FIG. 3.1.
FIG. 4.1 is the top view of another configuration of this invention.
FIG. 4.2 is the 1 — 1 cross section view of the configuration shown in FIG. 4.1
FIG. 4.3 is the 2 — 2 cross section view of the configuration shown in FIG. 4.1.
FIG. 5.1 is the top view of still another configuration of this invention.
FIG. 5.2 is the 3 — 3 cross section view of the configuration shown in FIG. 5.1.
FIG. 5.3 is the 4 — 4 cross section view of the configuration shown in FIG. 5.1.
FIG. 6.1 is the top view of yet another configuration of this invention.
FIG. 6.2 is the 5 — 5 cross section view of the configuration shown in FIG. 6.1.
FIG. 6.3 is the 6 — 6 cross section view of the configuration shown in FIG. 6.1.
FIG. 7.1 is the top view of yet still another configuration of this invention.
FIG. 7.2 is the front view of the configuration shown in FIG. 7 . 1 .
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1.1 shows the front perspective view of a configuration of this invention. The pillow has a basic construct of a traditional pillow, i.e. a rectangular sealed bag with loose filling of fibers, beans, herbs, feathers, or air, except the middle portion of the pillow has a lateral valley [ 11 ]. The valley [ 11 ] is formed by connecting the middle portion of the upper shell and the corresponding portion of the lower shell of the bag, e.g. by sewing them together. The bottom of the valley [ 11 ] is a line [ 121 ]. When the pillow is in use, the bottom of the valley [ 11 ] may be pressed down to the bed. On each side of the valley [ 11 ] is a plateau [ 12 ]. When the pillow is used in a hotel, the user can choose to rest his head in the valley [ 11 ] if he is accustomed to a lower pillow, or on the plateau [ 12 ] if he is accustomed to a higher pillow. During sleep or not, one can also conveniently use the valley [ 11 ] for the shoulder horizontal sleeping posture, and the plateau [ 12 ] for the shoulder vertical sleeping posture.
FIG. 1.2 is the top view of the configuration shown in FIG. 1.1.
FIG. 2.1 is the front view of a variation of the configuration shown in FIG. 1.1 and FIG. 1.2. It shows a broadened valley [ 13 ]. The bottom of the valley [ 13 ] is a strip [ 131 ]. With the valley [ 13 ], the pillow gives more room for one to turn his head in the valley [ 13 ] and provides more height difference between its plateau and valley when the pillow is in use. The strip [ 131 ] shown has a uniform width. However, a fan-out strip (not shown), i.e. the width at one end of the strip is narrower than that at the other end, provides additional effects. One may get a stretched feeling on his neck if the narrow end of the strip is closer to his shoulder, and a compressed feeling if the wider end is closer to his shoulder. These ideas of valley broadening are also applicable to other configurations of this invention.
FIG. 2.2 is the top view of the configuration shown in FIG. 2.1.
FIG. 3.1 is the front view of another variation of the configuration shown in FIG. 1 . It shows a shallow valley [ 14 ], i.e. the upper and lower shells of the pillow are pulled close to but not touching each other. It is obvious that this idea of providing less pillow height difference between its plateau and valley is applicable to all other configurations of this invention.
FIG. 3.2 is the top view of the configuration shown in FIG. 3.1.
FIG. 4.1 is the top view of another configuration of this invention. It shows that a lateral valley [ 15 ] only runs through a portion of the pillow width. The rest of the pillow is a plateau [ 16 ]. In addition to the comforts that can be provided by the configuration shown in FIG. 1., this configuration can also provide neck support by the portion of the plateau [ 16 ] at the end of the valley [ 15 ]. One can get neck support by placing the portion under his neck and rest his head in the valley [ 15 ]. To have a firmer neck support, a block [ 112 ] of firmer material, like foam rubber or a small air bag with sigher air pressure, may be used for the filling in the portion of the plateau [ 16 ] at the end of the valley [ 15 ].
FIG. 4.2 is the 1 - 1 cross section view of the configuration shown in FIG. 4.1
FIG. 4.3 is the 2 — 2 cross section view of the configuration shown in FIG. 4.1.
FIG. 5.1 is the top view of still another configuration of this invention. A laterally elongated concavity [ 17 ] is in the middle portion of the pillow. The concavity [ 17 ] is surrounded by a plateau [ 18 ]. This configuration provides neck support by using the portion of plateau [ 18 ] at either end of the elongated concavity [ 17 ]. The elongated concavity [ 17 ] provides room between the top of one's head and the portion of the plateau [ 18 ] at the other end of the concavity [ 17 ] such that he would not feel an uncomfortable pressure caused by the portion of plateau [ 18 ] on the top of his head. Likewise, to have a firmer neck support, a block [ 112 ] of firmer material, like foam rubber or a small air bag with higher air pressure, may be used for the filling in the portion of the plateau [ 18 ] at each end of the concavity [ 17 ].
FIG. 5.2 is the 3 — 3 cross section view of the configuration shown in FIG. 5.1.
FIG. 5.3 is the 4 — 4 cross section view of the configuration shown in FIG. 5.1. This figure shows that the bottom of the concavity [ 17 ] does not contain filling between the upper shell and the lower shell of the bag.
FIG. 6.1 is the top view of yet another configuration of this invention. The configuration has a cross concavity [ 110 ] in the middle of the pillow. The concavity [ 110 ] is surrounded by a plateau [ 111 ]. This configuration provides neck support like the configuration shown in FIG. 5 . When the pillow is in use, the height difference between the bottom of the concavity and plateau is more than that of the configuration shown in FIG. 5 . It also provides more room for one to turn his head in the concavity [ 110 ]. Likewise, to have a firmer neck support, a block [ 112 ] of firmer material, like foam rubber or a small air bag with higher air pressure, may be used for the filling in the portion of the plateau [ 111 ] at each end of the concavity [ 110 ]. It is obvious that the cross concavity [ 110 ] can be replaced by a concavity of ellipse, rectangle, heart, star, butterfly, letter, or other pattern. In the market, there are small circular concavities on a pillow/cushion for sofa/chair. They are more for ornament purposes. They can not be used for height choices or neck support of a sleeping pillow.
FIG. 6.2 is the 5 — 5 cross section view of the configuration shown in FIG. 6.1.
FIG. 6.3 is the 6 — 6 cross section view of the configuration shown in FIG. 6.1.
FIG. 7.1 is the top view of yet still another configuration of this invention. This configuration has two side-by-side connected small pillows [ 114 ]. The connection is made through one or more connectors [ 115 ] secured to the pillows [ 114 ]. Each of the connectors [ 115 ] is flat and flexible, like VELCRO, and can make the distance between the pillows [ 114 ] easily adjustable by user. The use of connectors [ 115 ] can serve the purpose of the configuration shown in FIG. 2.1 with more flexibility. The connectors can (not shown) also allow the user to overlap a corner of one of the two pillows [ 114 ] with the adjacent corner of the other pillow [ 114 ] such that the overlapped corners become a neck support. The height of the neck support depends on the amount of the overlap and is easily adjustable by the user.
FIG. 7.2 is the front view of the configuration shown in FIG. 7.1.
Although this invention has been described with a certain degree of particularity, it is to be understood that the present disclosure has been made by way of example only and that numerous changes in the detailed construction may be resorted to without departing from the spirit and scope of the invention as hereinafter claimed.
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Traditional rectangular sleeping pillows with filling are improved. There are several pillow configurations in this invention. Each configuration has two heights available for its user to choose. The user can also make choice of the neck support or not. The arrangement of the two heights also allows the user to easily get proper supports for two sleeping postures, i.e. shoulder vertical and shoulder horizontal. Portion of the pillow contour gives comfortable and secure feeling like baby sleeps on mother's breast. All the configurations can use existing pillowcase in the market.
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BACKGROUND AND SUMMARY OF THE INVENTION
The invention relates to a radial fanwheel with a hub and a plurality of fan blades, the blades being in an array that is disposed concentrically with respect to the hub and forwardly bowed (i.e., curved as if bent forwardly at its ends so as to form a forwardly open concave surface), the blades being linked to the hub by spokes.
Radial fanwheels of the type described above, also known as drum fanwheels, are used for single-flow blowers, i.e., blowers with a unilateral intake; or for double-flow blowers, i.e., blowers with a bilateral intake. It is known that the fan blades can be mounted to the hub by means of a disk, whereby the tips of the fan blades are held by rings or cover disks. When the disk, which serves as a connecting part, is connected with one of the two cover disks, the fanwheel is limited to a single-flow blower design. It is also possible to attach the connecting disk to the fan blades between the two covered disks, producing a radial fanwheel suitable for a double-flow blower. The arrangement of the disk determines the flow distribution, i.e., the air volume to be drawn in from one side or the other. If a different distribution is desired, another radial fanwheel with a suitably different arrangement of the connecting disk must be manufactured.
Radial fanwheels of this type are also oriented rotational-directionwise. Their asymmetrical design makes it impossible to convert them to a different rotational direction simply by turning them through 180°. Instead, different radial fanwheels must be manufactured for clockwise rotation and for counterclockwise rotation. These measures result in a considerable manufacturing cost increase and in costly stock maintenance.
It has also been proposed (German Patent Application No. P 29 39 385.9-15) to provide the connecting disk with apertures, so that, in effect, the fan blades are linked to the hub by spokes. This design has the advantage of producing a radial fanwheel which can be used as both a single-flow blower and a double-flow blower, since the air volumes drawn in are automatically distributed through the openings. In this design also, however, at least two different radial fanwheels must be manufactured to permit one arrangement with clockwise rotation and another arrangement with counterclockwise rotation, resulting in high manufacturing costs.
Thus, a principal object of the present invention is to achieve a radial fanwheel of the type described above that can be used either for a single-flow or a double-flow blower, with clockwise or counterclockwise rotation, independently of the intake direction. This object is attained in a preferred embodiment by virtue of the fact that backwardly-curved spokes are staggered with respect to one another and arranged successively around the circumference relative to the radial center plane, each of said spokes holding a fan blade in the vicinity of one of its ends in such a manner that each fan blade is connected at one end with the fan blade ahead of it in the circumferential direction and at the other end with the fan blade behind it.
This design makes it possible to devise a radial fanwheel whose structure is symmetrical with respect to the radial center plane, so that it can be used for either clockwise or counterclockwise rotation by simply turning it through 180°. It is also possible to use this radial fanwheel in either single-flow or double-flow blowers, since the spokes do not significantly impede the air flow and thereby permit free air distribution. An endless meander-shaped structure composed of fan blades and running in the circumferential direction of the radial fanwheel is conceptually part of this invention. Furthermore, this structure is manufacturable as a plastic part by using an injection molding machine, especially since no rings or cover disks are provided for the fan blades. In this regard, it is noted that the curved shape of the blades is produced by the shape of the mold cavity so that, while the term "bowed" is used relative to blades produced in such a manner, it should be understood to mean only that they are in the shape of a simple curve and not that the blades are actually "bent" from a straight configuration.
In order to produce a radial fanwheel of this type while designing the invention so that it is capable of adjusting automatically to different load conditions and forces which develop, especially in conjunction with a drive motor which changes its rotational speed as a function of load, a provision is made for the spokes and fan blades and/or the connecting elements linking the fan blades to be so dimensioned that the radial length of the spokes can change by elastic modification of the curvature of the spokes, and the diameter of the blade ring formed by the fan blades can be modified by elastic twisting and/or bending of the fan blades and/or of the connectors, depending on the loads which develop.
A radial fanwheel in accordance with the present invention has, firstly, the advantage that balancing is no longer required, since any slight imbalance which might possibly be present as a result of the injection molding technique will cause the radial fanwheel to deform slightly elastically during operation to conform to this imbalance, so that it runs smoothly after this deformation has taken place. There is no feedback of the imbalance through the elastic spokes, so that no balancing measures need be taken. A fanwheel of this type also has the advantage that it adapts to a certain extent to load conditions as they change, and serves to offset them. For example, if the load increases, the aerodynamic forces acting circumferentially on the fan blades cause the spokes (which are curved oppositely relative to the forwardly bowed blades) to flex, thereby reducing the diameter of the blade ring. In the case of the drive motor which changes its rotational speed as a function of load, a similar diameter reduction occurs when a reduction of the rpm reduces the centrifugal forces which stretch the spokes and expand the blade ring. In the opposite case, when the load decreases, the spokes stretch and increase the blade ring diameter in such fashion that the effect of the aerodynamic forces is less and the effect of the centrifugal force is greater.
In an advantageous embodiment, provision is made for the spokes, fan blades, and connecting elements to be so designed and/or dimensioned that, in the event of load-dependent deformation, essentially constant blade geometry is maintained. This measure ensures that the entry and exit angles of the fan blades likewise change as a function of load, and adjust themselves to the changed load. When the load decreases, the entrance and exit angles increase; they decrease when the load increases.
These and further objects, features and advantages of the present invention will become more obvious from the following description when taken in connection with the accompanying drawings which show, for purposes of illustration only, several embodiments in accordance with the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial axial view of a first embodiment of a fanwheel according to the invention, under different load conditions and/or at different rotational speeds;
FIG. 2 is a cross section along line II--II in FIG. 1;
FIG. 3 is a cross section along line III--III in FIG. 1;
FIG. 4 is a cross section along line IV--IV through the fan blades represented as lying in the plane of the drawing, in the embodiment shown in FIGS. 2 and 3;
FIG. 5 is a cross section similar to FIG. 4 through another embodiment; and
FIG. 6 is a cross section similar to FIG. 4 through a third embodiment of a radial fanwheel according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the embodiment according to FIGS. 1 to 4, a hub 1 is provided, said hub being connected by spokes 11 and 12 with a blade ring formed by fan blades 9 and 10. Fan blades 9 and 10 are connected together in such fashion that each of fan blades 9 or 10 is linked at one end with the following fan blades 9 or 10 via a connecting element 13, extending essentially circumferentially. As a result, fan blades 9 and 10 produce a meander-shaped endless structure, running circumferentially around the radial fanwheel. Each fan blade 9 and 10 is linked to the hub by a spoke 11 or 12, respectively. Spokes 11 and 12 are offset relative to each next successive spoke and linked to the hub, symmetrically with respect to a radially extending center plane P extending transverse to the longitudinal axis of the hub and displaced slightly outside the plane P. Plane P also being understood to be a plane of symmetry on either side of which the fanwheel is substantially symmetrical; the symmetry being interrupted by the portion on one side of the plane being mirror image of the other side but circumferentially offset. Spokes 11 and 12 are each tilted slightly axially outward in opposite directions, so successive spokes 11 and 12 form a rough V-shape. The spokes are connected to fan baldes 9 and 10 by smooth, continuous transitions at short distances from the corresponding ends. The endless meander-shaped structure made of fan blades 9 and 10 is thus held in two planes relative to hub 1, said planes being tilted in the rough shape of a V with respect to one another, thus reliably preventing wobbling of this structure, i.e., the blade ring. Spokes 11 and 12 have the form of ribs with flat, rectangular cross sections, so arranged that their narrow sides point in the axial direction in the vicinity of the hub and over most of their length, so that they are warped only for a short distance before the point at which they connect to fan blades 9 and 10. In this way, the air flow to the fan blades is impeded as little as possible.
As FIG. 1 shows, spokes 11 and 12 are bowed in circumferential direction D. This gives the spokes a certain spring action which serves to isolate vibrations which might otherwise be transmitted from the blade ring to the hub. The curvature ρ (=1/R) is chosen so that the spokes lead in circumferential direction D, thereby improving the flow to the blades.
In the embodiment shown in FIGS. 1 to 4, the successive fan blades 9 and 10, viewed in a direction radial to the rotational axis of the fanwheel, are each mounted at a slight angle, in alternate directions, to the rotational axis, as is shown particularly clear in FIG. 4. However, it is also possible to select a different arrangement of fan blades 9 and 10, for example, one corresponding to the embodiment shown in FIG. 5, whereby fan blades 9 and 10 extend alternately at angles to the rotational axis and parallel to the rotational axis of the radial fanwheel. In this way, one side can be used preferentially in a blower of the double-flow type, for example, as far as air intake is concerned.
Moreover, it is also possible to provide other shapes for the fan blades; for example, fan blades 9 and 10 shown in FIG. 6 are curved sinusoidally with respect to the rotational axis of the radial fanwheel and are linked together by round conncting elements 13. The diagonal and curved arrangement of the fan blades has the advantage that the noise generated by a radial blower equipped with a radial fanwheel of this type can be reduced, since fan blades 9 and 10 shear the incoming air at a tongue adjoining the outlet opening of a spiral housing, so that no abrupt load occurs which could cause noise to be generated.
Spokes 11 and 12 are curved in opposite directions relative to fan blades 9 and 10, so that fan blades 9 and 10, which are allocated to spokes 11 and 12, respectively, form segments of a sine curve with these spokes. Spokes 11 and 12 are, therefore, twice as long as fan blades 9 and 10. As FIGS. 2 and 3 show, spokes 11 and 12 taper from hub 1 to fan blades 9 and 10 slightly along their axes. In the same way, they can be made to taper additionally in terms of their circumferential extent, i.e., their thickness.
Spokes 11 and 12, fan blades 9 and 10, and connecting elements 13 are manufactured from an elastic plastic material of a relatively small thickness on the order of 0.5-2 mm, so that they can deform elastically even when relatively low forces develop. Depending on the nature of the forces, this deformation primarily takes the form of a change in the curvature (ρ=1/R) of spokes 11 and 12 in such fashion that they bow further in circumferential direction D, or stretch counter thereto, whereby the meander-shaped blade ring formed by fan blades 9 and 10 necessarily decreases and increases its diameter, respectively.
Connecting elements 13 are so designed that they extend from the outer ends of fan blades 9 and 10 for only approximately half their height, thus permitting a large diameter for an intake opening to a blower housing. When the diameter increases or decreases, connecting elements 13 preferably are slightly bent or compressed, as shown by arrows 14 or 15 (FIG. 4), about an essentially radial bending axis. Connecting elements 13 then ensure that, when the diameter changes, the blade geometry essentially remains constant, as will be described in greater detail hereinbelow. The connecting elements are then set at a slight angle to their original positions, relative to the radial direction. Compensation of the resultant differences is then produced by a slight twisting of fan blades 9 and 10.
The relatively high elastic deformability of the complete radial fanwheel, with the exception of the hub, results in considerable advantages. First of all, balancing of the fanwheel is eliminated, since any imbalance which may be present results in only an elastic deformation of the radial fanwheel during operation, whereby feedback of vibrations to hub 1 is avoided by the spring action of spokes 11 and 12. In addition, the relatively high deformability ensures that the radial fanwheel adjusts to changing load conditions in conjunction with a load-dependent rotation-changing drive motor, providing feedback to said motor. The radial fanwheel is preferably used in radial blowers for motor-vehicle ventilation, motor-vehicle heating, or motor-vehicle air-conditioning in conjunction with a drive motor which changes its rotational speed as a function of load. Different operation conditions and/or control states of the ventilation, heating, or air-conditioning systems change the mass throughput through the radial fanwheel, for example, as a consequence of changes in the dynamic pressure, valve control, heater or air-conditioner, or even as a function of whether a sunroof or window or the like is opened or closed in a vehicle. As a result of this mass throughput, the aerodynamic forces acting on the individual fan blades change as well, as indicated by the reference mark P L , shown as acting essentially in a circumferential direction, for example, in FIG. 1. In addition to these aerodynamic forces which act opposite to circumferential direction D, the centrifugal forces P Z , which are a function of the rotational speed, act upon fan blades 9 and 10 and spokes 11 and 12. As a result of their deformability, and as a function of the forces, a certain equilibrium is established which determines the shape of the radial fanwheel in each case.
For example, if the aerodynamic forces P L increase on the basis of the operating state shown at the center of FIG. 1, a modified equilibrium of forces will occur wherein spokes 11 and 12 will have a greater curvature ρ1 (=1/R 1 ). At the same time, the diameter of the blade ring formed by fan blades 9 and 10 will shrink (FIG. 1, right dashed lines). Since the blade geometry remains essentially constant, the entrance angle α will decrease to a value of α 1 and the exit angle β will decrease to a value of β 1 . This deformation and the associated adaptation to the changed load is reinforced further when a drive motor, which changes its rotational speed as a function of load, is provided, since an increase in the load reduces the motor rpm so that centrifugal forces P Z likewise become less, increasing the tendency toward greater curvature of the spokes.
In the opposite case, i.e., when the load drops, the influence of centrifugal forces P Z predominates, so that the spokes stretch more, i.e., they take on a reduced curvatureρ2 (=1/R 2 ). Since the blade geometry remains essentially constant, the entrance angle α 2 and the exit angle β 2 (FIG. 2, left) increase. Here again, the effect is further intensified when a drive motor with load-dependent rpm characteristics is used, i.e., a drive motor which increases its rpm when the load decreases.
The range of possible changes in the curvature ρ(=1/R) of spokes 11 and 12, as shown in FIG. 1, increasing or decreasing the diameter of the blade ring formed by fan blades 9 and 10, is 1 to 2 mm. For the sake of ease in illustration, FIG. 1 shows these changes as being more extensive.
The elasticity of the fanwheel has the further advantage that a slight wobble, caused, for example, by manufacture, does not have a negative effect, as might happen, for example, if connecting elements 13 were not absolutely parallel to the rotational axis.
While I have shown and described various embodiments in accordance with the present invention, it is understood that the same is not limited thereto, but is susceptible of numerous changes and modifications as known to those skilled in the art, and I, therefore, do not wish to be limited to the details shown and described herein, but intend to cover all such changes and modifications as are encompassed by the scope of the appended claims.
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The invention relates to a radial fanwheel, wherein the fan blades are connected to a hub by spokes. Each fan blade is connected by connecting elements to the adjacent fan blades in the vicinity of their ends. Specifically, the spokes and connecting elements, as well as the fan blades themselves, are elastically deformable by the loads which develop.
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TECHNICAL FIELD
[0001] The disclosed inventive concept relates generally to fasteners for use in coupling two components together. More particularly, the disclosed inventive concept relates to edge clip fasteners that are self-locking. A trigger is movably displaced from its initial, pre-locking position, to a locking position. In the locking position, the position of the trigger is locked while the component is fixed to the edge clip fastener. Also in the locking position, the trigger is entirely disposed within the body of the edge clip fastener.
BACKGROUND OF THE INVENTION
[0002] Clip fasteners replace traditional screw fixings in many applications and have may uses in a wide variety of industries. Broadly speaking, clip fasteners are utilized for fastening two or more components together. Challenges faced by industries include different types of tools needed for assembly and different materials to be fastened together. Other challenges include fastening locations, which may offer only limited access for both assembly during manufacture and removal or adjustment during maintenance. Each of these challenges has the potential for increasing assembly cost to manufacturers because of added tooling as well as extra assembly time.
[0003] Clip fasteners commonly find utility in the energy and automotive sectors. In the energy sector, clip fasteners are commonly used to hold solar panels to underlying framework. Also in the energy sector, clip fasteners are also used to fasten and ground photovoltaic modules and in the fastening of electric cables.
[0004] In the automotive sector, clip fasteners have many uses, including in air bag assembly, window construction, instrument panels and interior and exterior trim attachment. These are some examples of the many uses known for clip fasteners.
[0005] Modern demands on the design and construction of clip fasteners mean that new clip fastener solutions need to contribute to ease of assembly as used in production (particularly in view of increasing automation) and provide excellent attachment strength, while maintaining high reliability and low production costs. Compliance with the need for standardization and the requirements of the automotive industry has proved challenging to current clip fastener designs.
[0006] Accordingly, and as is the case in many industries, known clip fasteners approaches to attaching components together are undesirable and impractical. An improved arrangement for attaching two components together remains wanting.
SUMMARY OF THE INVENTION
[0007] The disclosed inventive concept overcomes the problems associated with edge clips by providing a simple and cost-effective response to the demands of the marketplace. Particularly, the self-locking (or self-latching or self-retaining) edge clip for attachment of a component according to the disclosed inventive concept includes a u-shaped clip body adaptable between a first position in which the component may be freely inserted to a second position in which the component is captured by the clip. The clip body includes upper and lower legs and a curved end that connects the legs. The clip body has an open end into which the component to be attached is inserted. The legs are movable between an initial, spaced apart arrangement in which the component may be inserted into the clip body, to a final component-engaging position, in which the component is captured between the legs. The edge clip of the disclosed inventive concept may have a broad variety of applications that include, but are not limited to, attachment of components in an automobile.
[0008] A slidably movable u-shaped trigger is attached to the clip body. According to the preferred embodiments, the u-shaped trigger is provided substantially if not entirely within the clip body. A trigger-guiding channel is formed on the inner wall of one or both of the legs of the clip body. The trigger is slidably movable in the channel. An interlock system comprising a first window and a second window formed in one of the legs of the clip body and a flange extending from the trigger. The first window is provided so that the trigger flange may be locked in its initial position in which the legs are held in their spaced apart positions by the trigger. The second window is provided so that the trigger flange may be locked in its final position in which the legs apply locking tension to the component. The second window may be formed in the curved end of the clip body.
[0009] Variations of the self-locking edge clip according to the disclosed inventive concept include a frangible bridge that attaches the trigger to the clip body. The frangible bridge may be broken for placement of the trigger within the clip body prior to attachment of the component. In another variation, the trigger includes an underside that slides along the inner wall of one of the legs, guided on both sides by a pair of spaced-apart lateral arms that extend over the opposed edges of the leg. In yet another variation of the disclosed inventive concept, the trigger may be ejected out of the clip body upon insertion of the component.
[0010] Upon insertion of the component into the clip body, the trigger is displaced from its initial position in which the trigger holds the legs apart to its final position when the trigger is pushed clip-inward, resulting in the legs applying a capturing tension to the component. One or more barbs may be provided that extend from the inside wall of one of the legs to help frictionally engage the component, thereby further assuring that, once locked into the edge, clip, the component is not easily released. Provision of the barbs in their various embodiment minimize or eliminate entirely the risk of scratching of the painted surface of the component being attached. By avoiding the scratching of the painted surface, the risk of corrosion is also minimized or entirely eliminated.
[0011] The above advantages and other advantages and features will be readily apparent from the following detailed description of the preferred embodiments when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] For a more complete understanding of this invention, reference should now be made to the embodiments illustrated in greater detail in the accompanying drawings and described below by way of examples of the invention wherein:
[0013] FIG. 1 is a perspective view of an edge clip according to a first embodiment of the disclosed inventive concept shown in its initial position;
[0014] FIG. 2 is a view similar to that of FIG. 1 , but illustrating the clip edge in cross-section;
[0015] FIG. 3 is a side view of the edge clip shown in FIG. 1 illustrating a component in position in the clip body awaiting insertion;
[0016] FIG. 4 is the same view as FIG. 3 but showing the edge clip and component in cross-section;
[0017] FIG. 5 is a top plan view of the edge clip shown in FIG. 1 again illustrating a component in the clip body awaiting insertion;
[0018] FIG. 6 is an end view of the edge clip and component combination of FIG. 5 in which the component is awaiting insertion;
[0019] FIG. 7 is a side view of the edge clip according to the first embodiment of the disclosed invention in its final position with the component fully inserted;
[0020] FIG. 8 is the same view as FIG. 7 but showing the edge clip in its final position together with the component in cross-section;
[0021] FIG. 9 is a top plan view of the edge clip according to the first embodiment of the disclosed inventive concept in its final position with the component fully inserted;
[0022] FIG. 10 is an end view of the edge clip and component shown in FIG. 9 ;
[0023] FIG. 11 is a perspective view of an edge clip according to a second embodiment of the disclosed inventive concept shown in its initial position;
[0024] FIG. 12 is a view similar to that of FIG. 11 , but illustrating the clip edge in cross-section;
[0025] FIG. 13 is a side view of the edge clip shown in FIG. 11 illustrating a component in position in the clip body awaiting insertion;
[0026] FIG. 14 is the same view as FIG. 13 but showing the edge clip and component in cross-section;
[0027] FIG. 15 is an end view of the edge clip and component combination of FIG. 14 in which the component is awaiting insertion;
[0028] FIG. 16 is a top plan view of the edge clip shown in FIG. 11 again illustrating a component in the clip body awaiting insertion;
[0029] FIG. 17 is a side view of the edge clip according to the second embodiment of the disclosed invention in its final position with the component fully inserted;
[0030] FIG. 18 is the same view as FIG. 17 but showing the edge clip in its final position together with the component in cross-section;
[0031] FIG. 19 is a top plan view of the edge clip according to the second embodiment of the disclosed inventive concept in its final position with the component fully inserted;
[0032] FIG. 20 is an end view of the edge clip and component shown in FIG. 19 ;
[0033] FIG. 21 is a perspective view of an edge clip according to a third embodiment of the disclosed inventive concept shown in its initial position;
[0034] FIG. 22 is a perspective view of the edge clip shown in FIG. 21 illustrating a component in position in the clip body awaiting insertion in which the edge clip and the component are shown in cross-section;
[0035] FIG. 23 is a perspective view of the edge clip shown in FIG. 21 illustrating a component in position in the clip body awaiting insertion;
[0036] FIG. 24 is a side view of the edge clip according to the third embodiment of the disclosed invention in its final position with the trigger has been fully inserted and the component is in its captured position;
[0037] FIG. 25 is a top plan view of the edge clip according to the third embodiment of the disclosed inventive concept in its final position with the component fully inserted;
[0038] FIG. 26 is a perspective view of an edge clip according to a fourth embodiment of the disclosed inventive concept shown in its initial position;
[0039] FIG. 27 is a view similar to that of FIG. 26 , but illustrating the clip edge in cross-section;
[0040] FIG. 28 is a view similar to that of FIG. 27 , but illustrating the trigger having been broken off of the lower leg of the clip body and inserted into the edge clip body to receive the component;
[0041] FIG. 29 is a perspective view of the edge clip according to the fourth embodiment of the disclosed inventive concept shown in its initial position with a component in position awaiting insertion;
[0042] FIG. 30 is the same view as FIG. 29 but shown in cross-section;
[0043] FIG. 31 is the same view as FIG. 29 but showing the component fully inserted and the edge clip in its final position;
[0044] FIG. 32 is the same view as FIG. 31 but shown in cross-section;
[0045] FIG. 33 is a perspective view of an edge clip according to a fifth embodiment of the disclosed inventive concept shown in its initial position;
[0046] FIG. 34 is a view similar to that of FIG. 33 , but illustrating the clip edge in cross-section;
[0047] FIG. 35 is a side view of the edge clip in its initial position as shown in FIG. 33 and further illustrating a component in position in the clip body awaiting insertion;
[0048] FIG. 36 is the same view as FIG. 35 but shown in cross-section;
[0049] FIG. 37 is a top plan view of the edge clip shown in FIG. 33 again illustrating a component in the clip body awaiting insertion;
[0050] FIG. 38 is a side view of the edge clip in its final position in which the trigger has been fully inserted and the component is in its captured position;
[0051] FIG. 39 is the same view as FIG. 38 but shown in cross-section; and
[0052] FIG. 40 is a plan view of the edge clip in its final position in which the trigger has been fully inserted and the component is in its captured position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0053] As those of ordinary skill in the art will understand, various features of the embodiments illustrated and described with reference to any one of the Figures may be combined with features illustrated in one or more other Figures to produce alternative embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. However, various combinations and modifications of the features consistent with the teachings of the present disclosure may be desired for particular applications or implementations.
[0054] Various embodiments of the disclosed inventive concept are illustrated in the figures and are discussed in conjunction therewith. Specifically, FIGS. 1 through 10 illustrate a first embodiment of the disclosed inventive concept. FIGS. 11 through 20 illustrate a second embodiment of the disclosed inventive concept. FIGS. 21 through 25 illustrate a third embodiment of the disclosed inventive concept. FIGS. 26 through 32 illustrate a fourth embodiment of the disclosed inventive concept. And FIGS. 33 through 40 illustrate a fifth embodiment of the disclosed inventive concept. It is to be understood that each embodiment as illustrated is suggestive and not intended as being limiting, as sizes and overall configurations may be varied without deviating from the scope and spirit of the various embodiments of the disclosed inventive concept.
[0055] Referring to the first embodiment of the disclosed inventive concept illustrated in FIGS. 1 through 10 , an edge clip, generally illustrated as 10 , is shown in perspective view. The edge clip 10 has multiple applications but is generally used to hold a component under tension to the clip, thus providing broad application across multiple industries. The edge clip 10 includes a generally u-shaped clip body 12 . The clip body 12 may be composed of any material capable of generating a clamp load to hold a component with enough tension so as to prevent the component from separating from the edge clip 10 .
[0056] The clip body 12 includes a first or upper leg 14 and a second or lower leg 16 . The first leg 14 and the second leg 16 are connected by a curved clip end 18 . Formed on the inner side of the first leg 14 is a first deep drawn channel 20 and formed on the inner side of the second leg 16 is a second deep drawn channel 22 . The widths of the deep drawn channels 20 and 22 may be other than those shown and are not necessarily the same.
[0057] To assure that the component is securely held to the clip body 12 , at least one but preferably two barbs are provided. Most preferably a first barb 24 and a second barb 24 ′ are formed on the first leg 14 . The barbs 24 and 24 ′ assure that only unidirectional movement of the component into the clip body 12 is possible. The barbs 24 and 24 ′ may have a variety of shapes, including but not limited to flat, sharp, round, and spiked.
[0058] The first leg 14 includes an upturned end 26 at its end opposite the curved clip end 18 . The upturned end 26 allows for easy insertion of the component into the clip body 12 . A first window 28 is formed in the deep drawn channel 20 of the first leg 14 . The first window 28 is relatively close to the upturned end 26 of the first leg 14 . An elongated second window 29 is also formed in the deep drawn channel 20 of the first leg 14 . The second window 29 extends into the curved clip end 18 .
[0059] A movable trigger 30 is provided within the clip body 12 . The movable trigger 30 includes first or upper trigger leg 31 having a clip body engagement flange 32 extending therefrom. The movable trigger 30 also includes a second or lower leg 34 that is attached to the first leg 31 by a curved trigger end 36 . The first leg 31 of the clip body 12 is slidably positioned in the deep drawn channel 20 of the first leg 14 of the clip body 12 . The second leg 34 of the clip body 12 is slidably positioned in the deep drawn channel 22 of the second leg 16 . The window 29 formed in the clip body 12 is sufficiently large so that the trigger 30 may pass therethrough upon insertion of the component as discussed below.
[0060] The clip body 12 is provided to the end user in its pre-attachment state as illustrated in FIGS. 1 through 6 . In this state, the movable trigger 30 is positioned toward the open end of the clip body 12 . In this position, the flange 32 of the trigger 30 engages the first window 28 . This engagement prevents the trigger 30 from prematurely being moved out of position. As illustrated in FIGS. 1 through 4 , the pre-attachment position of the trigger 30 maintains a widely spaced relationship between the ends of the first leg 14 and the second leg 16 , thereby allowing insertion of the component therebetween.
[0061] Upon initial insertion of a component 38 into the clip body 12 as illustrated in FIGS. 3 through 6 , the leading edge of the component 38 is placed into contact with the inside of the curved clip end 18 . As the component 38 is pushed clip-inward by the operator into the clip body 12 , the leading edge of the component 38 forces the flange 32 of the trigger 30 to become disengaged from the window 28 .
[0062] Clip-inward movement of the component 38 continues until the flange 32 of the trigger 30 is moved into and past the second window 29 , thereby being ejected out of the clip body 12 . With the component 38 inserted into the clip body 12 to its maximum position, the maximum tension applied to the component 38 by the barbs 24 and 24 ′ prevents release of the component 38 from the clip body 12 .
[0063] Referring to the second embodiment of the disclosed inventive concept illustrated in FIGS. 11 through 20 , an edge clip, generally illustrated as 50 , is shown in perspective view. Like the edge clip 10 referenced above, the edge clip 50 has multiple applications but is generally used to hold a component under tension to the clip, thus providing broad application across multiple industries. The edge clip 50 includes a generally u-shaped clip body 52 . The clip body 52 also may be composed of any material capable of generating a clamp load to hold a component with enough tension so as to prevent the component from separating from the edge clip 50 .
[0064] The clip body 52 includes a first or upper leg 54 and a second or lower leg 56 . The first leg 54 and the second leg 56 are connected by a solid curved clip end 58 . Formed on the inner side of the first leg 54 is a first deep drawn channel 60 and formed on the inner side of the second leg 56 is a second deep drawn channel 62 . The widths of the deep drawn channels 60 and 62 may be other than those shown and are not necessarily the same.
[0065] To assure that the component is securely held to the clip body 52 , at least one but preferably two barbs are provided. Most preferably a first barb 64 and a second barb 64 ′ are formed on the first leg 54 . The barbs 64 and 64 ′ assure that only unidirectional movement of the component into the clip body 52 is possible. The barbs 64 and 64 ′ may have a variety of shapes, including but not limited to flat, sharp, round, and spiked.
[0066] The first leg 64 includes an upturned end 66 at its end opposite the curved clip end 58 . The upturned end 66 allows for easy insertion of the component into the clip body 52 . A first window 68 is formed in the deep drawn channel 60 of the first leg 54 . The first window 68 is relatively close to the upturned end 66 of the first leg 54 . A second window 70 is also formed in the deep drawn channel 60 of the first leg 54 , although the second window 70 is relatively close to the curved clip end 58 .
[0067] A movable trigger 72 is provided within the clip body 52 . The movable trigger 72 includes first or upper trigger leg 74 having a clip body engagement flange 76 extending therefrom. The movable trigger 72 also includes a second or lower leg 78 that is attached to the first leg 74 by a curved trigger end 80 . The first leg 54 of the clip body 52 is slidably positioned in the deep drawn channel 60 of the first leg 54 of the clip body 52 . The second leg 78 of the clip body 52 is slidably positioned in the deep drawn channel 62 of the second leg 56 .
[0068] The clip body 52 is provided to the end user in its pre-attachment state as illustrated in FIGS. 11 through 15 . In this state, the movable trigger 72 is positioned toward the open end of the clip body 52 . In this position, the flange 76 of the trigger 72 engages the first window 68 . This engagement prevents the trigger 72 from prematurely being moved out of position. As illustrated in FIGS. 11 through 14 , the pre-attachment position of the trigger 72 maintains a widely spaced relationship between the ends of the first leg 54 and the second leg 56 , thereby allowing insertion of the component therebetween.
[0069] Upon initial insertion of the component 38 into the clip body 52 as illustrated in FIGS. 13 through 16 , the leading edge of the component 38 is placed into contact with the inside of the curved clip end 58 . As the component 38 is pushed clip-inward by the operator into the clip body 52 , the leading edge of the component 38 forces the flange 76 of the trigger 72 to become disengaged from the first window 68 . Clip-inward movement of the component 38 continues until the flange 76 of the trigger 72 is moved into engagement with the second window 70 , as illustrated in FIGS. 17 through 20 . With the component 38 inserted into the clip body 52 to its maximum position, the maximum tension applied to the component 38 by the barbs 64 and 64 ′ prevents release of the component 38 from the clip body 52 .
[0070] Referring to the third embodiment of the disclosed inventive concept illustrated in FIGS. 21 through 25 , an edge clip, generally illustrated as 100 , is shown in perspective view. Like the edge clips 10 and 50 referenced above, the edge clip 100 has multiple applications but is generally used to hold a component under tension to the clip, thus providing broad application across multiple industries. The edge clip 100 includes a generally u-shaped clip body 102 . The clip body 102 also may be composed of any material capable of generating a clamp load to hold a component with enough tension so as to prevent the component from separating from the edge clip 100 .
[0071] The clip body 102 includes a first or upper leg 104 and a second or lower leg 106 . The first leg 104 and the second leg 106 are connected by a solid curved clip end 108 . Formed on the inner side of the second leg 106 is a deep drawn channel 110 . The width of the deep drawn channel 110 may be other than that shown.
[0072] To assure that the component is securely held to the clip body 102 , at least one but preferably two barbs are provided. Most preferably a first barb 112 and a second barb 112 ′ are formed on the first leg 104 . The barbs 112 and 112 ′ assure that only unidirectional movement of the component into the clip body 102 is possible. The barbs 112 and 112 ′ may have a variety of shapes, including but not limited to flat, sharp, round, and spiked.
[0073] The first leg 104 includes an upturned end 114 at its end opposite the curved clip end 108 . The upturned end 114 allows for easy insertion of the component into the clip body 102 . A first window 116 is formed in first leg 104 . The first window 116 is relatively close to the upturned end 114 of the first leg 104 . A second window 118 is also formed in the first leg 104 . The second window 118 is relatively close to the curved clip end 108 .
[0074] A movable trigger 120 is provided within the clip body 102 . The movable trigger 120 includes first or upper trigger leg 122 having a clip body engagement flange 124 extending therefrom. The movable trigger 120 also includes a second or lower leg 126 that is attached to the first leg 122 by a curved trigger end 128 . The second leg 126 of the trigger 120 is slidably positioned in the deep drawn channel 110 of the second leg 106 .
[0075] The clip body 102 is provided to the end user in its pre-attachment state as illustrated in FIGS. 21 through 23 . In this state, the movable trigger 120 is positioned toward the open end of the clip body 102 . In this position, the flange 124 of the trigger 120 engages the first window 116 . This engagement prevents the trigger 120 from prematurely being moved out of position. As also illustrated in FIGS. 21 through 23 , the pre-attachment position of the trigger 120 maintains a widely spaced relationship between the ends of the first leg 104 and the second leg 106 , thereby allowing insertion of the component therebetween.
[0076] Upon initial insertion of the component 38 into the clip body 102 as illustrated in FIGS. 22 and 23 , the leading edge of the component 38 is placed into contact with the inside of the curved clip end 108 . As the component 38 is pushed clip-inward by the operator into the clip body 102 , the leading edge of the component 38 forces the flange 124 of the trigger 120 to become disengaged from the first window 116 . Clip-inward movement of the component 38 continues until the flange 124 of the trigger 120 is moved into engagement with the second window 118 , as illustrated in FIGS. 24 and 25 . With the component 38 inserted into the clip body 102 to its maximum position, the maximum tension applied to the component 38 by the barbs 112 and 112 ′ prevents release of the component 38 from the clip body 102 .
[0077] Referring to the fourth embodiment of the disclosed inventive concept illustrated in FIGS. 26 through 32 , an edge clip, generally illustrated as 150 , is shown in perspective view. Like the edge clips 10 , 50 and 100 referenced above, the edge clip 150 has multiple applications but is generally used to hold a component under tension to the clip, thus providing broad application across multiple industries. The edge clip 150 includes a generally u-shaped clip body 152 . The clip body 152 also may be composed of any material capable of generating a clamp load to hold a component with enough tension so as to prevent the component from separating from the edge clip 150 .
[0078] The clip body 152 includes a first or upper leg 154 and a second or lower leg 156 . The first leg 154 and the second leg 156 are connected by a solid curved clip end 158 . Formed on the inner side of the first leg 154 is a first deep drawn channel 160 and formed on the inner side of the second leg 156 is a second deep drawn channel 162 . The widths of the deep drawn channels 160 and 162 may be other than those shown and are not necessarily the same.
[0079] To assure that the component is securely held to the clip body 152 , at least one but preferably two barbs are provided. Most preferably a first barb 164 and a second barb 164 ′ are formed on the first leg 154 . The barbs 164 and 164 ′ assure that only unidirectional movement of the component into the clip body 152 is possible. The barbs 164 and 164 ′ may have a variety of shapes, including but not limited to flat, sharp, round, and spiked.
[0080] The first leg 154 includes an upturned end 166 at its end opposite the curved clip end 158 . The upturned end 166 allows for easy insertion of the component into the clip body 152 . A first window 168 is formed in the deep drawn channel 160 of the first leg 154 . The first window 168 is relatively close to the upturned end 166 of the first leg 154 . A second window 170 is also formed in the deep drawn channel 160 of the first leg 154 , although the second window 170 is relatively close to the curved clip end 158 .
[0081] A movable trigger 172 is provided within the clip body 152 . The movable trigger 172 includes first or upper trigger leg 174 having a clip body engagement flange 176 extending therefrom. The movable trigger 172 also includes a second or lower leg 178 that is attached to the first leg 174 by a curved trigger end 180 . A frangible attachment bridge 182 preliminarily attaches the trigger 172 to the second leg 156 of the clip body 152 .
[0082] The clip body 152 is provided to the end user in its pre-assembled state as illustrated in FIGS. 26 and 27 . In this state, the movable trigger 172 is suspended from the second leg 156 of the clip body 152 by the frangible attachment bridge 182 . The user then removes the movable trigger 172 from the second leg 156 by breaking the frangible attachment bridge 182 in any of several known ways, including, but not limited to, back-and-forth movement of the trigger 172 relative to the clip body 152 until the frangible attachment bridge 182 is weakened to the point of breakage.
[0083] Once separated from the clip body 152 , the movable trigger 172 is inserted into the clip body in such a way that the first leg 154 of the clip body 152 is slidably positioned in the deep drawn channel 160 of the first leg 154 while the second leg 178 is slidably positioned in the deep drawn channel 162 of the second leg 156 . The trigger 172 is inserted clip body-inward curved trigger end 180 first by the operator into the clip body 152 until the flange 176 engages the first window 168 of the first leg 154 . The proper, pre-attachment positioning of the trigger 172 within the clip body 152 is illustrated in FIG. 28 . In addition, and referring also to FIGS. 29 and 30 , the pre-attachment position of the trigger 172 is illustrated, showing how the trigger 172 maintains a widely spaced relationship between the ends of the first leg 154 and the second leg 156 . Thus positioned, the assembled clip body 152 is now ready for insertion of the component 38 .
[0084] Upon initial insertion of the component 38 into the clip body 152 as illustrated in FIGS. 29 and 30 , the leading edge of the component 38 is placed into contact with the inside of the curved clip end 158 . As the component 38 is pushed clip-inward by the operator into the clip body 152 , the leading edge of the component 38 forces the flange 176 of the trigger 172 to become disengaged from the first window 168 . Clip-inward movement of the component 38 continues until the flange 176 of the trigger 172 is moved into engagement with the second window 170 , as illustrated in FIGS. 31 and 32 . With the component 38 inserted into the clip body 152 to its maximum position, the maximum tension applied to the component 38 by the barbs 164 and 164 ′ prevents release of the component 38 from the clip body 152 .
[0085] Referring to the fifth embodiment of the disclosed inventive concept illustrated in FIGS. 33 through 40 , an edge clip, generally illustrated as 200 , is shown in perspective view. Like the edge clips 10 , 50 , 100 and 150 referenced above, the edge clip 200 has multiple applications but is generally used to hold a component under tension to the clip, thus providing broad application across multiple industries. The edge clip 200 includes a generally u-shaped clip body 202 . The clip body 202 also may be composed of any material capable of generating a clamp load to hold a component with enough tension so as to prevent the component from separating from the edge clip 200 .
[0086] The clip body 202 includes a first or upper leg 204 and a second or lower leg 206 . The first leg 204 and the second leg 206 are connected by a solid curved clip end 208 . To assure that the component is securely held to the clip body 202 , at least one but preferably two barbs are provided. Most preferably a first barb 210 and a second barb 210 ′ are formed on the first leg 204 . The barbs 210 and 210 ′ assure that only unidirectional movement of the component into the clip body 202 is possible. The barbs 210 and 210 ′ may have a variety of shapes, including but not limited to flat, sharp, round, and spiked.
[0087] A first window 212 is formed in the first leg 204 . The first window 212 is relatively close to the open end of the first leg 204 . A second window 214 is also formed in the first leg 204 , although the second window 214 is relatively close to the curved clip end 208 .
[0088] A movable trigger 216 is provided within the clip body 202 . The trigger 216 may be made from a wide variety of materials, although a pliable polymerized material such as nylon is preferred. The movable trigger 216 includes a front wall 218 that faces the open end of the clip body 202 . A component-receiving channel 220 is formed in the front wall 218 . A clip body engagement flange 222 is integrally formed with the trigger 216 . The trigger 216 further includes a back wall 224 that faces the curved clip end 208 . The back wall 224 preferably but not absolutely includes a channel 225 . The channel 225 provides flexibility to the back wall 224 so as to more readily fit against the inner surface of the curved clip end 208 .
[0089] The trigger 216 further includes a lower channel 226 having a pair of spaced-apart lateral arms 228 and 228 ′. The lateral arms 228 and 228 ′ engage the sides of the second leg 206 and allow the trigger 216 to slide linearly along the second leg 206 .
[0090] Upon initial insertion of the component 38 into the clip body 202 as illustrated in FIGS. 35 through 37 , the leading edge of the component 38 is placed into contact with channel 220 formed on the front wall 218 of the trigger 216 . As the component 38 is pushed clip-inward by the operator into the clip body 202 , the leading edge of the component 38 forces the flange 222 of the trigger 216 to become disengaged from the first window 212 . Clip-inward movement of the component 38 continues until the flange 222 of the trigger 216 is moved into engagement with the second window 214 , as illustrated in FIGS. 38 through 40 . With the component 38 inserted into the clip body 202 to its maximum position, the maximum tension applied to the component 38 by the barbs 210 and 210 ′ prevents release of the component 38 from the clip body 202 .
[0091] It is to be understood that while the first through fifth embodiments illustrated in the figures and discussed in conjunction therewith illustrate only a single trigger, two or more triggers positioned side-by-side may also be provided for attaching larger components. Other multiple trigger arrangements are possible, such that multiple components could be attached to a single edge clip. Accordingly, the illustration of single triggers is not intended as being limiting.
[0092] One skilled in the art will readily recognize from such discussion, and from the accompanying drawings and claims that various changes, modifications and variations can be made therein without departing from the true spirit and fair scope of the invention as defined by the following claims.
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A self-locking push-on clip fastener for securing two components together is disclosed. The clip fastener includes a u-shaped clip body that includes upper and lower legs and a curved end that connects the legs. The clip body has an open end into which the component to be attached is inserted. The legs are movable between an initial, spaced apart arrangement in which the component may be inserted into the clip body, to a final component-engaging position, in which the component is captured between the legs. A slidably movable u-shaped trigger is attached to the clip body. A trigger-guiding channel is formed on the inner wall of one or both of the legs of the clip body. The trigger is slidably movable in the channel. An interlock system comprising first and second windows is formed in one of the legs of the clip body and a flange extending from the trigger.
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This application is the national phase under 35 U.S.C. §371 of prior PCT International Application No. PCT/JP 96/02606 which has an International filing date of Sep. 12, 1996 which designated the United States of America, the entire contents of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a mattress having an excellent insulating property and provided with a high-grade feeling different from feathers and the like.
The invention further relates to a process for producing stuffing of the mattress and the like and a producing device used for the said process, and in detail the invention relates to a process for producing stuffing of a mattress or clothing and the like having an excellent insulating property and provided with a high-grade feeling different from feathers and the like and a producing device used for the said process.
2. Related Art
Hitherto, as stuffing of a mattress such as coverlet, bedding and the like and arctic clothes and the like, there have been used urethane, feather, hair, cotton or wool and the like having excellent insulating property, hygroscopicity and cushionability. In such mattress, when a short fiber was used for stuffing, there was a problem that the short fiber is slipped out of an inner layer. Therefore, various special treatments were applied to the inner layer, and a measure was planned to prevent the stuffing from slipping out. However, a process for applying any special treatment to the inner layer caused problems of not only lowering the touch and the feel but also a comparatively high producing cost.
Therefore, in recent years there has been developed a process for forming a continuous long fiber by twining or twisting short fibers together, using the said long fiber as stuffing, and preventing the stuffing from slipping out of an inner layer. Particularly, recently, there is developed silk applicable to the bedding field and the like by making the best use of the processing technique of raw silk. That is, as an available process for such silk, a silk thread prepared by twining a plurality of cocoon threads, each one of which is cotton like and floss made by waste cocoons unavailable as raw silk, are processed, and utilized as stuffing of the mattress, clothing, arctic outfits and the like.
However, a prior long fiber is continued by twining or twisting short fibers together, and in case of using it as stuffing of mattress, such long fiber per se becomes hard and invites a feeling of physical disorder in use and a lowering of the feel.
Furthermore, a silk thread prepared by twining a plurality of cocoon threads, each one of which is cotton-like, forms uneven twisted portions at the time of producing to become hemp-like; thus, making it impossible to obtain the touch of good quality. Moreover, in case of using floss made by waste cocoon, it is impossible to obtain the delicate touch, feel and high-grade feeling, and to suitably use such for stuffing of mattress and the like.
In case of using urethane, wool or cotton and the like, used until now as stuffing, such stuffing is excellent in mass-production and production cost, but rather unsatisfactory in touch and feel.
An object of the invention is, therefore, to prevent thread cutting of a long fiber, and to propose high-grade mattress provided with the touch, feel and insulating property different from feathers.
Moreover, another object of the invention is to propose a process for producing stuffing which can easily and positively produce mattress, clothing and arctic outfits and a producing device used for the said process.
SUMMARY OF THE INVENTION
A mattress of the invention is characterized in that a cocoon thread bundle of long fibers formed as a reeled thread by reeling cocoon threads off a plurality of cocoons and separating them one by one is sandwiched with inner layers from both the upper and lower sides to form the mattress body. Quilting is applied to appropriate portions of the mattress body. The circumference of the mattress body is covered with a surface cloth made of woven fabric, and the peripheral portion is fastened by a retention cloth.
The cocoon thread bundle of long fibers can be arranged in the longitudinal direction, the short-side direction or both the longitudinal direction and the short-side direction of the mattress. Moreover, it is possible to double the mattress body, to insert solid stuffing as a core member into the mattress body, and to cover the circumference of the mattress body with a surface cloth. In the mattress of the invention, the touch, feel and insulating property are improved. Also, thread cutting is prevented during a period of use, and a high-grade feeling is obtained.
Moreover, the invention relates to a process for producing stuffing which comprises steps of reeling cocoon threads off a plurality of boiled cocoons round a reel, sewing appropriate portions of the cocoon threads reeled round the reel, and cutting and processing a bundle of the sewed cocoon threads.
It is also preferable the bundle of the cocoon threads reeled round the reel is used as stuffing by sandwiching with two cloths.
Moreover, the invention relates to a device for producing stuffing which comprises a cocoon container for containing a plurality of boiled cocoons, an automatic reeler for reeling cocoon threads off cocoons within the cocoon container round a reel, a transverse suspension shaft arranged between the cocoon container and the reel, a sewing device having a long machine for sewing appropriate portions of the cocoon threads reeled round the reel, and a set table for cutting and processing a bundle of the sewed cocoon threads.
The reel is contractible in the longitudinal and/or vertical direction.
The above process and device can easily and positively produce stuffing of mattress and the like consisting of a bundle of cocoon threads having excellent insulating property, hygroscopicity and cushionability. That is, such stuffing is arranged in the state of separating cocoon threads of long fibers one by one and continuing from end to end of the mattress and the like, and as a result, a desired space is formed between threads, and an insulating property is excellent, every cocoon thread is independent, and there is no twisting or kinking trouble. Furthermore, since the cocoon thread per se contains sericin, there are moderate resiliency and toughness, thread cutting during a period of use can be mitigated, and an advantage of natural silk can effectively be exhibited, so that the high-grade feeling different from feathers can be obtained. Moreover, a bundle of cocoon threads produced as stuffing is sewed at appropriate portions so as to be free from fraying.
From the above, the stuffing produced from the process and the device of the invention can be utilized as the stuffing of not only mattress and the like such as a coverlet and a bedding but also a wrap, shortcoat, cushion or a pillow, and clothing, such as arctic outfits and the like.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detail description.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood form the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a cross section of one example mattress according to the invention.
FIG. 2 is a partly cutaway perspective view of the mattress according, to the invention.
FIGS. 3(a), 3(b) and 3(c) are partially cutaway plan views showing the arranged state of bundle of cocoon threads in the mattress according to the invention.
FIG. 4 is a cross section of another example mattress according to the invention.
FIG. 5 is a general view of one example stuffing producing device according to the invention.
FIG. 6 is a partial perspective view showing the use condition of the above device.
FIG. 7 is a perspective view showing a bundle of cocoon threads produced by the above device.
FIG. 8 is a perspective view showing a reel of the above device.
FIG. 9 is a perspective view showing a machine part of the above device.
FIG. 10 is a perspective view showing another example of a bundle of cocoon threads produced by the above device.
FIG. 11 is a perspective view showing another example reel of the a device.
FIG. 12 is a perspective view showing a further example reel of the above device.
FIG. 13 is a partial perspective view showing a transverse suspension shaft of the above device.
FIG. 14 is a partial perspective view showing another transverse suspension shaft of the above device.
FIG. 15 is a partial perspective view showing a further transverse suspension shaft of the above device.
FIG. 16 is a perspective view showing a pulley part inserted into the transverse suspension shaft of the above device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
One example of the invention is explained by referring to FIGS. 1 and 2. A mattress 1 shown in FIGS. 1 and 2 is formed by covering a stuffing 2, an inner layer 6 for sandwiching the stuffing 2 from the upper and lower sides and a mattress body 3 formed by the inner layer 6 with a surface cloth 8.
The stuffing 2 consists of a cocoon thread bundle 4 produced by drawing cocoon threads 5 out of about 3,000-5,000 cocoons, respectively, separating one by one and reeling the cocoon threads. The cocoon thread bundle 4 is pulled by a draft device and cut into suitable length in accordance with a use.
The cocoon thread 5 for constructing the said cocoon thread bundle 4 is a long fiber of 2.5 denier to 3.0 denier in thickness, and one cocoon thread 5 is arranged in the continued state from end to end of the mattress 1.
The cocoon thread bundle 4 is sandwiched by the inner layer 6 from both the upper and lower sides, and applied with a quilting 7 for preventing slippage of the cocoon thread bundle 4.
Moreover, around the circumference of the side layer 6, in order to prevent thread cutting of the quilting 7, a surface cloth 8 consisting of a woven fabric is covered, while the peripheral portion of the mattress 1 is fastened by lock processing with the use of a retention cloth 9.
FIGS. 3(a), (b) and (c) are partially cutaway plan views showing arrangement states of the cocoon thread bundle 4 in the mattress of the invention.
FIG. 3(a) shows a state of arranging the cocoon thread bundle 4 in the longitudinal direction of the mattress 1. The cocoon bundle 4 consists of a plurality of cocoons 5 arranged in the continuous state from an end I to the other end II of the mattress 1.
FIG. 3(b) shows a state of arranging the cocoon thread bundle 4 in the short-side direction of the mattress 1. The cocoon thread bundle 4 consists of a plurality of cocoons 5 arranged in the continuous state from an end III to the other end IV of the mattress 1.
FIG. 3(c) shows an arranged state by crossing the cocoon thread bundle 4 in the longitudinal direction and the short-side direction of the mattress 1.
Moreover, in the above (a), (b) and (c), the cocoon thread bundle 4 is sandwiched by the inner layer 6 from both the upper and lower sides, and applied with a quilting 7 for preventing slippage of the cocoon thread bundle 4. Furthermore, around the circumference of the inner layer 6, a surface cloth 8 is covered for preventing thread cutting and fraying of the quilting 7.
FIG. 4 shows another example of the invention. A mattress 11 doubles a mattress body 3, and inserts a solid stuffing 10 as a core member between the mattress body 3. The solid stuffing 10 can suitably be selected from those consisting of chemical fiber materials such as nylon, polyester and the like, properly having resilience by compression processing, or feathers, wool and the like according to the purpose of use. The circumference of the mattress 11 having the aforementioned core member 10 is covered with a surface cloth 12 and the peripheral portion is fastened by a retention cloth 13.
Moreover, when a resilient member is used as the solid stuffing 10, the mattress 11 appropriately has strength, and is preferable to be utilized as a mattress.
Next, a process and a device for producing stuffing according to the invention is explained by referring to the drawings.
FIG. 5 is a general view showing one example stuffing producing device 101 of the invention used for carrying out a process according to the invention. The stuffing producing device 101 is composed of a cocoon container 110, a transverse suspension shaft 120, a reel 130, an automatic reeling device 140, a set table 150 and a sewing device 160. In the cocoon container 110 are contained a plurality of cocoons 111 boiled using boiling water, steam and the like. Cocoon threads 112 of the cocoons 111 are reeled one by one by a reeler (not shown), passed through the transverse suspension shaft 120 and reeled off the reel 130 of the automatic reeling device 140. The said transverse suspension shaft 120 is positioned between the cocoon container 110 and the reel 130, and can be positioned, for example, in the state shown in FIG. 13, 14 or 15. In FIG. 13 the transverse suspension shaft 120 is fixed in a floor part 121, suspended between two supports 122 and set up substantially H-shaped. Also, in FIG. 14 the transverse suspension shaft 120 is suspended between two supports 124 fixed in the ceiling 123. Furthermore, in FIG. 15 the transverse suspension shaft 120 is suspended between side-wall faces 125 of a workshop and the like.
Moreover, as shown in FIG. 16, in the said transverse suspension shaft 120, it is preferable to rotatably mount a pulley part 126 consisting of polygons having suitable width. By that means, friction generated when the cocoon thread 112 passes through the transverse suspension shaft 120 is mitigated, reeling work is smoothly carried out and the cocoon thread 112 is prevented from cutting by friction. Moreover, for the transverse suspension shaft 120, various materials such as iron pipe, wire, wire rope, wood, string and the like can be used.
The automatic reeling device 140 is rotatably and detachably provided with a flat board-like reel 130. Such reel 130 is, as shown in FIG. 8, contractible in the longitudinal direction and the vertical direction for appropriately dealing with the size of mattress and the like. Moreover, by rotating the reel 130 in a certain direction, about 3,000 -5,000 cocoon threads 112 can usually be reeled off at one time.
The sewing device 160 is provided with a long machine 161 and a fastening frame 165. The long machine 161 consists of a pair of arms 162, detachable supports 163 and a machine part 164 being movable to the lengthwise direction of the arms 162. The fastening frame 165 is, at the time of sewing the cocoon thread 112, a fastener for fastening and fixing the reel 130.
Next, a process for sewing cocoon threads 112 is explained by referring to FIGS. 6 and 7. The cocoon threads 112 are reeled off by serially rotating a reel 130 in a certain direction. The reel 130 is moved to a sewing device 160 and mounted within a fastening frame 165. The reel 130 and the fastening frame 165 are inserted between arms 162 of the sewing device 160, a machine part 164 is moved to the longitudinal direction of the arms 162, and several portions of the cocoon threads 112 are sewn. In addition, the fastening frame 165 and the long machine 161 are movable in arrow directions, respectively, but for example, in case of moving the fastening frame 165, the long machine 161 is fixed, and in case of moving the long machine 161, the fastening frame 165 is fixed.
After sewing, the reel 130 is removed from the fastening frame 165 and moved to the set table 150. Then, both end portions 131 of the reel 130 are cut by a cutter, the cocoon threads 112 are removed from the reel 130 and a cocoon thread bundle 113 is formed. The cocoon thread bundle 113 is in the state of bundling filamentary cocoon threads 112, so that permeability, insulating property and touch are excellent. Therefore, the cocoon threads can be utilized as stuffing of bedding and the like, and and also as a wrap, shortcoat, cushion or pillow, clothing, arctic outfits and the like.
Next, another example of the mattress stuffing producing device according the invention is explained by referring to FIGS. 9 to 12.
FIG. 9 shows a tetragonal reel 132. In case of using the reel 132, first a cloth 133 such as gauze and the like is wound on the circumference of the reel 132. Thereafter, the reel 132 is rotated in a certain direction to reel off cocoon threads 112. When the cocoon threads 112 are reeled off, the whole is wound with a cloth 134 such as gauze and the like and temporarily fastened. After completing the above, one support 163 of the long machine 161 is removed, a side part 137 of the reel 132 is inserted into the portion of an arm 162, and one place is sewed by a machine part 164. Moreover, in case of the tetragonal reel 132, it is preferable to sew four sides while the reel 132 is rotated.
After sewing, the reel 132 is moved to a set table 150, and one place of the cocoon thread bundle 114 is cut by a cutter. Then, as shown in FIG. 10, filamentary cocoon threads 112 are in the state of being held by cloths 133, 134. Therefore, an anti-fraying effect of the cocoon threads 112 is improved. Moreover, in the state of being held by the cloths 133, 134, the cocoon thread bundle 114 can be utilized as stuffing of not only bedding and the like but also as a wrap, shortcoat, cushion or pillow, clothing, arctic outfits and the like.
FIG. 11 shows a trigonal reel 135, and in case of using the reel 135, first a cloth 133 such as gauze and the like is wound on the circumference of the reel 132. After that, the reel 132 is rotated in a certain direction to reel off cocoon threads 112. When the cocoon threads 112 are reeled off, the whole is wound with a cloth 134 such as gauze and the like and temporarily fastened. Moreover, in case of the trigonal reel 135, it is preferable to sew three sides while the reel 135 is rotated.
FIG. 12 shows a columnar reel 136, and in case of using the reel 136, first a cloth 133 such as gauze and the like is wound on the circumference of the reel 132, and the reel 132 is rotated in a certain direction to reel off cocoon threads 112. When the cocoon threads 112 are reeled off, the whole is wound with a cloth 134 such as gauze and the like and temporarily fastened. Moreover, in case of the columnar reel 136, it is preferable to sew plural portions while the reel 136 is rotated.
As explained above, the mattress of the invention separates long fibrous cocoons one by one and arranges them in the state continued from end to end of the mattress, so as to form appropriate spaces between threads, and to provide excellent insulating property. Moreover, every cocoon thread is independent, and there is no twisting or kinking trouble. Furthermore, since the cocoon thread per se contains sericin, there is moderate resiliency and toughness, thread cutting during a period of use can be mitigated, and the advantage of natural silk can effectively be exhibited, so that the high-grade feeling different from feathers can be obtained.
Moreover, the stuffing produced by the process for producing stuffing and the device of producing stuffing according to the invention is in a bundled state of a cocoon thread bundle, so that permeability, insulating property and touch are excellent; and therefore, the invention can widely be utilized as stuffing of not only bedding and the like, such as the mattress of the invention, but also as a wrap, shortcoat, cushion, pillow, clothing, arctic outfits, padding of chair and sofa and the like. Furthermore, cocoon threads are sewed in the state of winding round the reel, so that the cocoon threads can be prevented from fraying. Moreover, the reel is contractible in length and width, so as to produce a cocoon bundle of various sizes. Besides, in case of using a polygonal reel, stuffing is integrated by sandwiching with two cloths, and as a result, anti-fraying can be more improved.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims:
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The body of a mattress comprises a cocoon thread bundle of long fibers formed by reeling cocoon threads off cocoons and separating them one from another. The body the mattress also has inner layers sandwiching the bundle. The body is quilted at appropriate positions and covered by a suface cloth made of woven fabric, and the periphery of the body is fastened by a retention cloth. The mattress has touch different from, for example feather mattress and serves to reduce yarn breakage of the cocoon long-fibers which are used as the stuffing. The stuffing can be easily produced without fail by a process comprising the steps of reeling cocoon threads off boiled cocoons and winding them around a take-up reel, fusing the wound cocoon threads at appropriate positional, and cutting the fused bundles.
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FIELD OF THE INVENTION
The present invention relates generally to a roadway delineator and particularly to a roadway delineator that can be fitted to the side wall of a New Jersey-type concrete barrier of various shapes.
BACKGROUND OF THE INVENTION
New Jersey-type barriers are well known. They are longitudinally extending cast concrete structures typically used as median dividers to separate opposing traffic in roadways. In cross-section, the barriers have a broad, flat base and a vertical wall that tapers from wide to narrow starting at the base. These barriers are also used to protect construction crews working on the roadway.
During bad weather, road markings defining the edge of the roadway may not be visible to the motorist, especially when it is night and raining when the glare from the headlights could obscure the reflective road markings. Consequently, when a motorist loses sight of the edge of the road and veers off the pavement, he could conceivably hit the wide base of the barrier. Without the aid of markers, it would be hard to figure where the road ends and the barrier begins.
There is, therefore, a need to provide reflectors on the side walls of New Jersey-type barriers to delineate the extent of the lower portion of the barriers to alert the driver where the barrier begins even during bad weather when road markings defining the edge of the roadway may not be visible.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of the present invention to provide a roadway delineator for attachment to the side wall of a New Jersey-type concrete barrier to define the side wall and the base of the barrier under normal and inclement weather.
It is another object of the present invention to provide a roadway delineator that can be fitted to various shapes of the side walls of the New Jersey-type barriers.
In summary, the present invention provides a roadway delineator comprising first and second reflectors; a pivot joining respective one ends of the first and second reflectors; and the first and second reflectors have first and second tabs, respectively, for attachment to a side wall of a barrier.
The present invention also provides a roadway delineator, comprising first and second longitudinal reflectors joined together at respective one ends; tab secured to at least one of the first and second longitudinal reflectors for attachment to a side wall of a roadway barrier; and the first and second longitudinal reflectors are disposed at an angle relative to each.
These and other objects of the present invention will become apparent from the following detailed description.
BRIEF DESCRIPTIONS OF THE DRAWINGS
FIG. 1 is a perspective view of a roadway delineator made in accordance with the present invention.
FIG. 2 is a front elevational view of the delineator of FIG. 1, showing the upper and lower reflectors in alignment.
FIG. 3 is a right edge view of FIG. 2 .
FIG. 4 is a bottom edge view of FIG. 3 .
FIG. 5 is an fragmentary enlarged cross-section view taken along lines 5 — 5 and 5 ′— 5 ′in FIG. 3 .
DETAILED DESCRIPTION OF THE INVENTION
A roadway delineator R made in accordance with the present invention is disclosed in FIG. 1 . The delineator R is shown attached to the side wall 2 of New Jersey-type barrier 3 . The barrier 3 includes a wide base 5 from which the side wall 2 extends upwardly in a tapered manner. The cross-sectional shape or profile of the side wall 2 may vary in various areas of the country, although the general shape of a wide base and a narrow wall remains the same.
The delineator R has an upper reflector 4 and a lower reflector 6 joined in a pivoting manner with pivot 8 at their respective ends 10 . The surface of the reflectors 4 and 6 that face the traffic are covered with standard retro-reflective sheeting 12 (see FIG. 5 ). The pivot 8 allows the reflectors 4 and 6 to rotate relative to each other from 0° to 360° to allow the delineator to be fitted to differently angled side walls. The ends 10 are preferably semi-circular and the pivot 8 disposed on the center of the semi-circle so that no edges protrude from the ends 10 when the reflectors 4 and 6 are rotated. The opposite ends 14 of the reflectors 4 and 6 are pointed to direct the driver to where the road ends and the barrier begins with respect to the end 14 of the lower reflector 6 . Both the reflectors 4 and 6 are longitudinally shaped to advantageously help the driver visualize the contour of the side wall of the barrier.
Tabs 16 are each located at the respective ends 14 . The tabs 16 are used for affixing the delineator to the barrier side wall by standard means, such as with nails, screws, bolts, epoxies, etc. The tabs 16 are preferably integral with the respective reflectors 4 and 6 and are cut from the same sheet material. The tabs are shown rectangular; however, they may be of any shape. Although the tabs 16 are shown disposed perpendicular to the plane of the reflectors 4 and 6 , their orientation may be changed to suit the needs of the particular situation.
The reflectors 4 and 6 are preferably identical in shape for ease of manufacture.
The delineator R is useful in defining the side walls of the barrier where it is used in primary and secondary roads. By affixing the delineator R to the side walls of the barrier, with the reflective surfaces 12 facing the traffic, the lower and upper portions of the barrier are defined, providing a higher state of road definition. In bad weather situations when road markings may not be visible, such when it is night and raining when headlight glare on wet roads can sometimes obliterate the road markings or when snow covers the road markings, the delineator R provides greater visibility by highlighting the general shape of the barrier side walls and pointing to the edge of the base, thereby providing safer driving conditions. The driver is then better able to gauge his distance from the barrier. The pivot 8 allows the reflectors 4 and 6 to hinge or rotate relative to each other so that it may be fitted properly to the side walls of the barrier, regardless of its specific profile. Thus, the delineator R is not limited to a specific shape of the barrier.
The reflectors 4 and 6 are preferably fabricated from aluminum sheet which is cut to shape, including the tabs 16 . After the reflectors 4 and 6 are cut to shape, the tabs 16 are bent so that they are perpendicular to the face of the reflectors. Other materials, such as plastic, may also be used.
While this invention has been described as having preferred design, it is understood that it is capable of further modification, uses and/or adaptations following in general the principle of the invention and including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains, and as may be applied to the essential features set forth, and fall within the scope of the invention or the limits of the appended claims.
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A roadway delineator comprises first and second reflectors; a pivot joining respective one ends of the first and second reflectors; and the first and second reflectors have first and second tabs, respectively, for attachment to a side wall of a barrier.
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[0001] The present application claims benefit of priority to U.S. Provisional Application No. 61/458,696, filed on Nov. 30, 2010, entitle “Compact, High-Resolution Fluorescence Microscope,” which is incorporated by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention generally relates to a digital inverted or upright fluorescence microscope having excitation, emission, and imaging optics and sensor integrated into a short light path in a single compact assembly for high resolution, and using a CMOS sensor for image acquisition and control of image display on an electronic device without need for an ocular assembly.
BACKGROUND
[0003] Fluorescence and brightfield microscopes have become indispensable tools for science and medicine. Traditional laboratory microscopes with photo capabilities needed for research and medical diagnostics are large, cumbersome, fragile, and expensive to the extent that they are priced out of reach for many potential users, including science teachers. Accordingly, many researchers, clinicians, and educators lack access to microscopes for their work. Furthermore, many microscopes are complicated to use and maintain, which hinders their use in many applications.
[0004] Schools struggle with modern conventional microscopes. They are foreign and intimidating to many students. Their complicated operation results in frequent difficulties such as misalignment, inappropriate interocular distances, incorrect condenser focus, and damaged or dirty objective lenses, in some cases due to the physical inaccessibility of these parts to the user. In many classrooms, the number of students easily exceeds the ability of a teacher to assist and verify what the students are or are not seeing. Because of these difficulties, teachers have resorted to using sophisticated microscope simulations since microscopy is such an important component of the modern curriculum (http://virtualurchin.stanford.edu/microtutorial.htm).
[0005] Many modern disease diagnostic assays utilize fluorescence, whether intrinsic to the sample, provided by the binding of a fluorescent molecule or an antibody labeled with a fluorescent moiety specific to a disease epitope, indirect immunofluorescence, or in situ hybridization of a fluorescently labeled nucleic acid sequence to a genetic marker of disease, among other diagnostic approaches. These diagnostic assays are limited in their availability to parts of the world where the deleterious impact of these diseases is greatest, due in part to the operational complexity and expense of fluorescence microscopes. Malaria infects an estimated 225 million people worldwide, yet many more cases may remain undiagnosed. During its lifecycle, the parasite dwells within the confines of red blood cells where it can be observed in a blood smear with suitable contrast enhancement or, because red cells contain no chromosomes, with a simple membrane-permeant fluorescent dye that intercalates and stains DNA. Yet due to the expense and cumbersome nature of modern fluorescence microscopes, these simple diagnostic tests are not being performed at locations where they are needed.
[0006] We describe a highly economical and compact inverted fluorescence microscope system, incorporating a brightfield and oblique transmission imaging mode and having a simple, yet robust design, with broad applications in research, science education, and point-of-care medicine to address these unmet needs.
BRIEF DESCRIPTION OF THE FIGURES
[0007] FIG. 1A depicts a rear cross-sectional view of the layout of a compact high-resolution fluorescence microscope of the present invention.
[0008] FIG. 1B depicts a top cross-sectional view of a compact high-resolution fluorescence microscope of the present invention.
[0009] FIG. 2A depicts a cross-sectional view of an optical imager assembly of a compact high-resolution fluorescence microscope of the present invention.
[0010] FIG. 2B depicts another cross sectional view of an optical imager assembly of a compact high-resolution fluorescence microscope of the present invention.
[0011] FIG. 3A depicts a cross-sectional view of a focusing assembly of a compact high-resolution fluorescence microscope of the present invention.
[0012] FIG. 3B depicts another cross-sectional view of a focusing assembly of a compact high-resolution fluorescence microscope of the present invention.
[0013] FIG. 3C depicts cross-sectional view of a focusing assembly of a compact high-resolution fluorescence microscope of the present invention.
[0014] FIG. 4 is a photograph of an assembled compact high-resolution fluorescence microscope of the present invention.
[0015] FIG. 5A depicts an electrical subsystem of a compact high-resolution fluorescence microscope of the present invention.
[0016] FIG. 5B depicts another electrical subsystem of a compact high-resolution fluorescence microscope of the present invention.
[0017] FIG. 6 depicts a display of a host computer running the microscope control program whiles acquiring images cells.
[0018] FIG. 7 depicts an image of fixed Paramecium tetraurelia made using a compact high-resolution fluorescence microscope of the present invention.
[0019] FIG. 8 depicts an image of a horizontal section through a leaf of Vicia fava made using a compact high-resolution fluorescence microscope of the present invention.
[0020] FIG. 9 depicts an image of Spirogyra crassa made using a compact high-resolution fluorescence microscope of the present invention.
[0021] FIG. 10 depicts an image of bovine pulmonary arterial endothelial cells made using a compact high-resolution fluorescence microscope of the present invention.
[0022] FIG. 11 depicts an image of bovine pulmonary arterial endothelial cells made using a compact high-resolution fluorescence microscope of the present invention.
[0023] FIG. 12 depicts an image of transgenic nematodes made using a compact high-resolution fluorescence microscope of the present invention.
[0024] FIG. 13 depicts an image of transgenic nematodes made using a compact high-resolution fluorescence microscope of the present invention.
[0025] FIG. 14 depicts a brightfield image of a transverse section of the dermal layer of human skin containing a nevus or mole from a biopsy made using a compact high-resolution fluorescence microscope of the present invention.
[0026] FIG. 15 depicts a fluorescent image of a transverse section of the dermal layer of human skin containing a nevus or mole from a biopsy made using a compact high-resolution fluorescence microscope of the present invention.
[0027] FIG. 16 depicts an image of an unstained section of normal human small intestine showing auto-fluorescence made using a compact high-resolution fluorescence microscope of the present invention.
[0028] FIG. 17 depicts an image of a section from a small intestinal tumor obtained from a human patient made using a compact high-resolution fluorescence microscope of the present invention.
[0029] FIG. 18 depicts an image of fetal telencephalon-derived human neural stem cells obtained by time-lapse image acquisition.
[0030] FIG. 19 depicts an image of fetal telencephalon-derived human neural stem cells obtained by time-lapse image acquisition.
SUMMARY
[0031] The present invention recognizes the need for a compact, inexpensive fluorescence microscope capable of high-resolution imaging with high light throughput suitable for use in laboratory and field environments.
[0032] A first aspect of the present invention is an inverted fluorescence microscope.
[0033] A second aspect of the present invention is a method of using an inverted fluorescence microscope of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0034] Definitions
[0035] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Generally, the nomenclature used herein are well known and commonly employed in the art. Where a term is provided in the singular, the inventors also contemplate the plural of that term. The nomenclature used herein and the procedures described below are those well known and commonly employed in the art.
[0036] Introduction
[0037] The present invention recognizes the need for a compact, inexpensive microscope capable of high-resolution imaging with high light throughput suitable for use in laboratory and field environments.
[0038] As a non-limiting introduction to the breath of the present invention, the present invention includes several general and useful aspects, including:
1) an inverted fluorescence microscope including a stage for placing a sample for observation and a compact, integrated epifluorescence illumination and detection system; and 2) a method of using an inverted fluorescence microscope of the present invention.
[0041] These aspects of the present invention, as well as others described herein, can be achieved by using the methods, articles of manufacture and compositions of the matter described herein. To gain a full appreciation of the scope of the present invention, it will be further recognized that various aspects of the present invention can be combined to make desirable embodiments of the present invention.
I. An Inverted Fluorescence Microscope
[0042] The present invention includes an inverted fluorescence microscope including a stage for placing a sample for observation and a compact, integrated epifluorescence illumination and detection system.
[0043] In the present invention, a single-assembly light path directs excitation illumination from a miniaturized source to a sample and focuses the resulting fluorescence image onto an integrated CMOS (complementary metal-oxide-semiconductor) active-pixel sensor. Image data is transmitted from the sensor to a host computer or other electronic device by a standard universal serial bus (USB) for observation on a display screen. The present invention is unique in its design, unlike existing fluorescence microscope, enabling broad utility in research, diagnostics, and education.
[0044] The low light-loss imaging assembly includes one or more of the following:
1) an objective lens system for focusing the image of the sample on the sensor; 2) an excitation light source; 3) filters for selecting one or more wavebands of excitation light, for directing said light to the sample, and for selecting one or more wavebands of light emitted by the sample; 4) tube or projection lenses; and 5) an electronic imaging sensor.
[0050] The sensor is arranged in a compact manner in a single assembly without reflecting mirrors to decrease internal reflection, maximize light throughput, and enable formation of a high-resolution image. The integrated CMOS sensor has analog and digital signal and image processing functions integrated with the active pixel array onto a single fabricated semiconductor wafer, enabling facile control of image acquisition and post-acquisition processing under computer direction through a fast, standard communication bus, such as USB. The imaging assembly is mounted to the sample stage via a focusing mechanism also mounted to an enclosure or chassis on which said stage is mounted, such that an optical axis is mechanically defined and pinned at multiple fulcrum points, to provide exceptional stability of the image on the sensor and resistance to vibration and other mechanical shock.
[0051] Wide-field fluorescence microscopes in common use obtain high resolution images with long and complex light paths in which excitation light directed to the sample and light emitted or scattered by the sample are directed to their intended targets by the use of multiple reflecting or refracting surfaces (for example, U.S. Pat. No. 7,639,420). In addition, multiple compound lenses containing numerous elements to correct spherical and chromatic aberrations are used to obtain high-resolution images of the sample. However, light intensities in the sample attenuate with the inverse square of the distance, and each reflecting or refracting surface in an optical path decreases light throughput in the optical system, such that fluorescent samples emitting weak light intensities may not be detected because insufficient light reaches the detector, whether the eye or a camera. The present invention surmounts this shortcoming by focusing on the more important optical elements of the fluorescence microscope and placing them on the shortest, direct optical path between sample and sensor. Optionally removing from a fluorescence microscope the optical interface to an eye—the ocular eyepiece—enables the construction of vastly smaller, simpler, cheaper, more robust, and more sensitive microscopes.
[0052] Another aspect addressed by the invention is the electronic sensor used to record the fluorescence image of the sample. The literature reports that the need for eyepieces can be reduced by the use of a digital imager (see, for example, U.S. Pat. No. 7,599,122) such as CCD (charged coupled device) or standard CMOS pixel arrays. CCD and standard CMOS cameras have relatively large power requirements for control circuitry, external to the pixel array, preferably to time image acquisition, clock light-induced pixel charge out of the array, convert the analog voltage signal of each pixel to a digital value, and format the imaging array data for computer displays and other camera functions. These functions, preferable for the operation of the array as a camera, are bulky and result in a relatively large camera container, because they cannot reasonably be integrated onto the semiconductor wafer on which the CCD or standard CMOS array is fabricated. This container is typically mounted into the microscope platform, resulting in the need for steering the image to the camera port, requiring additional optical lensing elements to achieve a focused image. In addition, the external circuitry generates significant heat, which increases the dark thermal noise of the CCD or CMOS array. Even when this heat is dissipated by a radiator or fan, achievement of an acceptable noise level often requires additional cooling of the imaging array. Furthermore, CCD cameras have a tendency to bloom or create streaking artifacts if too much charge is deposited in their pixels. Larger pixels of the CCD, 10 to 13 μm linear dimension, offer greater dynamic range, but come at greater cost of silicon, and also require higher magnification of the optical system. In contrast, integrated CMOS imaging detectors are not prone to blooming because they do not employ a “bucket brigade” algorithm to transfer charge to the readout amplifier. Instead, each active pixel element is read out through its own individual amplifier. Their pixels can be made smaller, to the range of 2 to 3 μm, and thus lower optical magnification is required to achieve higher image magnifications. The decreased pixel size decreases the noise charge accumulated in the dark. Moreover, a side channel FET, integrated into each active pixel element, removes thermal charge accumulating in said element during the dark, when an image is not being captured, to keep the noise low, thus eliminating the need for cooling (see, for example, U.S. Pat. No. 7,102,672). The present invention obviates these difficulties by the use of an integrated CMOS instead of standard CMOS imager. The integrated CMOS imaging sensor has a high dynamic range active pixel array in which image control functionality and dark charge control are integrated monolithically on the imaging array wafer, resulting in a very small, fully functional image sensor package, in other words, a complete camera on a chip.
[0053] Another aspect addressed by the invention is means of control of the electronic sensor and, hence the resulting image. External clocking and timing, acquisition control, digital signal processing, and image formatting functions in CCD or simple CMOS cameras cannot reasonably be integrated onto the pixel array semiconductor, and instead are optionally present as separate device elements connected to the array by external connectors. This invention takes advantage of the placement of clocking and timing, image acquisition and formatting, digital signal processing, and system control functions into circuits within the physical package of the integrated CMOS imaging array, such that power consumption is greatly reduced, the physical size of the container is drastically decreased, and image sensor functionality is increased, enabling greater control of the resulting fluorescence image. The invention realizes these advantages of the integrated CMOS imaging sensor by making further use of the USB data communication standard for system control at the register level on the integrated CMOS sensor by the host computer, and for formatting and transferring imaging data to same for display. This allows direct control of functions determining image quality, such as signal gain, exposure time, output image frame rate, as well as switching to automated control modes, in which internal system control algorithms are used to set gain and exposure to enable mapping the intensity range of the image to the dynamic range of the active pixel array.
[0054] The technical challenge of the invention may be attained in accordance with the invention by providing a microscope comprising a horizontal stage for placement of a sample to be observed through an observation hole, with the stage serving as the top surface of the microscope enclosure. The essential elements of the fluorescence microscope are mounted on a single fixture, the imager tube, located below the observation hole inside the microscope container. These elements include an objective lens mounted to the top surface of the fixture such that its optical axis is oriented perpendicular to the plane of the stage and its field of view is centered at the center of the observation hole, a dichroic filter mounted below the objective at a 45° angle to the optical axis, and an illumination tube mounted to the fixture in a position so as to direct light toward the dichroic filter in a direction perpendicular to the optical axis. The illumination tube contains a light source, which in a preferred embodiment is a light-emitting diode (LED) mounted to a miniature power-conditioning circuit, a series of condenser lenses, which allows control of vergence of the excitation light on the sample, and an excitation barrier filter, which selects one or more wavebands of light in ranges of wavelengths less than the cut-on transmission wavelength of the dichroic filter. The axis of the illuminating light is oriented at a 90° angle with respect to the optical axis defined by the objective, such that the dichroic filter reflects the selected excitation light to the sample on the stage at the center of the field of view. The emission barrier, multiple-barrier, or long-pass filter is mounted to the fixture below the dichroic mirror to select desired wavelengths of fluorescence emitted by the sample for observation. A series of projection lenses mounted in tandem below the emission filter serve to focus this selected fluorescence on the image sensor.
[0055] In a preferred embodiment of the invention, the imager tube assembly is mounted to a focusing mechanism that is in turn mounted to the chassis of the container. The image of the sample is focused on the sensor by adjusting the vertical distance between the objective lens entrance pupil and the sample. The chassis mounting resists vibrations that degrade image quality and improves resolution of the image.
[0056] In an alternate embodiment, the focusing mechanism can control the stage. The focusing mechanism can be mechanically connected to a human interface device such as a knob, or it can use an electromechanical mechanism controlled through an electronic user interface.
[0057] In a preferred embodiment, the image sensor is a high-density array of wide dynamic range active CMOS pixels monolithic with a set of analog and digital control and processing circuitry embedded on the same semiconductor wafer. The integrated CMOS sensor enables the image detector to be compact and economical without circuit boards and processors located on platforms external to the sensor wafer, which greatly improves functionality and decreases power requirements, which decreases the dark noise of the imaging pixels and enables detection of low levels of light.
[0058] In a further aspect of this preferred embodiment, the control and processing circuitry of the image sensor is interfaced to a computer by a Universal Serial Bus. The bus allows communication between the sensor and host computer. The image sensor is programmed by the host computer to acquire and format the image data in a manner compatible for display on the computer monitor by this bus. The standard communication format enables the sensor to be programmed to control image acquisition by the integrated CMOS active pixel array, and to control processing of the acquired image under direction by the user. Other standard computer interfaces, such as Ethernet, can embody the same functionality.
[0059] In a further aspect of the preferred embodiment, a manual or automated x-y caliper is mounted to the sample stage, to enable the sample to be fixed in horizontal dimension for clamping the sample in the field of view and to enable controlled surveying of the sample at specific locations.
[0060] In a further aspect of the preferred embodiment, a brightfield illumination source is attached to the external surface of the container to allow transmission illumination of the sample for location of regions of interest to be placed within the field of view, and to enable adjustment of the plane of focus within the sample.
[0061] In a further aspect of the preferred embodiment, the USB connection provides power from the host computer to the sensor, the fluorescence light source, the external brightfield light source, and other useful parts of the microscope.
[0062] This arrangement reduces light losses by elimination of reflective elements normally used to steer light in other microscope designs. The microscope does not use oculars or eyepieces for focusing or observation, but instead relies on an integrated CMOS active pixel imaging array to produce a digital image displayed in real time on a computer. The imaging array controls image acquisition on the sensor without the need for external circuitry, which enables significant processing of the image before transmission to the computer. The microscope eliminates the need for refractive index matching or adjustment typically needed for high-resolution high-magnification imaging.
[0063] FIG. 1A and FIG. 1B show respectively a rear and top external perspective of the layout of a preferred embodiment of the inverted microscope. The container comprises a sample stage ( 1 ) sitting atop an enclosure defined by the main unit case 2 a and rear cover 2 b. The stage ( 1 ) is an anodized aluminum or other metal or stiff material fabricated to an end-to-end flatness of ≦0.06 mm. The bottom half of the stage is fabricated in a manner to create an understage that extends below the top surface of the enclosure to rest within the footprint of the enclosure. The edges of the top surface of the stage extending beyond the understage may extend beyond the horizontal footprint of the container. This overhang enables large samples, such as cell and tissue culture flasks, to be supported in a stable manner on the stage. The understage portion of stage ( 1 ) is machined to dimensions identical to the horizontal footprint defined by the main unit case 2 a and rear cover 2 b. The stage ( 1 ) is attached to the enclosure by screws through holes in main unit case 2 a and rear cover 2 b where they overlap the rim of the understage portion. These attachments mount stage ( 1 ) firmly to the enclosure and minimize vibrations and bending and other motions that could cause instability of the image on the sensor.
[0064] Base ( 3 ) is a metal or other stiff material plate machined to substantial flatness, with plastic or rubber feet to enable the container to sit flat on a table, bench, or other working surface. The enclosure is mounted to base ( 3 ) by screws at the bottom of the container in a manner such that the top surface of stage ( 1 ) is horizontal within ±0.2 mm. These arrangements of the external layout of the inverted microscope provide a stable platform for optical observation of the sample with minimum vibration
[0065] Electrical connections to the microscope are made by connectors mounted in holes through the enclosure. These connections include the USB connection for the sensor ( 4 ), the connection from the power supply for the fluorescence illumination ( 5 ), the connection for the brightfield illumination source ( 6 ), and connections for other functions. Connections 5 and 6 may be used when it is not desired to obtain power for the fluorescence and brightfield illumination sources from the USB connection. In addition, switches for brightfield and fluorescence illuminators are mounted on the enclosure to enable independent actuation of each mode of illumination.
[0066] The outer surface of the enclosure, main unit case 2 a and rear cover 2 b, may be painted or otherwise covered with a material having pleasing appearance, such that brands or other labels may be attached to provide the user with information of interest or need.
[0067] Since other modifications and changes varied to fit particular operating requirements and environments will be apparent to those skilled in the art, the invention is not considered limited to the example chosen for purposes of disclosure, and covers all changes and modifications which do not constitute departures from the true spirit and scope of this invention.
[0068] Internal Layout of Microscope Components
[0069] Referring again to FIG. 1A and FIG. 1B , the general internal layout of components in a preferred embodiment of the inverted microscope is shown. In this preferred embodiment, the focusing assembly ( 7 ) is mounted to the bottom of the stage at two or more distinct horizontal locations to establish a horizontal axis for focusing motions. As is described further in “Focusing assembly”, this enables provision of a stable mechanical axis for lifting and lowering the optical imaging assembly ( 8 ) in the motions required for focusing the image of the sample on the sensor. In the preferred embodiment, the optical imaging assembly ( 8 ) is mounted to the focusing assembly ( 7 ) to enable focusing while preserving mechanical stability.
[0070] Optical Imager Assembly: Imager Tube and Objective
[0071] Referring to FIG. 2A and FIG. 2B , the optical imager assembly is built with an imager tube ( 9 ), to which other components of the assembly are mounted. The objective lens ( 10 ) is mounted to the hole through the top of the image tube ( 9 ) with sides of the hole machined to the same screw thread size as on the base of the objective lens housing to secure a tight fit. The objective lens is positioned below the circular observation hole cut through the stage ( 1 ).
[0072] In the preferred embodiment, a wide variety of objective lenses may be used. One optional criterion is that the lenses are fabricated from non-fluorescent materials, such as fused silica, quartz, or calcite, to decrease the intrinsic autofluorescence of the microscope. They may be compound lenses designed with finite tube lengths, and the dimensions of the optical imaging assembly are designed to accommodate 160 mm tube lengths, the industrial standard. Alternatively, the lenses may be infinity-corrected assemblies, in which case projection lenses are inserted in the imager tube to enable the sample image to be focused on the image sensor. Many different objective lenses manufactured with standard microscope mounting screw threads can be used in the inverted microscope. Representative, but not exclusive example of such lenses include the Plan 40× 0.65 NA 0.5 mm working distance, Plan 20× 0.4 NA 7.3 mm working distance, and Plan 10× 0.25 NA 7.5 mm working distance objectives (Meiji Techno, Japan), although many other lenses, including video camera lenses and have been used and found suitable.
[0073] In an alternative embodiment, further cost and size reductions are possible by using simple infinity-corrected lenses designed for webcams and low-magnification applications. Because of the small (2-5 micron) pixel dimensions of integrated CMOS imaging sensors, optical magnification greater than 5-10× will exceed the diffraction limit and add no further resolution to the image. Such low magnifications may be achieved with simpler lenses than microscope objectives. Low magnification lenses may perform better in the microscope by inverting them front-to-back.
[0074] In the preferred embodiment, the diameter of the observation hole is at least 1 mm greater than the outermost diameter of the objective lens housing to enable unimpeded motion of the objective housing during focusing through the stage 1 , and to enable removal of an objective lens when changing said lenses.
[0075] Optical Imager Assembly: Fluorescence Filters and Epi-Illumination
[0076] Below the objective lens, a hole is machined through the side of imager tube to accept the filter tube ( 11 ). The sides of this hole are smooth such that the filter tube is correctly positioned and mounted to the tube by the tightness of the press fit and by a retaining screw. The filter tube ( 11 ) is centered in the hole by a surrounding o-ring. The end of the filter tube sitting in the space below the objective is machined to a 45° angle with respect to the optical axis defined by the central axis of the objective (axis A in FIG. 2B ) and the central longitudinal axis of the filter tube ( 11 ). The mounting arrangement described enables this end to be positioned in this prescribed manner. The dichroic filter ( 12 ) is mounted to this 45° angle surface by the use of two retaining screws with washers in two holes flanking the outer edges of the dichroic filter ( 12 ). Flock paper inserted on the top and bottom surfaces of the dichroic filter ( 12 ) where the washers contact the filter are used to enable a compression mounting of the filter without damage to the glass. The dichroic filter is selected so as to allow the desired wavelengths of light emanating from the epi-illumination light source to be reflected to the sample through the objective lens so as to excite the fluorophores in the sample, yet also to allow the wavelengths of light emitted by said fluorophores to be transmitted through the dichroic filter.
[0077] The end of the filter tube ( 11 ) protruding from the imager tube ( 9 ) is machined to accommodate the epi-illumination system ( 13 ). The epi-illumination system is also configured as a cylindrical tube that is accepted into a counter-bored hole in the filter tube and centered and positioned in place with retaining screws through the filter tube. The illumination tube holds the epi-illumination light source ( 14 ) at the internal end of the tube. In the preferred embodiment, the light source is a light-emitting diode (LED), such as a LUXEON Rebel (Philips Lumileds Lighting Co., San Jose, Calif.) with an emission spectrum providing significant luminance at the excitation wavelength(s) of the fluorophore(s) of interest in the sample. Behind the light source is the miniaturized circuit board ( 15 ) containing the current-voltage control apparatus for powering and gating the light source output. The circuit board is connected to the connector for the fluorescence illumination ( 5 ) in FIG. 1A and FIG. 1B by leads that, in the preferred embodiment, are connected to a manual switch located in the main unit case 2 a for powering the light source on and off.
[0078] The epi-illumination from the light source is collimated or focused on the sample by reflection from the dichroic mirror and passing through the objective lens. To achieve greater control of the degree of vergence of the epi-illuminating light upon the sample, a condenser optical circuit ( 16 ) comprising one or more lenses of the desired front and back curvatures and intervening spacers is interposed between the light source and the end of the filter tube ( 11 ) internal to the optical imager unit ( 9 ). This optical circuit is composed of lenses separated by spacers and assembled as a stack before insertion into the filter tube ( 11 ) side hole. The first element of the stack is the excitation filter ( 17 ), which is a single or multiple band pass interference filter that is tuned to transmit the desired wavelength(s) of light present in the illumination from the light source to excite the fluorophores in the sample. The arrangement allows the condenser optical circuit ( 16 ) to absorb undesired heat from the light source, if present, before the excitation wavelengths are selected by the excitation filter ( 17 ).
[0079] In an alternate embodiment of the invention, the light source in the epi-illumination system 13 is a laser diode that emits one or more wavelengths of light overlapping the excitation spectrum or spectra of the fluorophore or fluorophores in the sample. In this embodiment, the excitation filter ( 17 ) can be removed to increase the intensity of epi-illumination at the sample.
[0080] In the preferred embodiment, the emission filter ( 18 ) is located below the dichroic filter in the imager tube ( 9 ) in a counter-bored cut-out of the imager tube. The emission filter ( 18 ) faces the dichroic filter and the back end of the objective. The emission filter is selected to pass optimally the waveband(s) of light emitted by the fluorophore(s) in the sample without transmission of the excitation. Below the emission filter are projection lenses ( 19 ) inserted into a stack when infinity-corrected objectives are used. The entire stack of projection lenses ( 19 ) and emission filter ( 18 ) are fixtured in the imager tube by retention nut ( 19 a ). The imager tube at the emission filter-projection lens is threaded along its length, such that when finite-tube objectives are used, and the projections lenses are not present, the nut snugly seats the emission filter ( 18 ) into the imager tube.
[0081] Optical Imager Assembly: Image Sensor
[0082] The image sensor ( 20 ) is arranged below the projection lens assembly in the direction of sample side to image side to receive an image of the sample focused by the objective lens and projection lenses, and converts the optical signal into an electronic signal. In a preferred embodiment, the image sensor ( 20 ) is mounted to a circuit board that is mounted to the bottom surface of the imager tube ( 9 ). In another aspect of the preferred embodiment, the image sensor ( 20 ) is an integrated high performance, low-voltage CMOS imaging active pixel array in which functional elements for timing and control of image acquisition and readout of the resulting electronic image are embedded monolithically within the circuitry of the semiconductor wafer on which the imaging pixel array is created. These functional elements include row addressing, column sample and hold, an amplifier for each pixel with gain control, analog-to-digital conversion, black level calibration, digital signal processing, image formatting for computer display compatibility, image output, registers for system control, registers for interface control, and an internal timing generator such as a phase-locked loop. The circuit board on which the wafer is mounted contains circuit elements for input/output control and voltage regulation in a compact package that seats within the diameter of the imager tube ( 9 ). Suitable image sensors include CMOS imager chips used in digital cameras, webcams, and cellular telephones, such as the 9712, 9715, and 6552 (Omnivision Technologies, Sunnyvale, Calif.) as well as others.
[0083] In a preferred embodiment of the invention, the image sensor communicates with the host computer by a USB version 2.0 bus. A multiple-lead electrical cable connects the circuit board of image sensor 20 to a USB bridge located within the enclosure ( FIG. 1A and FIG. 1B ). The USB bridge, in turn, is connected to the USB connector 4 located on the main unit cover 2 a ( FIG. 1A and FIG. 1B ). The USB bus is used to configure the image sensor registers, to provide an external clock for image acquisition and readout, to establish timing parameters necessary for reading out the image data in a computer-compatible format, to encode the image data into a display format, such as display resolution (e.g., 640×400 pixels SVGA, 1280×800 pixels WXGA format, or greater resolution formats), to establish the rate at which formatted image frames are read out of the sensor, to choose automatic or manual gain and exposure of image acquisition by the sensor, to set manual gain values or exposure times for image acquisition and processing, or other signal and image processing functions. All or some control of the image sensor is enacted through the USB by software running on the host computer.
[0084] Focusing Assembly:
[0085] Referring to FIG. 1A and FIG. 1B and FIG. 3A , FIG. 3B , and FIG. 3C , the optical imaging assembly ( 8 ) is mounted to the focusing assembly ( 7 ) by an interface plate ( 21 ).
[0086] Referring to FIG. 3A and FIG. 3B , the focusing knob ( 21 a ) is mounted by a set screw to the shaft protruding through a hole drilled through the main unit case ( 2 a ). This shaft terminates in a planetary reduction drive ( 22 ), which is mounted by an L-bracket to the underside of the stage ( 1 ) by two screws that are tightened so as to position the rotational axis of the shaft parallel to the horizontal plane of the top surface of the stage ( 1 ) and perpendicular to the object side to image side of the optical imaging assembly ( 8 ). Planetary reduction drive ( 22 ) is connected to shaft ( 23 ) by a compression fitting consisting of an outer rubber or other pliant material o-ring concentric with an inner plastic or other pliant material cylindrical washer having radial thickness such that when shaft ( 23 ) is pushed into the counter-bored receptacle in the planetary reduction drive ( 22 ), a tight fit is made. This method of attaching shaft ( 23 ) to drive ( 22 ) enables the optical imager assembly ( 8 ) to be traversed through the full range of vertical distance enabled by focusing assembly. The flexible compression coupling, however, absorbs any force of collision between the front lens of the objective lens ( 10 ) with the sample to prevent damaging the front lens, the sample, or the focusing assembly.
[0087] The opposite end of shaft ( 23 ) is inserted in a hole drilled through the mounting block ( 24 ). Mounting block ( 24 ) is attached to the underside of the stage by at least two screws through the block. The through-hole in mounting block ( 24 ) is precision milled to have a diametrical tolerance of preferably 2 μm such that shaft ( 23 ) fits snugly, but is still able to rotate without detectable sticking. The end of shaft ( 23 ) terminates with a circular brass disk ( 25 ). On the side of the disk facing the optical imager assembly, a spiral groove is milled, preferably having a width >2 mm and a depth >3 mm, to accept a dowel pin ( 21 b ) inserted into the interface plate ( 21 ) and to enable three complete circular turns of the disk between maximum upward and downward positions of the optical imaging assembly ( 8 ), which in a preferred embodiment, is a distance of at least 25 mm This allows for different heights of samples and desired planes of focus in samples on the stage 1 . The groove may be box ended or may have a radius, but in the preferred embodiment, the length of the dowel pin ( 21 b ) protrusion into the groove is less than the groove depth such that the primary contact between dowel pin ( 21 b ) and disk is along the side wall of the spiral. This enables the up and down focusing traverse to be smooth. In a preferred embodiment, the diameter of the disk is >25 mm and the pitch of the spiral is approximately 3 mm, such that three complete turns of the spiral traverse a full length of 75 mm.
[0088] Interface plate ( 21 ) is attached to the mounting block ( 24 ) through a linear bearing slide ( 26 ). The outer sleeve of the slide ( 26 ) is faced to the mounting block ( 24 ) and attached to the block by four socket head-cap screws inserted through the opposite side of the block such that only the threaded portions of the screws extend beyond the mounting block. The accepting holes for these screws in the linear slide ( 25 ) sleeve are located near the corners of the sleeve. The inner slide of the linear motion slide ( 26 ) is attached to the interface plate ( 21 ) by socket head cap screws inserted into holes with countersunk cutouts for the head caps from the mounting block ( 24 ) side with threaded holes drilled into the inner slide. The linear slide ( 26 ) is located near the center of the interface plate ( 21 ) to provide a balanced mechanical support for the interface plate ( 21 ) and its attached optical imager assembly ( 8 ), as the imager assembly ( 8 ) is lifted and lowered by the dowel pin ( 21 b ) via the interface plate ( 21 ).
[0089] This focusing assembly ( 7 ) and its method of attachment to the optical imager assembly ( 8 ) provide mechanical support for the main elements of the microscope during focusing motions. The entire weight of the optical imager assembly ( 8 ) is borne by focusing assembly ( 7 ). The focusing assembly is mounted to the underside of the stage at two distinct locations, the L-bracket attachment for planetary reduction drive ( 22 ), and the mounting block ( 24 ) that supports the optical imager assembly ( 8 ) at the dowel pin and restricts its motion to a vertical direction by the linear motion slide ( 26 ). The two-location attachment of the focusing drive train—comprising the focusing knob ( 21 a ) and its shaft, planetary reduction drive ( 22 ) and its shaft ( 23 ) terminating at the spiral disk ( 25 ) provides two fulcrums for establishing and maintaining the horizontal mechanical axis for rotational motion of the focusing assembly. This requires machining of mounting block ( 24 ) such that the center of the through-hole for shaft ( 23 ) can be placed at a vertical distance below the underside of stage 1 within a tolerance of 0.1 mm. The L-bracket attachment of planetary reduction drive ( 22 ) is machined such that the vertical location of the corresponding center of the shaft within the drive can be placed at a vertical distance below the underside of stage ( 1 ) within the same tolerance. In addition, focusing assembly ( 7 ) is assembled in a specific order to achieve the optimal orientations of the horizontal focusing axis with respect to the top surface plane of stage ( 1 ). The circular spiral disk ( 25 ) is mounted to shaft ( 23 ) and inserted through the acceptance hole in mounting block ( 24 ), which is loosely screwed to the underside of stage ( 1 ). The planetary reduction drive ( 22 ) is then inserted into the acceptance slot of its L-bracket so that its shaft extends through the hole in the main unit case 2 a, and the L-bracket is loosely attached to underside of stage ( 1 ). Only after the flexible compression fit at the end of shaft 23 is pressed into its receptacle in the planetary reduction drive ( 22 ) and shaft ( 23 ) is positioned horizontal to the underside of stage ( 1 ) and parallel to the front wall of unit case 2 a are the L-bracket tightly screwed to the underside of stage ( 1 ), planetary reduction drive ( 22 ) firmly screwed to said L-bracket, and mounting block ( 24 ) tightened to the underside of stage ( 1 ). Alignment of shaft ( 23 ) with the stage ( 1 ) underside and unit case 2 a wall are easily performed with a straight-edged ruler or other metric device. Finally, the linear bearing slide ( 26 ) is attached to interface plate ( 21 ), and both interface plate ( 21 ) and the outer sleeve of the linear bearing slide ( 26 ) are attached to the mounting block ( 24 ). The screw-holes for these attachments are located at positions on the mounting block that allow easy access when the shaft ( 23 ) is already attached to the block. The microscope assembly is finished by attaching the optical imager assembly ( 8 ) to the interface plate ( 21 ) at two slightly offset locations, one directly below the dowel pin and one located on the opposite side of the linear bearing slide ( 26 ). These attachment locations maintain the optical axis of the optical imager assembly ( 8 ) vertical with respect to the plane of the stage ( 1 ) and prevent toppling.
[0090] A photograph of the assembled microscope is shown in FIG. 4 .
[0091] Microscope Control:
[0092] Referring to FIG. 1A and FIG. 1B , in a preferred embodiment, electrical power to the excitation light source is available from either an external power source connected to connector 5 or the USB control connector 4 . Electrical power to the remaining subsystems is derived from the 5 V USB power. Both connectors 4 and 5 terminate on an electrical control board ( 4 a ) that contains the electrical subsystems of the microscope, with the exception of the excitation light source ( 14 ), and image sensor ( 20 )
[0093] In a preferred embodiment, the microscope is controlled by a program running on the host computer that initially configures the on-chip control registers of the integrated CMOS sensor to continuously acquire image data and output said data in a specified format and at a specified image rate to a volatile buffer in the USB interface, from which the host continuously reads the formatted data to a buffer in the memory of the host computer from whence it is displayed through a graphical user interface. In a further specification of the preferred embodiment, the program runs on the host in a mode in which the memory required for its operations is protected from being overwritten by the computer's operating system, and assertions to the operating system from the program are handled with a priority enabling continuous display of complete images acquired by the sensor in a manner that appears smooth and pleasing to the human eye. In a further specification of the preferred embodiment, the host program enables the user to select between modes in which the image sensor uses on-chip processing of the light intensity values in an image to control its gain, exposure time, the rate at which it outputs complete, formatted image frames, and other image acquisition parameters, or uses values for said parameters selected by the user and written to the appropriate control registers of the sensor.
[0094] Referring to FIG. 5A and FIG. 5B , power is delivered to the microscope from the USB connector to the host computer. The block diagram of power distribution and control of the brightfield and excitation light sources and the image sensor is outlined as a block diagram in FIG. 5A . USB power is delivered by the USB connector from the host computer. Current limitation and voltage regulation of this 5 V supply is used to power the brightfield led, the image sensor ( 20 ), the USB interface, and the local microcontroller. When external power is present, the local controller switches the excitation light source ( 14 ) power source from the 5 V USB supply to the external power source.
[0095] Control of the excitation light source power source ( 27 ) is depicted in FIG. 5B . Power is derived for the microscope from the host computer ( 28 ) via the USB connector ( 29 ). The USB connection from the host computer ( 28 ) delivers USB power ( 29 a ) to the microscope, and enables control communication ( 29 b ) with the local microcontroller ( 30 ). In the absence of external power supplied to the external power connector ( 31 ), the local controller ( 30 ) enters USB power mode for the light source ( 27 ). In USB power mode, local controller ( 30 ) closes the USB SPST power switch ( 32 a ) after first opening the external power SPST switch ( 32 b ), whose outputs are connected in common to one terminal of the light source ( 27 ), and sets its control output ( 33 ) high to the AND gate ( 34 ). Illumination by the light source ( 27 ) is controlled by its current, which is determined by a voltage-controlled current regulator ( 35 ) set to a desired value by a constant voltage reference ( 36 ) also connected to USB power ( 29 a ). The output of the constant voltage reference ( 36 ) of the USB supply is connected to the inverting input of the comparator ( 37 ) to which is connected the output of a digital-to-analog converter or DAC ( 38 ) at its non-inverting input. The DAC ( 38 ) outputs a current setting sent to it by the host computer ( 28 ) via USB control communication. In USB power mode (in the absence of external power), the current setting output from the DAC ( 38 ) is set by the host computer ( 28 ) to a value greater than that of the output of the constant voltage reference ( 36 ), such that the output of the comparator ( 37 ) is high, and said output is sent to the AND gate ( 34 ) and to the local controller ( 30 ). The output of said AND gate ( 34 ) is used to control the input switch ( 39 ) of the current regulator ( 35 ). When said output is high, the input switch ( 39 ) connects the current regulator ( 35 ) to the output of the constant voltage reference ( 36 ) derived from USB power, hence supplying the light source ( 27 ).
[0096] When external power is supplied to the microscope through the external power connector ( 31 ), the connection to the local controller ( 30 ) causes said controller to enter external power mode by opening USB SPST power switch ( 32 a ) and closing external SPST power switch ( 32 b ), thus connecting one terminal of the light source ( 27 ) to the external power source, and to signal the status of excitation light source power to the host computer ( 28 ). Said host, in turn, sends the desired current level for the current regulator ( 35 ) to the DAC ( 38 ). In addition, the local controller ( 30 ) pulls its control output ( 33 ) to the AND gate ( 34 ) low, such that output of said AND gate sent to the input switch ( 39 ) is low. This causes the input switch ( 39 ) to connect current regulator ( 35 ) to the DAC ( 38 ), thus supplying the excitation light source with external power.
[0097] In a preferred aspect of the present invention, the host computer ( 28 ) can switch the desired current setting of the light source ( 27 ) by toggling its input to DAC ( 38 ) between a high value and a low value so as to provide one or more pulses of illumination light, independently of whether said light source ( 27 ) derives power from USB or an external source. These pulses can have durations less than one microsecond and can have periods elapsing between successive pulses of sufficient duration to enable time-resolved fluorescence from the sample to be acquired by the image sensor.
[0098] In a preferred embodiment, the host program provides the ability for the user to save any image stored in the frame buffer to a file on an archiving device either present within or attached to the host computer, such as a hard disk drive. In a further specification of the preferred embodiment, the image file may be automatically named with a name that includes the date and time at which the image was acquired and stored. In a further aspect of the preferred embodiment, the user may configure the host program to save multiple acquired images at a user-specified periodic interval, for either a fixed period of time or continuously until storage is manually stopped by the user, and that the names of these sequentially saved files indicate the number of the file in the sequence. When the user-specified interval is zero, the host program archives each image from the memory buffer in a sequence of contiguous frames analogous to a video stream. An example of the graphical user interface of the host control program including forms for control of gain, exposure, and light source power and control of time lapse acquisition and saving of images is shown in FIG. 6 .
[0099] An x-y caliper can be attached to the stage surface for holding microscope slides, cover slips, and other samples firmly. Motion of the caliper in each direction may be made to position the sample at precise locations by the aid of marked vernier distance scales. The caliper enables the sample to be scanned over the field of view to obtain field images separated by accurate distances. The caliper is attached to the stage by knurled screws that can be manually tightened into threaded holes drilled through the upper surface of the stage. This allows the caliper to be removed from the stage to accommodate large, bulky samples, such as tissue culture flasks, multiwell plates, and other samples that are unable to be clamped by the caliper.
[0100] Transmission brightfield illumination of the sample is readily achieved with a light source placed above the observation hole of the stage. In a preferred embodiment, a white LED at the end of a flexible gooseneck connector is attached to connection 6 ( FIG. 1A and FIG. 1B ) on the main unit case. This connector terminates inside the enclosure in a circuit board-mounted voltage regulator that powers the led. The location and direction of the brightfield illumination are adjusted manually above or around the sample to achieve the desired type of illumination. For example, acute illumination of the through tissue culture flasks made of stressed, and thus birefringent plastic slightly polarizes the illuminating light, and enables contrast in the sample to be generated by interference modulation. In an alternative example, illumination of the sample at a highly oblique grazing angle enables an image to that generated by phase-contrast. Transmission white light illumination is useful for locating regions of the sample to be observed under fluorescence epi-illumination and for obtaining an accurate focus position.
[0101] In a preferred embodiment, the host computer may control both epi-illumination and brightfield light sources to enable simultaneous acquisition of both brightfield and fluorescence views of the sample within the same image acquired by the image sensor. This enables the source of fluorescence emissions to be localized within a sample to within non-fluorescent but otherwise refractive or reflective elements of said sample. In addition, the epi-illumination may be pulsed during the acquisition time of an image frame by the image sensor in order to decrease fluorescence noise from the sample recorded by the sensor in the image.
[0000] II. A Method of using an Inverted Fluorescence Microscope
[0102] The present invention includes a method of using an inverted fluorescence microscope of the present invention. The method includes providing a sample and providing a microscope of the present invention. The sample is engaged with the microscope as described herein, and an image is generated. Preferably, there are no structures to allow a human operator to view the image directly, such as those structures provided in traditional microscopes. The image is displayed on a screen and optionally stored on a storage media. The image can be a still shot, as single frame, a video or a time lapse image. The image can be a grey-scale, a single color, or multiple colors.
EXAMPLES
[0103] Because other modifications and changes varied to fit particular operating requirements and environments will be apparent to those skilled in the art, the invention is not considered limited to the example chosen for purposes of disclosure, and covers all changes and modifications which do not constitute departures from the true spirit and scope of this invention.
Example 1
[0104] This example establishes the ease of use of a microscope of the present invention and computer interface and output with a microscope of the present invention.
[0105] Ease of use of the microscope is shown in FIG. 5A and FIG. 5B , which is a captured screen shot of the host computer running the control program for the preferred embodiment. An image of human neural stem cells derived from 13 week-old fetal telencephalon growing in a T25 polystyrene tissue culture flask with the growth surface coated with mouse laminins and observed with brightfield illumination through the top of the flask and with a Meiji 20× magnification 0.4 N.A. 7 mm working distance objective is shown in the image display area of the graphical user interface. The image displayed is the last one acquired during time lapse acquisition and saving of images once every 10 min. The acquisition sequence had been running continuously for 5 days when this screen capture was obtained. The four basic tools for operation of the program are located along the bar at the top of the display, and include icons (1) for snapping a single image from live, continuous display of sequential images from the sensor, (2) for starting and stopping time-lapse acquisition, (3) for setting up parameters for time-lapse acquisition, and (4) for user help in operating the program. Under the tool bar is a form for direct reading and writing of control registers in the intergrated CMOS sensor; this form can also be closed and removed from the display during normal operation. Control forms for gain, exposure, and illumination power and for entering time-lapse acquisition control parameters, such as the time interval between saved images, the total period of time during which images are acquired, the file seed name, and the path to the storage location of the saved images, are shown overlapping the displayed image. These forms can be closed or otherwise hidden from view during operation of the microscope.
Example 2
[0106] This example establishes the application of a microscope of the present invention for educational purposes.
[0107] Brightfield images obtained with the educational set of microscope slides “The 5 Kingdoms” (cat. no. E2-70-4016, Neo/Sci, 80 Northwest Blvd., Nashua, N.H.) with the use of the Meiji 40× magnification 0.65 N.A. 0.5 mm working distance objective in the preferred embodiment is shown in FIG. 7 , FIG. 8 and FIG. 9 . FIG. 7 is an image of fixed Paramecium tetraurelia. Key definitive morphological features of the protozoans, including cilia and micronuclei, can be resolved. FIG. 8 is an image of a horizontal section through a leaf of Vicia fava (broad bean). The stomata that regulate water exchange between the leaf and the atmosphere and cell nuclei are clearly observed. FIG. 9 is an image of Spirogyra crassa, a filamentous freshwater green alga. To the left of the image, the helical arrangement of photosynthetic chloroplasts around prominent cell nuclei is visible in the vertical filament. Extending across the image are two filaments undergoing lateral conjugation, with two compartments in zygophore stage visible at the right. As “The 5 Kingdoms” microscope slide set is aimed to junior high and middle school science education, these examples in FIG. 7 , FIG. 8 and FIG. 9 demonstrate the capabilities of the preferred embodiment as an educational tool.
Example 3
[0108] This example establishes the application of a microscope of the present invention for research and educational purposes.
[0109] Usefulness of the preferred embodiment is demonstrated for research and education is demonstrated in the fluorescence images of bovine pulmonary arterial endothelial cells (BPAEC) shown in FIG. 10 and FIG. 11 . BPAEC were cultured on a gelatin-coated no. 0 coverslip for 3 days, fixed with buffered 4% formaldehyde for 15 min, washed three times in buffer, incubated for 3 hrs in BODIPY FL-labeled phallacidin (Life Technologies, Cat. No. B607), washed 3 times in buffer and mounted on a microscope slide by techniques well-known to those skilled in the art. The slide was affixed to the x-y stage caliper with tape and mounted on the stage of the preferred embodiment with the coverslip facing the objective lens. Phallacidin binds to filamentous (F) actin, one of the predominant structural proteins of eukaryotic cells that maintain their shape and integrity, and enable their motility.
[0110] FIG. 10 was obtained with a Meiji 100× N.A. 1.25 infinity-corrected oil-immersion objective with 0.14 mm working distance. FIG. 11 was obtained with a Meiji 40× N.A. 0.65 infinity-corrected air objective with a 0.5 mm working distance.
[0111] The preferred embodiment of the invention was configured for fluorescence as follows: Light from a LUXEON Rebel Blue LED (Part. No. LXML-PB01-0040, Philips Lumileds Lighting Co., San Jose, Calif.) powered with a continuous current of 700 mA was passed through a 475 nm center-wavelength filter with a full-width at half-maximum (fwhm) passband of 35 nm (Semrock, Inc., Rochester, N.Y.) custom-cut to fit in the excitation filter position ( 17 ) of the optical imager assembly ( FIG. 2 ) and the filtered illumination light was reflected to the sample with a 506 nm-edge dichroic beamsplitter (Part. No. FF506-Di03, Semrock) also custom-cut to fit at the dichroic mirror position ( 12 ). Fluorescence emitted by the sample was passed through a 535 nm center wavelength filter with a fwhm passband of 43 nm (Semrock) custom-cut to fit in the emission filter position ( 18 , see FIG. 2 ). Projection (tube) lenses used to focus light collected by the objectives were a 10 mm diameter planoconvex lens with +20 mm focal length, in tandem with 2 12.5 mm dia. achromat lenses, the first with a 40 mm focal length, and the second with a 100 mm focal length. An integrated CMOS sensor (OVT 9715, Omnivision Technologies, Sunnyvale, Calif.) was used to capture the image.
[0112] The 100× oil immersion image of the labeled BPAEC in FIG. 10 reveals considerable structural details of the arrangement of F-actin in these cells. As the depth of field of the 100× objective is so thin (<1 μm), the sample was focused at the cells in the center of the image, such that the cells along the bottom of the image, which were at different heights in the gelatin coating compared to the cells at the center, have been allowed to be less well-focused. The nuclear and perinuclear region is revealed as either brightly labeled, or surrounded by a thick F-actin ring. Farther away from the nuclear region, the filaments are less thick, yet still thicker that the very thin filaments near the periphery of the cells where the cells extend motile protrusions toward unoccupied areas of the growth surface.
[0113] FIG. 11 was obtained after replacing the 100× objective lens with the 40× air objective and reattaching the stage caliper with attached microscope slide. Due to the ˜2 μm depth of field of the lower magnification objective, the cells throughout the field of view appear to be in focus. The pattern of actin staining observed in greater detail in FIG. 9 is revealed in FIG. 10 to be typical for the cells throughout the slide culture. In addition, it is noteworthy that even with mechanical replacement of the objective requiring removal of the rear cover of the preferred embodiment, the center of the field of view in FIG. 10 is at the same location in FIG. 11 .
Example 4
[0114] This example establishes the application of a microscope of the present invention for research purposes.
[0115] Further utility of the preferred embodiment for research is illustrated in FIG. 12 and FIG. 13 , which were obtained in a setting of college instruction in molecular biology. For this study, transgenic nematodes, Caenorhabditis elegans, were generated by parental transduction with a transposable genetic element encoding Emerald Green Fluorescent Protein (EmGFP) under control of a myosin II promoter element with an intervening nuclear localization signal sequence fused to the N-terminus of the EmGFP. Therefore, the construct is expressed in muscle cells of the nematode. FIG. 12 shows an image of the progeny of these transgenic nematodes obtained with a 40× objective in the fluorescence configuration of the preferred embodiment as described in Example 3. The fluorescence intensity confined to bright oval shapes along the worm are nuclei of muscle cells in the plane of focus, whereas the larger regions of decreased intensity are nuclei of muscle cells located out of said plane. FIG. 13 is an image of a comparable nematode progeny of a parental line transduced with the same EmGFP construct, but in addition transfected with a plasmid bearing a short-hairpin interfering RNA (RNAi). The RNAi sequence was directed to the N-terminus of the EmGFP transcript, such that transcription of the hairpin resulted in knock down of EmGFP. The image of the animal in FIG. 13 reveals significant attenuation of nuclear fluorescence compared to that in FIG. 12 .
Example 5
[0116] This example establishes the application of a microscope of the present invention for diagnostic purposes.
[0117] Usefulness of the preferred embodiment in diagnostics is illustrated in FIG. 14 and FIG. 15 , which are brightfield and fluorescence images, respectively, of a transverse section of the dermal layer of human skin containing a nevus or mole from a biopsy. The section, obtained and viewed in a dermatology clinic, was stained with hematoxylin and eosin by procedures known to those skilled in the art. FIG. 14 is an image of the section under clinic room light, and shows the nevus along the epidermal layer or stratum griseum of the skin with protuberances down into the dermis. In the image acquired under fluorescence illumination shown in FIG. 15 , collagen and elastin fibers are stained intensely by the eosin. A clinician uses the relative intensity of this fluorescence staining to determine the extent to which the nevus has altered the suppleness of the underlying skin and to judge whether the mole exhibits dysplasia or is a melanoma warranting excision.
Example 6
[0118] This example establishes the application of a microscope of the present invention for diagnostic purposes.
[0119] Further utility of the preferred embodiment in diagnostics is shown in FIG. 16 and FIG. 17 . FIG. 16 shows an unstained section of normal human small intestine obtained in fluorescence with the preferred embodiment, showing the intense autofluorescence of the intestinal epithelium lining the villi consistent with gastrointestinal health. FIG. 17 shows a section from a small intestine tumor obtained from a human patient, showing the profound disorganization of tissue fluorescence characteristic of tumor growth.
Example 7
[0120] This example establishes the application of a microscope of the present invention for research purposes when multiple fluorescent dyes are present in the sample.
[0121] For this example, a specimen is labeled with multiple fluorescent dyes, each of which is maximally excited to fluorescence emission at a different excitation wavelength, and each of which emits maximally a different wavelength of light. Such multiple dye labeling is well-known to those skilled in the art, and may be obtained by indirect immunofluorescence of different epitopes in a sample with primary antibodies raised against said epitopes in different mammalian species, followed by binding isotype-matched secondary antibodies with each secondary antibody labeled with a different fluorescent dye.
[0122] A microscope of the present invention is configured for fluorescence as follows: Light from a LUXEON Rebel Blue LED (Part. No. LXML-PB01-0040, Philips Lumileds Lighting Co., San Jose, Calif.) powered with a continuous current of 700 mA is passed through an excitation filter having at least two center-wavelengths with non-overlapping fwhm passbands sufficiently narrow such that at least two wavelengths of well-separated light are produced. This filter is placed in the excitation filter position ( 17 ) of the optical imager assembly ( FIG. 2 ). The filtered illumination light is reflected to the sample with a dichroic beamsplitter located at the dichroic mirror position ( 12 ). The dichroic beamsplitter is selected so that the edge wavelength reflects the wavelengths of excitation light. Fluorescence emitted by the sample is passed through an emission filter located at the emission filter position ( 18 , see FIG. 2 ) having center-wavelengths matched to the wavelengths emitted by the multiple fluorescent dyes. The fwhm passbands surrounding these center wavelengths are chosen such that each dye's fluorescence emission is well-separated from the other dyes. Projection (tube) lenses are used focus light collected by the objective lens onto an integrated CMOS sensor (OVT 9715, Omnivision Technologies, Sunnyvale, Calif.) is used to capture the image. Fluorescence by the multiple dyes is separated into separate images, one for each dye, by the host computer applying a selection algorithm to the Bayer color pattern of the resulting image.
Example 8
[0123] This example establishes the application of a microscope of the present invention for research purposes for acquiring one or more simultaneous brightfield and fluorescence images in which fluorescence noise is decreased by pulsing the excitation light source.
[0124] The sample is illuminated by the brightfield light source. The host computer program then pulses the epi-illumination light source with a signal less than 10 μsec in duration with a delay allowing read out of image data from the sensor to be triggered at a user-specified delay. The resulting image shows fluorescence overlayed on a brightfield image of the sample.
Example 9
[0125] This example establishes the application of a microscope of the present invention for research purposes by using time-lapse acquisition of multiple images of a dynamic biological process.
[0126] The glass bottom (0.15 mm thin) of a FluoroDish (Cat. No. FD-35, World Precision Instruments, Ltd., Hertforshire, UK) was coated with 10 μg/ml Poly-L-Ornithine in water for 24 hr at 37° C. After washing with phosphate-buffered saline, the glass surface was coated with 10 μg/ml mouse laminins in water for 24 hr. The surface was seeded with the neural stem cells described in Example 1 at a density of 100,000 cells per cm 2 . A microscope of the present invention was placed in a humidified incubator maintained continuously at a temperature of 37° C., and the covered FluoroDish was placed on the stage. The sample was observed with a 40× objective. The program on the host computer was configured to illuminate the brightfield LED for 4 sec once every 10 min, during which time an image was acquired from the sensor and archived with a file name containing indicia of the date and time that the image was acquired. FIG. 18 is an image obtained after the fetal neural stem cells had settled on the laminin-coated glass surface within 6 hr of seeding. FIG. 19 is an image acquired 5 days later, revealing the expression of extensive lamellipodia exploring the laminin-coated surface, and the formation of proliferation colonies.
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Heo, Y. S. and H J. Song 2011 Characterizing cutaneous elastic fibers by eosin fluorescence detected by fluorescence microscopy. Ann Dermatol. 23: 44-52.
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Wang, C.-C. 2001 A study of CMOS technologies for image sensor applications. Thesis, Massachusetts Institute of Technology, 196 pp.
Burghartz, J. N., H.-G. Graf, C. Harendt, W. Klingler, H. Richter, and M. Strobel. 2006. HDR CMOS imagers and their applications. Proceedings of the International Conferences on Solid State and Integrated Circuits Technology. 1:6-9.
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The present invention provides a compact, inexpensive fluorescence microscope capable of high-resolution imaging with high light throughput suitable for use in both laboratory and field environments, and methods of use. A simple and inexpensive fluorescence microscope allows health care workers to perform various medical assays at the point of care instead of having to collect and transport biological samples to distant labs, and subsequently return the results to the patient. The microscope of the present invention is also useful for educational use and field use, and other uses as well.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 60/595,318, filed Jun. 22, 2005, and is a continuation-in-part patent application of U.S. patent application Ser. No. 11/276,500, filed Mar. 2, 2006, now U.S. Pat. No. 7,555,936, which claims the benefit of U.S. Provisional Application No. 60/658,932, filed Mar. 4, 2005. The contents of these prior applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention generally relates to structures subject to stresses that can lead to structural failure, such as structures that contact or contain static or flowing fluids, examples of which include tires, airfoils, and pipes of types used in mobile machinery, automotive, aerospace, manufacturing, and process equipment. More particularly, this invention relates to structures equipped with life-sensing means in terms of wear, fatigue, and/or other structural breakdowns within the structure, and means for transmitting an output of the sensing means to detect an impending structural failure.
Ongoing interest exists in developing methods for detecting the failure of conduits that transport fluids. For example, U.S. Pat. No. 5,634,497 to Neto, U.S. Pat. No. 6,386,237 to Chevalier et al., and U.S. Pat. No. 6,498,991 to Phelan et al. disclose the detection of a worn hose by sensing the electrical resistivity in one or more wires embedded in the wall of the hose. These patents focus on detecting a discontinuity in the embedded wires, such as would result from breakage of the wires due to wear as opposed to sensing a gradual increase in resistivity attributable to wear or deformation of the hose or its wires.
U.S. Pat. No. 5,343,738 to Skaggs differs by disclosing a method for capacitively sensing the failure of a hose. In Skaggs, a fuel leakage through an inner layer of a hose is sensed on the basis of the leaked fuel altering the dielectric properties of an insulating material between a pair of copper wires embedded in the hose. Similar to Skaggs, U.S. Pat. No. 5,992,218 to Tryba et al. discloses sensing water leakage through a hose on the basis of the leaked water increasing the conductivity of an electrical insulating layer between a pair of conductor layers separated by the insulating layer. U.S. Pat. No. 5,969,618 to Redmond also discloses a method for detecting the failure of a hose on the basis of electrical conductivity. Redmond's hose is formed to have an annulus containing separated wires, and the failure of the inner layer of the hose is sensed when fluid leaks into the annulus and closes an electric circuit containing the wires.
Another approach to sensing an impending failure of a hose is disclosed in U.S. Pat. No. 4,446,892 to Maxwell. Maxwell discloses a fluid (oil) transport hose formed by at least two plies and a sensing element therebetween. In one embodiment of Maxwell, the sensing element is responsive to the electromagnetic properties of fluid present between the plies as a result of a failure of an inner ply of the hose. In a second embodiment of Maxwell, the sensing element is responsive to the failure of an inner ply of the hose by presenting an open circuit. The sensing element is said to preferably be a coil of fine wire wrapped around the inner ply and connected to means responsive to changes in the electrical impedance (AC) of the coil. Such changes are said to occur from fluid seepage into the material contacting with the coil or deformation of the inner ply, both of which change the inductance of the coil. In an alternative embodiment in which the sensing element is primarily intended to be responsive to the seepage of fluid (oil) between the plies of the hose, Maxwell employs parallel non-touching wires connected to means responsive to a change in conductance between the individual wires or to a change in the capacitance between the wires.
The prior art discussed above is particularly concerned with conduits through which a fluid is conveyed from one location to another, as opposed to fluid vessels such as hydraulic hoses, pipes, and tires in which little if any flow may occur and/or in which structural fatigue of a vessel wall from pressure cycles is often the most important factor in the life of the vessel. Furthermore, sensing systems of the type suggested by Maxwell are generally useful in relatively low pressure systems where the detection of seepage within the hose wall could provide an adequate warning of impending failure. However, in vessels subjected to fluids at relatively high pressures, once seepage occurs catastrophic failure is likely to occur in a matter of seconds, not hours or even minutes. Therefore, it would be desirable to sense an imminent fatigue failure of a relatively high-pressure vessel, as well as other structures subjected to high cyclical pressures. It would also be desirable to predict when a structural failure of such structures will occur, so that the structure can be safely used for its full life and then replaced before any damage occurs to any fluid system containing the structure or to any objects surrounding the structure.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a structure of a type that is subjected to stresses which can lead to structural failure. Such structures particularly include those that contact or contain a static or flowing fluid at high pressures, including tires, airfoils, and pipes of types used in mobile machinery, automotive, aerospace, manufacturing, and process equipment. The structure is equipped with means responsive to distortions within the structure caused by extrinsic and intrinsic sources, such as the result of external forces applied to the structure and internal forces created as a result of wear, fatigue, and/or other structural breakdowns within the structure, so as to be capable of detecting an impending structural failure.
According to the invention, the structure includes first and second conductive layers and an intermediate layer therebetween formed of a dielectric, semiconductive, or resistive material, such that the first, second, and intermediate layers form in combination an electrical element, namely, a capacitive or resistive element. The electrical element is located within the structure so as to be physically responsive to transitory and permanent distortions of the structure resulting from extrinsic and intrinsic sources. The structure further includes means for applying an electrical potential to at least one of the first and second layers so as to generate an electrical signal from the electrical element, means for sensing changes in the electrical signal generated by the electrical element in response to the electrical element physically responding to the transitory and permanent distortions, and means for transmitting the changes in the electrical signal to a location remote from the structure.
As applied to particular structures, such as tires, airfoils, pipes, etc., the conductive layers can be in the form of structural reinforcement layers, as well as passive layers that do not positively or negatively affect the overall structural integrity of the structure. Various sensing techniques can be utilized with the invention that are responsive to distortions in the first, second, and/or intermediate layers. In tire applications, such responsiveness can be used to monitor regular cyclic loading as the tire rotates, as well as irregular loading or load distributions that occur from changing road and vehicle dynamics, cuts and punctures in the tire, excessive speed or load, tire imbalance, bruising, impacts with curbs, hardening, improper mounting and damage during mounting, impending tread separation, impending burst failure, etc. As such, by monitoring distortions resulting from a variety of sources, the present invention provides the capability of continuously monitoring a structure and eventually removing the structure from service before a catastrophic failure occurs.
Other objects and advantages of this invention will be better appreciated from the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-section through a bead of a tire sealed against a rim, and shows a pair of conductive layers within the tire separated by an intermediate layer to form an electrical circuit in accordance with an embodiment of the invention.
FIG. 2 is a perspective view of a tire with partial cutaways to expose conductive and intermediate layers located within the tread of the tire in accordance with an embodiment of the present invention.
FIGS. 3 and 4 schematically represent cross-sectional views through the tread of a tire and show sensor inserts that can be used to electrically connect to conductive layers within the tread of the tire in accordance with yet another embodiment of the present invention.
FIG. 5 is a cross-section through the tread of a tire and shows belt wires that can be used as conductive layers within the tire of FIG. 2 in accordance with another embodiment of the present invention.
FIGS. 6 and 7 show two alternative patterns for belt wires that can be used as conductive layers for the tire of FIG. 2 in accordance with the invention.
FIG. 8 schematically represents the inclusion of a grid to assist in monitoring the sidewalls of a tire in accordance with the present invention.
FIG. 9 schematically represents the inclusion of proximity sensors to assist in monitoring a tire in accordance with the present invention.
FIGS. 10 and 11 show different views of a pipe with a pair of conductive layers separated by a intermediate layer to form an electrical circuit in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
As represented in FIGS. 1 through 11 , the present invention involves creating an electrical circuit within a manufactured structure subjected to high cyclical or intermittent forces, including but not limited to relatively high-pressure vessels such as tires, pipes, etc., and sensing changes in the electrical circuit that occur in response to transitory and permanent distortions of the structure. Such distortions can be the result of extrinsic and intrinsic sources, including extraneously applied forces and internal forces resulting from wear, fatigue, and other structural breakdowns within the structure. The electrical circuit contains conductive layers separated by dielectric, semiconductive, or resistive layers to form one or more capacitive or resistive elements by which changes in capacitance, resistance, or inductance can be sensed. The layers of the circuit are configured to enable sensing of an imminent fatigue failure, remaining life, and damage to the high-pressure structure, and can be coupled to data processing circuitry capable of predicting when a structural failure of the structure will occur, so that the structure can be safely used for its full life and then replaced before any damage occurs to any system containing the structure or to any objects surrounding the structure.
The invention can be applied to essentially any structure capable of having a multilayer wall construction for contacting or containing a flowing or static fluid under relatively high pressure. Notable examples include pneumatic tires and pipes. In the context of tires, the invention is also applicable to solid tires, such as solid rubber tires that can be constructed to contain multiple layers near their treads. Other applications include composite aircraft wings made up of multiple layers, whose outer airfoil surfaces are subjected to cyclical or intermittent forces resulting from changes in air pressure, etc.
FIG. 1 is a cross-section through a bead 12 of a tire 10 sealed against a rim 14 (either the inside or outside rim side), and shows a pair of conductors 16 and 18 within the tire 10 separated by an intermediate layer 20 . The conductors 16 and 18 are individually connected to conductive strips 22 and 24 on the rim 14 that are electrically insulated from the rim 14 , assuming the rim 14 is formed of an electrically conductive material. The intermediate layer 20 may be formed of a dielectric material such that the conductors 16 and 18 and intermediate layer 20 form a capacitor, or may be formed of a semiconductive or electrically resistive material such that the conductors 16 and 18 and intermediate layer 20 form a resistive circuit. As will be evident from the following discussion, the conductors 16 and 18 and intermediate layer 20 can be a functionally active or passive components of the tire construction.
FIG. 2 is a partial cutaway view of the tire 10 , in which the conductors 16 and 18 and intermediate layer 20 of FIG. 1 are represented as including or otherwise electrically integrated with three layers immediately adjacent the tread 26 of the tire 10 . As such, these layers are hereinafter referred to as conductive layers 16 and 18 and intermediate layer 20 . As evident from FIG. 2 , essentially the entire tire 10 is a circuit containing an electrical inductive or resistive sensing of changes in the thickness or electrical conductivity of the layer 20 . By applying a voltage across the layers 16 and 18 via the conductive strips 22 and 24 ( FIG. 1 ), an electrical signal is generated that can be detected and wirelessly transmitted by a transmitting device 34 to a receiving unit (not shown) installed on the vehicle to which the tire 10 is mounted. The transmitting device 34 can use, for example, existing pressure sensor and chip technology developed to monitor tire pressure. The transmitting device 34 preferably contains circuitry to process the raw analog data resulting from the electrical signal, perform analog-to-digital data conversion, and transmit the digital data wirelessly to the remote receiving unit, such as a node of a vehicle controller network. Conditions within and beneath the tread 26 are not desirable for the transmitting device 34 because of, for example, excessive accelerations. Therefore, the transmitting device 34 is shown embedded in one of the sidewalls 28 , preferably adjacent the rim 14 , so that the device 34 is located where acceleration levels are minimized. Conductive transmission elements 36 preferably interconnect the transmitting device 34 with the conductive and intermediate layers 16 , 18 , and 20 that form the sensing element of this invention. To inhibit failure from fatigue, the transmission elements 36 can be formed from extremely thin metal components in the sidewalls 28 . One such example would be the use of coated photo-etched strands that can be made in thicknesses of as little as about 0.0005 inch (about ten micrometers) from a wide variety of metals. Alternatively, the transmission elements 36 can be defined by conductive rubber paths selectively formed in the sidewalls 28 .
FIGS. 3 and 4 schematically represent another alternative transmission technique that makes use of sensor/transmitter inserts 44 and 46 to electrically connect to the conductive layers 16 and 18 within the tire 10 of FIG. 2 . The inserts 44 and 46 preferably contain the circuitry required to receive, process, and transmit the electrical signals from the conductive layers 16 and 18 , and may be powered by a battery (not shown), an induced current, or another less conventional method. The inserts 44 and 46 are shown as capable of being installed in the tire 10 through the exterior of the tire tread 26 , though other locations are possible, including the sidewalls 28 and beads 12 . For a better understanding of FIGS. 3 and 4 , the layers of the tire 10 are generally depicted to include the tread 26 , an under-tread material 38 , the conductive layers 16 and 18 , the intermediate layer 20 , a body ply 40 , and an inner liner 42 . In FIG. 3 , the insert 44 is represented as being of a type that is preferably forced into a preformed hole and secured with adhesive. The insert 44 has multiple contact points 45 for contact with the conductive layers 16 and 18 , and a blunt end to avoid puncturing the inner liner 42 of the tire 10 . In FIG. 4 , the insert 46 has two pin-like contacts 47 , each going to a different conductive layer 16 or 18 in the tire 10 . The insert 46 is configured to be forcibly pushed into the tire 10 and held in place with barbs on the contacts 47 . The head of the insert 46 on the tire exterior preferably contains the circuitry and transmitter and can serve to limit the penetration of the contacts 47 to prevent puncturing of the inner liner 42 . An advantage of the inserts 44 and 46 is that they can be installed in the tire 10 after constructing and curing the tire 10 to protect their electronic components from the harsh conditions experienced during the curing process. Additional advantages with this approach include the ability to check the tire 10 for defects before shipping, and the ability for replacement in case of a malfunction or defect.
A dielectric intermediate layer 20 formed of a silicon-based dielectric material has been shown to achieve a capacitive sensitivity of ten to one when placed between layers 16 and 18 formed of a metal. Though rubber materials of the type conventionally used in tire manufacture would exhibit reduced sensitivity, a sensitivity of even two to one (or possibly less) is believed to be attainable with such materials and acceptable for use with this invention. As such, each of the conductive and intermediate layers 16 , 18 , and 20 may be formed of a base material of rubber, steel, or other materials that are conventionally used in tire construction, and whose electrical properties can be modified as necessary to obtain the desired conductive/resistive electrical properties for the particular layer 16 , 18 , and 20 . For example, materials of the type conventionally used as steel reinforcement bands in tires can be used as the conductive layers 16 and 18 . Concentric conductive layers 16 and 18 of this type can have a conventional construction, size, and shape similar to steel reinforcement bands widely used in tire construction, or differ in any of these characteristics. As an alternative, either or both of the conductive layers 16 and 18 could be formed by increasing the conductivity of an elastomeric (e.g., rubber) layer of the tire 10 through additions of conductive materials during rubber compounding. By applying an electric current to one of the conductive layers 16 or 18 , capacitance can be measured to capture changes in the distance between the conductive layers 16 and 18 .
Another alternative is available with existing tire constructions reinforced with steel wire belts whose individual wires are electrically isolated from each other. An example of this type of tire construction is depicted in FIG. 5 , which shows the two conductive layers 16 and 18 formed by two sets of wires 30 and 32 , in which each wire 30 and 32 is electrically insulated from the other wires 30 and 32 , and the layers 16 and 18 formed by the sets of wires 30 and 32 are separated by a dielectric (e.g., rubber) intermediate layer 20 . FIG. 6 depicts a plan view of a typical arrangement for this type of reinforcement, in which the multiple wires 30 of the conductive layer 16 are orthogonal to the multiple wires 32 of the other conductive layer 18 . Pairs of these wires 30 and 32 within either or both conductive layers 16 and 18 can be coupled to form multiple capacitors within the tire 10 . Another alternative is to modify this type of reinforcement belt by electrically connecting the wires 30 or 32 in series as depicted in FIG. 7 , so that either or both conductive layers 16 and 18 define continuous conductive paths around the tire 10 .
The performance and condition of the tire 10 can also be monitored by locating sensing structures within the sidewalls 28 of the tire 10 . For example, sidewall performance and loading can be monitored with measurements taken from the sidewalls 28 to directly or indirectly observe road and vehicle dynamics that may provide an indication of loss of control and, in the case of freight trucks, indicate unsafe conditions due to overloading. For this purpose, another optional feature of the present invention is to provide one or more capacitive grids in the sidewalls 28 of the tire 10 that are separate from the conductive and intermediate layers 16 , 18 , and 20 . As represented in FIG. 8 , each grid 29 can be located similar to the transmission elements 36 seen in FIG. 2 , and powered and sensed in a manner similar to the layers 16 , 18 , and 20 as represented in FIGS. 1 and 2 . The grids 29 can have a variety of alternative configurations, and the size and number of grids 29 can be tailored to achieve the desired level of sensitivity. For example, twelve individual grids 29 could be incorporated into each sidewall 28 around the perimeter of the tire 10 , with the grids 29 spaced about thirty degrees apart. Side-loading of the sidewalls 28 can be further monitored with optical or other types of proximity sensors 48 to measure the distance between, for example, the tire beads 12 and the corners of the tread 26 , as schematically represented in FIG. 9 . Pressure and temperature may also be measured with appropriate sensors (not shown) to further monitor the condition of the tire 10 .
The resulting combination of a dielectric intermediate layer 20 with the conductive layers 16 and 18 forms a capacitor consistent with the previous embodiments. This approach also permits detection of electrical currents sent separately through the conductive layers 16 and 18 , with changes in conductivity (resistance) evidencing strain and eventual breakage of the reinforcement wires 30 and 32 within these layers 16 and 18 .
Those skilled in the art will appreciate that the conductive layers 16 and 18 as configured in FIGS. 2 through 7 are conducive to being incorporated into a variety of structures subjected to cyclical or intermittent loading, including aircraft wings and other airfoils capable of having laminate constructions. For example, the orthogonal sets of wires 30 and 32 that define the conductive layers 16 and 18 can be formed of an electrically conductive material that may contribute to the strength or toughness of a wing, or at least have negligible adverse impact on the structural properties of the wing.
As noted above, an alternative to capacitive sensing involves forming the intermediate layer 20 of a semiconductive or resistive material. For example, the two conductive layers 16 and 18 (e.g., of a type discussed above) can be separated by a semiconductive intermediate layer 20 formed of a conductive adhesive or a rubber material whose conductivity is increased with carbon or another conductive material. By passing a current through the three conductive and intermediate layers 16 , 18 , and 20 , resistance can be measured, with the resistance level depending on the condition of the three materials that form the conductive and intermediate layers 16 , 18 , and 20 .
By locating the conductive and intermediate layers 16 , 18 , and 20 immediately beneath the tread 26 of the tire 10 (or, for example, within the sidewalls 28 of the tire 10 ), the conductive and intermediate layers 16 , 18 , and 20 are subjected to regular cyclic loading as the tire 10 rotates, as well as irregular loading or load distributions that occur from changing road and vehicle dynamics, cuts, excessive speed, punctures, imbalance, bruising, impacts with curbs, hardening, improper mounting or damage during mounting, impending tread separation, and impending burst failure. As a result, the conductive and intermediate layers 16 , 18 , and 20 are subject to physical distortions, both transient and permanent, that alter the electrical signal generated when a voltage is applied across the layers 16 and 18 . By detecting and appropriately processing the electrical signal, trends and abrupt changes in the condition of the tire 10 can be sensed that indicate such things as vehicle control characteristics (skidding, swerving, etc.), vehicle loading characteristics (overloading), condition of the tread 26 (tread life, separation, and/or damage), etc.
FIGS. 10 and 11 show cutaway views of the invention applied to a pipe 50 , and particularly a multilayer pipe 50 formed of plastic, rubber, or other relatively flexible materials that are susceptible to fatigue failure. In FIGS. 10 and 11 , the pipe 50 is represented as having two conductive layers 56 and 58 separated by an intermediate layer 60 formed of a dielectric, semiconductive, or resistive material. Together, these layers 56 , 58 , and 60 form capacitive, inductive, or resistive circuits as described for the embodiments of FIGS. 1 through 8 . FIG. 11 shows a connector 52 for the two conducting layers 56 and 58 at one end of the pipe 50 . The connector 52 is preferably integrated into a coupling flange (not shown), and can be attached with a termination coupler (not shown) to measure fatigue and breakdown of the pipe wall on the basis of the same sensing capabilities as the tire 10 of FIGS. 1 through 8 . As an example, a length of the pipe 50 could be equipped with sensing circuitry at one of its ends, with additional sensing circuitry periodically located along the length of the pipe 50 to sense individual sections of the layers 56 , 58 , and 60 , or to sense two sections of the layers 56 , 58 , and 60 with a multiplexer between. A hose coupler can be adapted to make electrical contact with the conductive layers 56 and 58 within the pipe 50 .
While the invention has been described in terms of specific embodiments, it is apparent that other forms could be adopted by one skilled in the art. For example, the physical configuration of the tire 10 and pipe 50 could differ from that shown, and materials and processes other than those noted could be use. Therefore, the scope of the invention is to be limited only by the following claims.
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A structure subjected to stresses that can lead to structural failure. The structure includes first and second conductive layers and an intermediate layer therebetween formed of a dielectric, semiconductive, or resistive material, such that the first, second, and intermediate layers form in combination an electrical element, namely, a capacitive or resistive element. The electrical element is located within the structure so as to be physically responsive to transitory and permanent distortions of the structure resulting from extrinsic and intrinsic sources. The structure further includes applying an electrical potential to at least one of the first and second conductive layers so as to generate an electrical signal from the electrical element, sensing changes in the electrical signal generated by the electrical element in response to the electrical element physically responding to the transitory and permanent distortions, and transmitting the changes in the electrical signal to a location remote from the structure.
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CROSS REFERENCE TO RELATED APPLICATIONS
This document claims the benefit of the filing date of U.S. Provisional Patent Application 61/585,583 entitled “TIRE PUNCTURE REPAIR TOOL” to Kong that was filed on Jan. 11, 2012, the contents of which are hereby incorporated by reference.
BACKGROUND
1. Technical Field
Aspects of this document relate generally to tire puncture repair apparatuses.
2. Background Art
Flat tires are a frustration to most, if not all drivers at some point in the life of an automobile. Flat tires are often the result of a puncture in the tire, a puncture caused by nails, screws, or other natural or manmade debris. Various tire puncture repair tools exist to repair tubeless tires. Conventional tire puncture repair tools able to be used at the site of the flat tire with the tire on the rim (as opposed to removing the tire from the rim in a repair shop), however, do not securely fasten within the tire. For screw types, the puncture repair screw may slip out of the puncture, or significant air loss may occur even when the puncture repair screw is within the puncture of the tire due to the structure of the screw-type device.
SUMMARY
A first aspect of a tire puncture repair apparatus, comprises a handle, a puncture repair screw, the puncture repair screw comprising a screw head, a cylindrical shaft extending from the screw head opposite the neck, an at least partially threaded and solid right circular cone that uniformly narrows from the shaft to a tip opposite the shaft, and a conic-helical thread coiled about the right circular cone between the tip and the shaft, and an integral neck, narrower than the screw head and positioned between the handle and the puncture repair screw coupled to the screw head, and wherein a shaft diameter is substantially equal to a cone diameter at the right circular cone's maximum diameter.
In particular implementations and embodiments, the tire puncture repair apparatus may comprise one or more of the following. The thread may comprise an angled ridge. The thread may be coiled about the cone beginning at least at an intersection of the cone and the shaft and ending at a location before the tip. The handle may comprise a winged formation. An angled valley may be located between each coil of the conic-helical thread. A rounded valley may be located between each coil of the conic-helical thread. The conic-helical thread may comprise a right handed conic-helical thread. The handle may comprise at least two wings extending away from the puncture repair screw in mirrored opposing directions from each other to form the handle. At least one grip element may be on the at least two wings. The shaft may comprise a helical shaft thread coiled about the shaft.
A second aspect of a tire puncture repair apparatus comprises a handle, a puncture repair screw coupled to the handle, the puncture repair screw comprising a screw head coupled to the handle and a uniformly tapered screw thread, the uniformly tapered screw thread comprising an angled ridge wrapped about a right circular cone in the form of a conic helix.
In particular implementations and embodiments, the tire puncture repair apparatus may comprise one or more of the following. A breakable neck may be coupled between the puncture repair screw and the handle. The puncture repair screw may comprise a shaft coupled between the screw head and the uniformly tapered screw head, and a tip opposite the shaft. The uniformly tapered screw head may taper from the shaft such that a shaft diameter is equal to a cone diameter at the right circular cone's maximum diameter. The thread may be coiled about the cone beginning at least at an intersection of the cone and the shaft and ending at a location before the tip. The handle may comprise at least two wings extending away from the puncture repair screw in mirrored opposing directions from each other to form the handle. At least one grip element may be located on the at least two wings. An angled valley may be located between each coil of the conic-helical thread. A rounded valley may be located between each coil of the conic-helical thread.
Aspects and applications of the disclosure presented here are described below in the drawings and detailed description. Unless specifically noted, it is intended that the words and phrases in the specification and the claims be given their plain, ordinary, and accustomed meaning to those of ordinary skill in the applicable arts. The inventors are fully aware that they can be their own lexicographers if desired. The inventors expressly elect, as their own lexicographers, to use only the plain and ordinary meaning of terms in the specification and claims unless they clearly state otherwise and then further, expressly set forth the “special” definition of that term and explain how it differs from the plain and ordinary meaning Absent such clear statements of intent to apply a “special” definition, it is the inventors' intent and desire that the simple, plain and ordinary meaning to the terms be applied to the interpretation of the specification and claims.
The inventors are also aware of the normal precepts of English grammar. Thus, if a noun, term, or phrase is intended to be further characterized, specified, or narrowed in some way, then such noun, term, or phrase will expressly include additional adjectives, descriptive terms, or other modifiers in accordance with the normal precepts of English grammar. Absent the use of such adjectives, descriptive terms, or modifiers, it is the intent that such nouns, terms, or phrases be given their plain, and ordinary English meaning to those skilled in the applicable arts as set forth above.
Further, the inventors are fully informed of the standards and application of the special provisions of 35 U.S.C. §112, ¶ 6. Thus, the use of the words “function,” “means” or “step” in the Detailed Description or Description of the Drawings or claims is not intended to somehow indicate a desire to invoke the special provisions of 35 U.S.C. §112, ¶ 6, to define the invention. To the contrary, if the provisions of 35 U.S.C. §112, ¶ 6 are sought to be invoked to define the inventions, the claims will specifically and expressly state the exact phrases “means for” or “step for, and will also recite the word “function” (i.e., will state “means for performing the function of [insert function]”), without also reciting in such phrases any structure, material or act in support of the function. Thus, even when the claims recite a “means for performing the function of . . . ” or “step for performing the function of . . . ,” if the claims also recite any structure, material or acts in support of that means or step, or that perform the recited function, then it is the clear intention of the inventors not to invoke the provisions of 35 U.S.C. §112, ¶ 6. Moreover, even if the provisions of 35 U.S.C. §112, ¶ 6 are invoked to define the claimed aspects, it is intended that these aspects not be limited only to the specific structure, material or acts that are described in the preferred embodiments, but in addition, include any and all structures, materials or acts that perform the claimed function as described in alternative embodiments or forms of the disclosure, or that are well known present or later-developed, equivalent structures, material or acts for performing the claimed function.
The foregoing and other aspects, features, and advantages will be apparent to those artisans of ordinary skill in the art from the DESCRIPTION and DRAWINGS, and from the CLAIMS.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will hereinafter be described in conjunction with the appended drawings, where like designations denote like elements, and:
FIG. 1 is a perspective view of a tire puncture repair tool;
FIG. 2 is a front view of a tire puncture repair tool;
FIG. 3 is a side view of a tire puncture repair tool;
FIG. 4 is a top view of a tire puncture repair tool;
FIG. 5 is a bottom view of a tire puncture repair tool;
FIG. 6 is a cross sectional view taken along section line 6 - 6 in FIG. 2 ;
FIG. 7A-C are a sectional views of a tire puncture repair tool in a tire; and
FIG. 8 is a front view of a second implementation of a tire puncture repair tool.
DESCRIPTION
This disclosure, its aspects and implementations, are not limited to the specific components or assembly procedures disclosed herein. Many additional components and assembly procedures known in the art consistent with the intended tubeless tire puncture repair tools and/or assembly procedures for a tubeless tire puncture repair tool will become apparent for use with implementations of tire puncture repair tools from this disclosure. Accordingly, for example, although particular tire puncture repair tools are disclosed, such tire puncture repair tools and implementing components may comprise any shape, size, style, type, model, version, measurement, concentration, material, quantity, and/or the like as is known in the art for such tire puncture repair tool and implementing components, consistent with the intended operation of tire puncture repair tools.
Implementations of a tire puncture repair tool 100 disclosed herein provide a puncture repair screw 150 configured to improve the functionality and effectiveness of the tire puncture repair tool. As shown in FIGS. 1-5 , an implementation of a tire puncture repair tool comprises a handle 100 , a puncture repair screw 150 , a neck 110 connecting the puncture repair screw 150 and the handle 105 . The handle 105 may comprise a variety of sizes, shapes, and configurations that allow a user to apply rotational force to the handle to rotate the puncture repair screw.
In a particular implementation, the handle 105 comprises winged edges 155 that extend radially outward beyond the diameter edge of the screw head to allow for greater torque when manually rotating the tire puncture repair tool 100 . Various implementations may further comprise at least one grip element 157 on or near the winged edges 155 of the handle. The at least one grip element may comprise any size, shape or texture that gives the user an increased grip on the tire puncture repair tool when in use. In the illustrated implementation, the at least one grip comprises rounded ridges. In other implementations, the at least one grip element 157 may comprise squared or pointed ridges. In still other implementations, the at least one grip element 157 may comprise a rough surface or any material that increases the friction between the user's hand and the handle 105 of a tire puncture repair tool 100 .
An implementation of the tire puncture repair tool 100 may further comprise a support structure 159 positioned between and/or coupled to the opposing arms of the winged edges 155 . The support structure may, in various implementations, perform a variety of functions, including but not limited to: increased surface area for gripping the handle 105 ; support for the winged edges 155 , or a print location for names, logos, and the like.
The neck 110 of the tire puncture repair tool may comprise any size, shape or configuration that allows a user to rotate the puncture repair screw 150 by rotating the handle 105 when the puncture repair screw 150 is at least partially within a tire, then separate the handle 105 from the puncture repair screw 150 once the puncture repair screw 150 is secure within the tire. In FIG. 1 , the neck 110 comprises narrow extension between the handle 105 and the screw head 115 . Once the puncture repair screw 150 is within a tire, a user may either continue rotating the handle 105 until the neck 110 breaks, or may alternatively bend the handle 105 in various directions perpendicular to the puncture repair screw 150 until the neck 110 breaks. When the neck 110 breaks, the handle 105 may be removed from the puncture repair screw 110 , the puncture repair screw 110 remaining within the tire puncture.
In an implementation, the puncture repair screw 150 comprises a screw head 115 coupled to the neck 110 , a shaft 120 , a screw thread 125 , a right circular cone 140 , and a tip 145 distal to the screw head 115 . As illustrated in FIG. 1 , in an implementation the shaft 120 extends from the screw head 115 in a direction distal to the neck 110 . The shaft 120 illustrated in FIG. 1 comprises a cylindrical shaft 120 ; in other implementations, however, the shaft may comprise any shape or dimension.
Implementations of a puncture repair screw 150 may further comprise a right circular cone 140 that narrows uniformly from the shaft 120 the tip 145 . The juncture or intersection of the cone 140 and the shaft 120 may comprise a rounded or angled intersection. As shown in FIG. 6 , the cone 140 may comprise a maximum diameter 165 that is equal or substantially equal to a diameter 160 of the shaft 120 . In other implementations, the maximum diameter 165 of the cone 140 is greater than the diameter 160 of the shaft 120 . In still other implementations, the diameter 160 of the shaft may decrease as the shaft approaches the screw head 115 .
Though not always completely visible due to the position of the screw thread 125 , the right circular cone 140 narrows at uniform rate from the shaft 120 to the tip 145 . The rate of narrowing may vary according to different implementations or designs for specific tires. In an implementation, the cone 140 is substantially solid. In other implementations, the cone 140 may comprise a hollow or filled cone 140 .
The tire puncture repair tool 100 may further comprise a conical-helical thread 125 coiled or otherwise disposed on or about the cone 140 between the tip 145 and shaft 120 . In a particular implementation, the thread 125 continues at least partially onto the shaft. The thread 125 may similarly continue all the way to the tip 145 in some implementations. In the implementation shown in FIG. 1 , the ridge 135 at the beginning of thread 125 is aligned with the intersection of the shaft 120 and the cone 140 . In some implementations, portions of the thread 125 extend beyond the intersection of the shaft 120 and the cone 140 so that the thread 125 , and in some implementations the ridge 135 , extend onto the shaft 120 . Where the thread 125 begins and/or ends, the thread 125 may begin perpendicular to the cone 140 at its ridge 135 radial height, or may gradually slope to meet the cone 140 .
A puncture repair screw 150 that comprises a shaft 120 that continues to at least the beginning of the screw thread 125 is advantageous. Such a configuration lessons the likelihood of the screw 150 falling out of the tire or air leaking through the tire puncture when the puncture repair screw 150 is within the tire. In a particular implementation, the distance between the beginning of the screw thread 125 and the screw head 115 is less than the thickness of an average tire, or more particularly the tire into which the puncture repair screw 150 is designed to be inserted. Puncture repair screws 150 may be designed with differing distances between the beginning of the screw thread 125 and the screw head 115 to function best for differently sized tubeless tire tread and wall thicknesses.
As illustrated in FIG. 3 , in some implementations, the valleys 130 between the ridges 135 of the screw thread 125 meet the slope or boundary of the right circular cone 140 . In FIG. 3 , dashed lines represent the continued uniform slope 170 of the cone 140 . In the implementation of FIG. 3 , the bottoms of the valleys 130 meet the slope 170 of the cone 140 . In other implementations, the valleys 130 may not reach the slope 170 of the cone, or may extend beyond the slope 170 of the cone.
The thread 125 coils down or along the cone 140 in a uniform manner in an implementation, such that the ridges 135 of the thread 125 appear parallel to one another when viewed from the front or the side (see FIGS. 2 and 3 ). Because the cone 140 tapers uniformly and the thread 125 coils along the cone 140 in a uniform manner in this implementation, a flat plane may be formed on the peaks of the screw thread in a cross-sectioned view, shown in FIG. 6 . Furthermore, when view from the front or side, the puncture repair screw 150 may comprise any number of ridges 135 . In the implementation of FIGS. 1-6 , the puncture repair screw comprises six ridges 135 .
As best illustrated in FIG. 6 , the thread 125 of a puncture repair screw 150 may comprise an angled ridge 135 . The particular angle of the ridge 135 may comprise any angle, such as but not limited to a right angle, and obtuse angle, or an acute angle. The screw thread 125 illustrated in FIGS. 1-6 comprises a sharp-angled peak at the apex of the screw thread ridge 135 . In contrast, conventional screw type tire repair tools comprise a screw thread having a well rounded ridge. A sharp-angled peak is advantageous over rounded ridges because the sharp-angled peak lessens the likelihood of the screw falling out of the tire or air leaking through the tire puncture when the puncture repair screw is within the tire.
In particular implementations, the angle of the walls forming the screw thread 125 is at approximately 30-60 degrees relative to the slope 170 of the cone 140 , and in particular implementations at approximately 40-50 degrees relative to the slope 170 of the cone 140 .
FIG. 8 illustrates another implementation of a tire puncture repair tool 800 . In the illustrated implementation, the tire puncture repair tool comprises a handle 105 similar to implementations of handles 105 previously discussed in this document. A tire puncture repair tool may further comprise a more rounded neck 810 or a neck similar to the neck 110 previously discussed in relation to tire puncture repair tool 100 . As further illustrated in FIG. 8 , a tire puncture repair tool may comprise a flat head 815 between the neck 810 and the shaft 820 , or alternatively a head 115 similar to head 115 described in relation to tire puncture repair tool 100 .
Similar to the aspects of tire puncture repair tool 100 , tire puncture repair tool 800 may comprise a cylindrical shaft 820 that extends from the head 815 to a right circle cone 840 . The right circle cone 840 illustrated in FIG. 8 narrows uniformly from the shaft 820 to the tip 845 . As previously described in relation to other implementations, the cone 840 comprises a maximum diameter that is equal to or substantially equal to a diameter of the shaft. In other implementations of tire puncture repair tool 800 , the maximum diameter of the cone 840 is greater than the diameter of the shaft 820 . In still other implementations, the diameter of the shaft 820 decreases or increases as the shaft approaches the screw head 815 .
Though not completely visible due to the position of the cone thread 825 , the right circular cone 840 narrows at a uniform rate from an end of the shaft 820 to the tip 845 . Tire puncture repair tool 800 further comprises a conical-helical cone thread 825 coiled or otherwise disposed on or about the cone 840 between the tip 845 and the shaft 820 . While the cone thread 825 illustrated in FIG. 8 comprises angle peaks 835 and rounded valleys 830 , other implementations of the tire puncture repair tool may comprise a cone thread 825 similar to that illustrated in relation to tire puncture repair tool 100 . Furthermore, while cone thread 825 continues all from the top of the cone 840 substantially to the tip 845 , in other implementations the cone thread 825 may begin at or near the top of the cone 840 and end before the tip 845 .
Tire puncture repair tool 800 further comprises a helical shaft thread 855 coiled or otherwise disposed on or about the shaft 820 between the head 815 and the cone 840 . The shaft thread 855 may comprise angled or rounded peaks 860 , and angled or rounded valleys 865 . In the implementation illustrated in FIG. 8 , the shaft thread 855 comprises angled peaks 860 and rounded valleys 865 . According to various aspects, the helical shaft thread 855 may be tightly coiled, resulting in more coils, or loosely coiled, resulting in fewer coils. In other implementations, aspects discussed in reference to tire puncture repair tool 100 may be combined with various aspects of tire puncture repair tool 800 .
Implementations of a tire puncture repair tool 100 , 800 may comprise of a variety of materials, including but not limited to plastic or metal-based solids. In an implementation, at least a portion of a tire repair puncture tool is comprised of glass infused plastic. This or other implementations may utilize a polypropylene or other thermoplastic polymers.
In particular implementations, the tire puncture repair tool 100 may be utilized by first inserting the tip 145 into a puncture hole of a tire. Although utilization of tire puncture repair tool 100 is referenced, tire puncture repair tool 800 may be utilized in a similar fashion. The puncture repair screw 150 may then be pushed further into the tire by rotating the handle 105 such that the puncture repair screw correspondingly rotates. Once the screw head 115 is at the surface level of the tire, the handle 105 may be bent until the neck 110 breaks, separating the handle 105 from the repair screw 150 .
Referring now to FIGS. 7A-C , various implementations of a tire puncture repair tool 100 may be used to plug a puncture 215 in a tubeless tire 200 . In FIG. 7A , a cross-sectioned view of a tread portion of a tire 200 is shown. FIG. 7A also illustrates an example of a tire puncture 215 , the tire puncture 215 extending from the outside surface 205 of the tire 200 through to the inside surface 210 of the tire 200 . Nails, screws or other construction material on the roads often cause tire punctures of this type. Although the puncture 215 is shown at a particular location on the tire 200 in FIG. 7A , the tire puncture repair tool 100 may be utilized to at least temporarily repair a puncture 215 anywhere on a tire 200 . FIG. 7B illustrates the tire puncture repair tool 100 after been inserted into the puncture 215 on the tire 200 . According to aspects of various implementations, the tire puncture repair tool 100 may be inserted in to the puncture 215 by pressing the tip 145 of the puncture repair screw 150 into puncture 215 on the outside of the tire, then rotating the puncture repair screw 150 by rotating the handle 105 of the tire puncture repair tool 100 .
The configuration of the tire puncture repair tool 100 in relation to the thread 125 assists in the insertion of the puncture repair screw 150 into the puncture 215 . For example, by providing a uniformly narrowing cone 140 and screw threads 125 , the puncture repair screw 150 is less likely to wobble or move about as the puncture repair screw 150 is inserted into the puncture 215 . Distinct from a conventional screw that has a consistent diameter for a majority of the length, the threaded portion of the puncture repair screw 150 includes a uniformly narrowing cone. The peak ridges 135 of the thread 125 , distinct from prior art approaches to designing a repair screw, provides increased grip or traction to draw the puncture repair screw 150 into the tire 200 as the tire puncture repair tool 100 is rotated from outside the tire 200 .
As previously described and illustrated more fully FIGS. 7B and C, the length of shaft 120 of the puncture repair screw 150 between the start of the thread 125 and the neck of the tool, is configured to be substantially equal to but not greater than the distance between the inside surface 210 and the outside surface 205 of the tire 200 . This feature provides increased functionality to the tire puncture repair tool 100 . The initial ridge 135 of the screw thread 125 is, in various implementations, aligned with the end of the shaft 120 . This peaked ridge 135 , then, also acts to provide resistance against the puncture repair screw 150 slipping out of the puncture 215 . Shafts that are either too long or too short, certainly too long, may be less efficient in repairing the puncture because air may escape more easily even when the puncture repair screw is in place, or the puncture repair screw may more easily slip out of the puncture 215 . Accordingly, various implementations of a tire puncture repair tool 100 may comprise different lengthened shafts 120 sized to specifically fit a variety of tires 200 .
FIG. 7C illustrates a puncture repair screw 150 within a puncture 215 after the handle 105 has been separated from the puncture repair screw 150 . Once the puncture repair screw 150 is within a tire, a user may either continue rotating the handle 105 until the neck 110 breaks, or may alternatively bend the handle 105 back and forth in various directions until the neck 110 breaks. When the neck 110 breaks, the handle 105 may be removed from the puncture repair screw 110 , the puncture repair screw 110 remaining within the puncture 215 .
It will be understood that implementations are not limited to the specific components disclosed herein, as virtually any components consistent with the intended operation of a method and/or system implementation for tire repair puncture tool may be utilized. Accordingly, for example, although particular tire repair puncture tools may be disclosed, such components may comprise any shape, size, style, type, model, version, class, grade, measurement, concentration, material, weight, quantity, and/or the like consistent with the intended operation of a method and/or system implementation for a tire repair puncture tool may be used.
In places where the description above refers to particular implementations of a tire puncture repair tool, it should be readily apparent that a number of modifications may be made without departing from the spirit thereof and that these implementations may be applied to other tire puncture repair tool. The accompanying claims are intended to cover such modifications as would fall within the true spirit and scope of the disclosure set forth in this document. The presently disclosed implementations are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the disclosure being indicated by the appended claims rather than the foregoing description. All changes that come within the meaning of and range of equivalency of the claims are intended to be embraced therein.
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A tire puncture repair apparatus may include a handle, a puncture repair screw, and an integral neck between the handle and the puncture repair screw. The puncture repair screw may include a screw head, a cylindrical shaft extending from the screw head opposite the neck, a partially threaded and solid cone that uniformly narrows from the shaft to a tip opposite the shaft, and a conic-helical thread coiled about the cone between the tip and the shaft. The diameter of the shaft may be approximately equal to the diameter of the cone at the widest point of the cone. The thread on the cone may include an angled ridge and may be coiled around the cone from the intersection of the shaft and the cone to before tip of the cone.
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FIELD OF INVENTION
The present invention generally relates to coolant solutions used in automotive cooling systems. More specifically, the present invention relates to coolant solutions which inhibit corrosion in automotive cooling systems.
BACKGROUND AND SUMMARY OF THE INVENTION
Concentrated alcohol-based solutions are conventionally added to water in automotive cooling systems so as to provide anti-freeze protection. These water/alcohol heat transfer fluids are further inhibited from attack on the metal forming the automotive cooling systems by numerous corrosion-inhibiting additives.
The use of inorganic sodium silicates as corrosion-inhibiting agents is well known. However, sodium silicates tend to gel when used in corrosion-inhibiting effective amounts in alcohol-based coolant solutions. This "gelation" of the corrosion-inhibiting inorganic sodium silicates is problematic since the corrosion-inhibiting effectiveness of the silicate is detrimentally affected. The art has thus attempted to solve the gelation problem by various additives which serve to counteract the tendency of inorganic sodium silicates to gel in alcohol-based antifreeze solutions as evidenced, for example, by U.S. Pat. Nos. 4,149,985, 4,457,852 and 4,44460,478.
The present invention is directed to minimizing (if not eliminating entirely) the tendency of inorganic sodium silicates to gel in alcohol-based antifreeze solutions while simultaneously offering maximum corrosion-inhibiting effectiveness. Broadly, therefore, the present invention is directed to novel anti-corrosion coolant solutions for automotive cooling systems which include a synergistic corrosion-inhibiting effective amount of a sodium silicate having an unusually low ratio of silica to sodium oxide. More specifically, the present invention is directed to alcohol-based liquid solutions for automotive cooling systems which include an anti-corrosive effective amount of (i) a sodium silicate corrosion inhibitor having a ratio of silica (SiO 2 ) to sodium oxide (Na 2 O) of greater than 1.0 to about 2.5 (preferably between about 1.8 and 2.2).
The sodium silicate is typically employed in the alcohol-based liquid coolant system solutions of this invention in an amount sufficient to yield between about 0.01 to 0.2 wt. % silica (more preferably between 0.05 to about 0.06 wt. % silica) based on the total weight of the liquid solution.
The solutions according to the present invention may contain other additives conventionally employed in anti-freeze concentrates. For example, inorganic salts (e.g., sodium phosphate) may be employed in minor amounts up to about 1.5 wt. % based on the total solution weight.
While not wishing to be bound by particular theories, it is believed that by controlling the R value, it is also possible to reduce the corrosion of aluminum. By varying the SiO 2 to Na 2 O ratio (R), the corrosion rate is significantly minimized at an R of greater than about 1.0 to about 2.5, and most preferably about 1.8 to about 2.2.
Commercial antifreeze/coolants generally have polarization resistance (R p ) values in the range of about 10 5 to 10 6 Ohms/cm 2 . The degree of polymerization of silicate may be a function R. Aqueous silicate structure theory has been discussed in Iler, The Chemistry of Silica, Chapter 2, John Wiley & Sons, N.Y., 1979, hereby incorporated by reference.
At 1.0 R, the silicate of N=1 is essentially monomeric. The monomer provides very little corrosion protection. At 2.0 R, a silicate dimer may exist (N=2). At R values above 1.0 and below 2.0, a mixture of monomers and dimers may exist. This species forms a particularly stable film.
At an R value of above 2.3 to about 3.0, the N value is 15. It is believed that a geodesic sphere containing SiO 2 groups forms. This geodesic sphere is a weak inhibitor.
Further aspects and advantages of this invention will become clearer after careful consideration is given to the detailed description of the preferred exemplary embodiments thereof which follows.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plot of the corrosion potential (E corr ) data versus time for silicate solutions having a SiO 2 to Na 2 O ratio of 2.0 (curve A) and a SiO 2 to Na 2 O ratio of 2.5 (curve B).
FIG. 2 is a plot of polarization resistance data versus R values for silicate solutions having a SiO 2 to Na 2 O ratio range of 1.0 to 3.3.
FIG. 3 is a scanning electron photomicrograph, magnification 1000×, of the 1.8 R exposed sample following Electrochemical Impedance Spectra (EIS) and E corr measurements.
FIG. 4 is a scanning electron photomicrograph, magnification 1000×, of the 1.0 R exposed sample following Electrochemical Impedance Spectra (EIS) and E corr measurements.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will become clearer after careful consideration is given to the following nonlimiting examples.
The present invention discloses a critical SiO 2 to Na 2 O ratio (R) of about 1.0 to about 2.5 which has a significant influence on the reaction of a silicate with aluminum.
A good inhibitor system for aluminum must be able to maintain the Al 2 O 3 inner barrier layer and also form a tough outer layer that can withstand depassivating processes. Silicate forms a tough outer layer but the toughness appears to be dependent upon the ratio (R) value. The above-described silica to sodium oxide ratio appears to lay down protective films which appear to prevent the penetration of the oxide layer by chloride.
Corrosion potential (E corr ) measurements and electrochemical impedance spectra (EIS) were used to study the silicate in the inhibition of aluminum. It has been found that silicate alone protects aluminum. Especially at unusually low ratios of silica to sodium oxide of between about 1.8 to 2.2, the protection was greatly enhanced as evidenced by the reduction of noise and the elevation of both E corr and the polarization resistance (R p ).
While not wishing to be bound by any particular theory, it is believed that unstable protective films are probably the cause of electrochemical noise. Thus, it follows that the elimination of or reduction of noise would indicate improvement in the protectiveness of a film. Therefore, noise reduction in the E corr versus time plot shown in FIG. 1 and EIS complements the elevation of E corr R as a tool in the improvement of inhibitor interaction with metal surfaces.
Generally, silicates are manufactured by fusing silica with sodium carbonate using a silica to sodium oxide ratio (w/w) of about 3.2. This product is referred to as 3.2 R silicate. The 3.2 R glass is treated with appropriate amounts of caustic and dissolved in water to make the other silicates: 1.0 R, 1.8 R, 2.5 R and 3.2 R. The manufacture of lower ratio glasses is avoided because the high caustic content wears down the fusing vessels although 2.0 R glass may be prepared to be converted to 1.0 R.
In the examples which follow, reagent grade sodium chloride and sodium metasilicate (having a ratio of SiO 2 to Na 2 O of 1.0, and henceforth referenced as "1.0 R") were used. The silicate with a SiO 2 /Na 2 O ratio of 1.8 was obtained commercially as a specially filtered solution containing 24.1% SiO 2 and 13.4% Na 2 O (referenced henceforth as "1.8 R").
Distilled water was employed to prepare all solutions, it being understood that, in practice, the corrosion inhibitors will be employed in an alcohol-based (e.g., ethylene glycol or propylene glycol) liquid concentrate solution which is then added by the consumer to the water in an automotive coolant system to achieve approximately a 50/50 blend of water and glycol so as to provide anti-freeze protection.
In this connection, although the solutions that were tested were non-alcoholic aqueous solutions, the data is expected to be applicable to 50/50 alcohol/water solutions as well. The solutions that were evaluated in the following examples also contained 100 ppm of sodium chloride so as to enhance localized corrosion. That is, the sodium chloride was present in the solutions so as to evaluate the respective efficacy of the various additives in overcoming the corrosive aggressiveness of the chloride ion.
Keithley Model 616 and 614 digital electrometers were used to measure the corrosion potentials which were recorded on a two channel Houston Instrument recorder. For electrochemical impedance spectroscopy (EIS), a Solartron 1255 frequency analyzer/EG&G PARC Model 273 Potentiostat/Galvanostat combination was used. The experiments were conducted using EG&G PARC Model 388 software and the modeling and graphics were carried out using Boukamp software as described in B. A. Boukamp, "Non-linear Least Squares Fit of AC-Impedance Measurements", Computer Aided Acquisition and Analysis of Corrosion Date, Electrochem. Soc., 146 (1985), hereby incorporated by reference).
The test cells consisted of a 500 ml flat-bottomed beaker as described in S. T. Hirozawa, "Study of the Mechanism for the Inhibition of Localized Corrosion of Aluminum by Galvanostaircase Polarization", Corrosion Inhibition. NACE, pp. 105-112 (1988) and F. Mansfeld, Corrosion, 36, 301 (1981) (both of which are expressly incorporated hereinto by reference), with the exception being that the silver/silver polysulfide reference electrode was substituted for the SCE. The working electrode was 3003-H14 (UNS A93003) aluminum in sheet form whereas the counter electrode was a pair of ultrafine graphite rods. Circles having diameters of 1.5 cm were cut and prepared according to ASTM Practice G1 using 600 grit diamond slurry on a flat lapping machine by Metals Samples and used without further preparation. The specimens were mounted in flat specimen holders.
The solutions were prepared in the cell and attached to the cell cover which had provisions for the electrodes and a thermocouple. Data recording began after the positive lead of the electrometer was connected to the working electrode, and the negative lead was connected to the reference electrode. The solution was continually stirred and heated until the solution temperature stabilized at 82.2° C. (180° F.) for fifteen (15) minutes (thereby simulating the temperature of an automotive coolant system), after which stirring was discontinued. The EI Spectra evaluation was begun 5.5 hours after the solution heater was turned on.
EXAMPLE 1
A plot of E corr vs. time was prepared from the E corr data at 82.2° C. using the above procedures and appears as accompanying FIG. 1. As shown, the ratio of the 2.O R solution significantly reduced noise (curve A) as compared to the 2.5 R solution (curve B). In addition, it will be observed that the E corr data in FIG. 1 for the 2.O R solution was significantly elevated over the E corr data for the 2.5 R solution thereby indicating greater corrosion-inhibiting effectiveness.
Electrical Impedance Spectra (EIS) were obtained for various R values. From these spectra the polarization resistance (R p ) was determined. The corrosion rate varies inversely with R p ; thus, the larger the R p value, the lower the corrosion rate.
FIG. 2 is a plot of polarization resistance data versus R values for silicate solutions having a SiO 2 to Na 2 O ratio range of 1.0 to 3.3. FIG. 2 shows a significant maxima about 2.O R. The corrosion rate at this ratio is approximately 3 times lower than for the next closest data point (1.8 R).
FIG. 3 is a scanning electron photomicrograph, magnification 1000×, of the 1.8 R exposed sample of aluminum following EIS and E corr measurements. The surface of the sample is smooth and free of pits.
FIG. 4 is a similar electron photomicrograph to that shown in FIG. 3, however, for R=1.0, the sample has open pits and surface roughness caused by corrosion. Both FIGS. 3 and 4 confirm the electrical measurements.
The E corr data, EIS and micrograph data demonstrate the effectiveness of a low ratio of SiO 2 to Na 2 O significantly reduces the corrosive effects on aluminum.
Thus, 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, but on the contrary, is intended to cover various modifications and equivalents included within the spirit and scope of the appended claims.
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Non-corrosive anti-freeze solutions for automotive cooling systems include an anti-corrosive effective amount of a sodium silicate corrosion inhibitor. The sodium silicate has an unusually low ratio of silica to sodium oxide of greater than 1.0 to about 2.5. This relatively low ratio of silica to sodium oxide prevents gelation from occurring while maintaining maximum anti-corrosive effectiveness of alcohol-based solutions containing the same.
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BACKGROUND OF THE INVENTION
The present invention relates to means for improving the flavour of cheeses and of cheese specialities.
Pressed cheeses without surface flora, which are manufactured essentially with lactococci, have little flavour; its development requires very long ripening times, of the order of 3 to 6 months or even more, for cheeses of the Gouda or Cheddar type, whereas most of these pastes are marketed after considerably shorter ripening times (of the order of a few weeks).
One of the principle objectives of cheese manufacturers is to enhance the flavour of these cheeses, without substantially modifying their manufacturing technology, and without extending the ripening time.
DESCRIPTION OF THE RELATED ART
The enzymatic degradation of amino acids is one of the routes of production of flavour molecules. Indeed, amino acids, and in particular aromatic amino acids, branched amino acids and sulphur-containing amino acids are precursors of flavour compounds of the aldehyde, alcohol, acid or thiol type. Some of these compounds have been identified in cheeses and participate in their flavour [(DUMONT et al., Lait 54:31-43, (1974); MC CUGAN, J. Agric. Food Chem. 23:1047-1050, (1975), GREEN and MANNING, J. Dairy Res. 49:737-748, (19382), NEY and WIROTAMA, Z. Lebensm. -Unters, -Forsch. 146:337-343, (1971)].
It has therefore been proposed to enhance the proteolysis in cheeses so as to increase the quantity of free amino acids. The proteolytic system of lactococci has been widely studied, several peptidases have been purified and characterized and their genes have been cloned and sequenced [LAW and MULHOLLAND, Int. Diary J. 5:833-854, (1995)]. Genetically-modified strains which overexpress these peptidases have been constructed; the use of such strains for the manufacture of “Cheddar” type cheeses was recently described [MC GARRY et al., Appl. Environ. Microbiol. 60:4226-4233, (1994), CHRISTENSEN et al., Int. Dairy J. 5:367-379, (1995)]. However, although the over-expression of peptidases increases the accumulation of the free amino acids, it does not significantly affect the development of flavour. It therefore appears that the factors limiting the development of flavour do not exist at the level of the production of free amino acids, but are also involved in their degradation.
Activities for converting amino acids into flavour compounds nevertheless exist in lactococci. ENGELS and VISSER, [Neth. Milk Dairy J. 50:3-17, (1996)] have shown that flavours typical of Gouda could be generated by incubating cellular extracts of lactococci with methionine. The enzyme assumed to be responsible for this conversion has been purified and characterized; it is a cystathionine β-lyase [ALTING et al., Appl. Environ. Microbiol. 61:4037-4042, (1995)].
It has also been observed that lactococci were capable of degrading in vitro aromatic amino acids and branched amino acids into flavour compounds of the hydroxy acid and acid type. The first step of the degradation of these amino acids is a transamination which requires the presence of an acceptor keto acid [THIROUIN et al., abstr. M4, Club des Bactéries Lactiques (Lactic Acid Bacteria Club)—7th colloquium, Paris, France (1995)]. The transamination is also involved in the degradation of methionine to methanethiol [ALTING et al., Fifth symposium on Lactic acid bacteria: Genetics, metabolism and applications, Veldhoven, The Netherland, Sep. 8-12 1996].
Using a strain of L. lactis ssp cremoris, the Inventors' team has purified and characterized an amino transferase, and observed that in a simple liquid medium containing glucose, this enzyme could, in the presence of α-ketoglutarate, catalyse the transamination of the three aromatic amino acids (phenylalanine, tryptophan and tyrosine), of leucine and of methionine; this enzyme is active under temperature, pH and ionic strength conditions similar to those encountered during the refining of cheese [YVON et al., Appl. Env. Microbiol., 63, 414-419 (1997)]. The Inventors' team has moreover identified two other aminotransferases which are active on branched amino acids, and which use α-ketoglutarate and, to a lesser degree, oxaloacetate as amino group acceptor. These keto acids may come from the degradation of glutamate or of aspartate, which are always present in cheeses in a large quantity, or they may be synthesized from acetyl-CoA, since the portion of the Krebs cycle between oxaloacetate and α-ketoglutarate appears to be operational in lactococci [LOUBIERE et al., Le Lait 76 (1-2): 5-12, (1996)].
However, the Inventors have observed that in experimental cheeses manufactured with the abovementioned strain of L. lactis ssp cremoris, the degradation of the aromatic amino acids was in fact very low (2 to 5%) which suggested the existence of factors limiting this degradation in cheeses. Among these limiting factors, the most probable existed at the level of the diffusion of the amino acids and their transport inside the energetically drained bacteria cells (because of the fact that at the time of refining, practically all the sugars which can be used as energy source have already been consumed).
However, the Inventors made the hypothesis that the quantity of acceptor keto acids present in cheese represented the first limiting factor.
To verify this hypothesis, the Inventors have, in the first instance, studied, in simple liquid media, the effect of the addition of simple α-ketoglutarate and of oxaloacetate on the degradation of aromatic and branched amino acids by whole lactococci cells. They have thus observed that the addition of α-ketoglutarate increased the degradation of the aromatic and branched amino acids, and that the addition of oxaloacetate increased that of the branched amino acids. They then sought to confirm this result in cheeses, and observed that in this case, only the addition of α-ketoglutarate had an action on the degradation of the amino acids.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to the use of keto acids and in particular of α-ketoglutarate as preparation additive, for enhancing the flavour of a cheese or of a cheese-flavoured food product whose preparation comprises a step of maturation (ripening) in the presence of lactic acid bacteria, and in particular of lactococci. This enhancement of the flavour results from the increase in the catabolism of the amino acids by the said bacteria.
The present invention may be used within the framework of the manufacture of various types of cheese. It is particularly advantageous for the manufacture of pressed cheeses without surface flora, in particular of cheeses with artificial rind. It may also be used within the framework of the manufacture of food products on which it is desired to confer a cheese flavour, among which there may be mentioned in particular food produces in which at least one of the ingredients is obtained from a curd or a milk protein concentrate (casein+whey proteins), such as enzyme-modified cheese bases (<<Enzyme Modified Cheese >>), cheese specialities, processed cheeses, low-fat cheeses.
The subject of the invention is in particular a process for the production of a cheese or of a cheese-flavoured food product, characterized in that a preparation additive comprising at least one keto acid chosen from the group consisting of α-ketoglutarate, and the keto acids which are direct precursors of flavour compounds, such as α-ketoisocaproate, ketoisovalerate, and phenylpyruvate, is used to enhance the flavour of the said product.
DETAILED DESCRIPTION OF THE INVENTION
According to a preferred embodiment of the present invention, the preparation of the said product comprises a maturation step in the presence of at least one lactic acid bacterium belonging to one of the genera Lactococcus, Lactobacillus, Streptococcus and Leuconostoc, and the said additive is added to the said product, prior to the said maturation step or during it.
According to a preferred embodiment of the present invention, the said lactic acid bacterium is chosen from the group consisting of Lactococcus lactis ssp lactis, Lactococcus lactis ssp. cremoris, Lactococcus lactis ssp. diacetylactis, Lactobacllus delbrueckii lactis, Lactobacillus delbrueckii bulgaricus, Lactobacillus plantarum, Lactobacillus helveticus, Lactobacillus paracasei, Streptococcus thermophilus.
When the said additive comprises α-ketoglutarate, the transamination reaction produces, on the one hand, precursors of flavour compounds and, on the other hand, glutamate, which is in fact a taste enhancer. When it comprises keto acids which are direct precursors of flavour compounds, these may, like α-ketoglutarate, play a role of acceptor for the transamination reactions, and may also be directly degraded into various flavour compounds, which makes it possible to obtain different tastes depending on the keto acid(s) chosen.
The quantity of additive which is used may vary according to the degree of flavour enhancement which it is desired to obtain. For example, α-ketoglutarate may generally be used in an amount of 0.5 to 10 mg per gram of non-matured product (non-matured product is understood to mean the drained curd, or the ultrafiltration retentate, in the case of products obtained by ultrafiltration of milk).
To carry out the invention, the said additive may be introduced directly or indirectly into the product during manufacture. The direct introduction may be easily carried out, for example, by soaking the non-matured product or during maturation, in a solution of α-ketoglutarate, or by impregnating the product with a concentrated solution of α-ketoglutarate, before or after salting, or by adding the keto acid(s) to the salt or to the brine used for the salting, or at the time of lactose removal in the case of lactose-free cheeses, or alternatively, in the case of the products obtained by ultrafiltration, by adding to the ultrafiltration retentate.
Advanatageously, when the α-ketoglutarate is introduced into the brine used for the salting, it is added thereto in an amount of 10 to 100 grams per liter of brine.
The indirect introduction may be made by the addition of a strain capable of producing α-ketoglutarate from the glutamate present in cheeses. This may be either a strain of lactococcus or of another lactic acid bacterium, or another refining microorganism, which strain may have been selected or genetically modified.
The subject of the present invention also covers the cheeses capable of being obtained by the process in accordance with the invention.
The present invention will be understood more clearly with the aid of the additional description which follows, which refers to nonlimiting examples showing the influence of the addition of a keto acid on the catabolism of amino acids by lactococci, and of the addition of α-ketoglutarate to cheeses on their organoleptic qualities, and on the degradation of the amino acids in these cheeses.
EXAMPLE 1
Effect of the Addition of α-Ketoglutarate or of Oxaloacetate on the Degradation of Amino Acids by the Cells of Lactococci in Liquid Medium
The catabolism of amino acids by lactococcus cells was studied in various media, in the presence or in the absence of keto acids.
Two series of media were used.
A first series is composed of 100 mM Tris/HCl buffer, pH 8 with 2 mM of the non-labelled studied amino acid, and 0.05 μm of the same amino acid which has been tritiated. 10 mM of α-ketoglutarate or of oxaloacetate were added to these basal media.
The second series of media is composed of the same 100 mM Tris/HCl buffer, pH 8, with 2 mM of the non-labelled amino acid and 0.05 μM of the tritiated amino acid, plus 0.3% of glucose. As above, 10 mM of α-ketoglutarate or of oxaloacetate were added to the basal media.
The cells derived from 4 ml of a culture of the strain in a chemically defined medium [SMID and KONINGS, J. Bacteriol, 174:5286-5292, (1990)] are incubated in 0.5 ml of the different media, at 37° C. Aliquots are collected after 10, 20 and 40 hours of incubation, the cells are removed by centrifugation (8000 g, 5 min), and the metabolites are separated by HPLC and identified by comparing their retention time with those of standard compounds. The separation is carried out on a NOVAPACK reversed-phase column (2 mm×150 mm, WATERS) equilibrated with 95% of solvent A (trifluoroacetic acid at 0.115%) and 5% of solvent B (0.1% trifluoroacetic acid, 60% acetonitrile) at a flow rate of 03 ml/min. The metabolites are eluted with a linear gradient of 5 to 20% of solvent B over 35 min. The column is then washed for 5 min with solvent B and then reequilibrated under the initial conditions. The metabolites are detected by UV absorbance at 214 nm and then the eluent (0.3 ml/min) is mixed with the ULTIMA-FLO AP scintillation feed (PACKARD) (0.7 ml/min) for the continuous-flow detection of radioactivity. The standard compounds used are phenylalanine, phenylethylamine, phenylpyruvate, phenylacetaldehyde, phenylethanol, phenylacetate and phenyllactate.
Results
The results are summarized in Table I below, which indicates, for each of the amino acids tested, the quantity of amino acid degraded (as % of the initial quantity), after 10 hours of incubation.
TABLE 1
Without glucose
With glucose
Amino
without
with
with
without
with
with
acid
keto acid
ketoglutarate
oxaloacetate
keto acid
ketoglutarate
oxaloacetate
Tyrosine
3
46
—
10
71
—
Phenylalanine
5
40
7
13
62
10
Tryptophan
8
58
—
19
79
—
Leucine
4
60
20
20
80
—
These results show that in liquid media not containing ketoglutarate, the degradation of the three aromatic amino acids and of leucine is low. It is close to 5% in 10 hours in the media without glucose and 10 to 20% in the media containing glucose.
The addition of α-ketoglutarate to these media considerably increases the degradation of all these amino acids. In the media without glucose, 40 to 60% of the amino acids are degraded in 10 hours and the degradation reaches 75 to 80% in 40 hours. In the media containing glucose, 60 to 80% of the amino acids are degraded in 10 hours and their degradation is complete after 40 hours.
The addition of oxaloacetate has no effect on the degradation of the aromatic amino acids but substantially increases that of leucine.
The principle metabolites detected are the keto acids corresponding to each amino acid, as well as their degradation products (hydroxy acids and carboxylic acids).
EXAMPLE 2
Effect of the Addition of α-Ketoglutarate to Cheeses on the Degradation of Phenylalanine
Manufacture of Uncooked Pressed Cheese with Artificial Rind
Five small cheeses of the Saint-Paulin type (250 g) were manufactured from 10 liters of partially skimmed milk (32 g of fat per liter) and pasteurized for 1 min at 750° C. The milk is inoculated at the rate of 2% with an overnight culture of Lactococcus lactis (strain NCDO763 of Lactococcus lactis ssp cremoris ) in skimmed milk. The renneting is carried out immediately at 33° C. using 0.03% of rennet (520 mg/l of chymosin, SBI, France). During the stirring, lactose is partially removed from the curd by replacing 30% of the whey with water at 32° C. The curd is then moulded in KADOVA-type moulds and pressed.
Salting and Ripening of the Cheeses
After pressing, one of the cheeses is cut into small cylinders of about 3 g (mini cheeses) for the analysis of the degradation of phenylalanine.
Two brines were used for the mini cheeses intended for the analysis of the degradation of phenylalanine. The first contains 0.1 g of NaCl and 31.25 μCi (0.25 nmol) of tritiated phenylalanine (L-[2,3,4,5,6- 3 H]phenylalanine) per ml. The second brine contains, in addition to the constituents of the first, 50 mg of α-ketoglutarate per ml. The pH of the two brines is adjusted to 5.7. A mini cheese is immersed in 8 ml of each brine for 1 hour.
After salting, the cheeses are stored in a refrigerator overnight; the next day, they are coated with edible wax and placed in a cellar at 13° C.
Extraction and Analysis of the Products of Degradation of Phenylalanine in the Cheeses
After 10 days of ripening, about 1 g of cheese is homogenized in 2.5 ml of citrate buffer (0.2M sodium citrate, pH 2.2, 0.2 g of EDTA and 0.1 ml of pentachlorophenol at 5% per liter). The mixture is filtered on paper and the filtrate is precipitated in the presence of sulphosalicylic acid at a final concentration of 3%. The precipitate is removed by centrifugation (5 min at 18,000 g) and the supernatant is filtered on a 0.45 μm filter. The products of degradation of the phenylalanine are then separated and identified by HPLC as described in Example 1 above.
Results
The HPLC separation profiles obtained after 10 days of ripening at 13° C. show that only 3 to 4% of the labelled phenylalanine was degraded in the control cheese, whereas 17% was degraded in the cheese ripened in the presence of α-ketoglutarate. Phenylpyruvate, as well as its degradation products phenyllactate and phenylacetate were identified among the metabolites formed.
EXAMPLE 3
Effect of the Addition of α-Ketoglutarate to Cheeses on their Organoleptic Quality
250 g cheeses of the Saint-Paulin type are manufactured as described in Example 2 above.
Two of these cheeses are immersed for 3 hours in 2 liters of brine containing 250 g of NaCl per liter and 2 others in 2 liters of brine containing 250 g of NaCl and 50 g of α-ketoglutarate per liter.
Moreover, two other cheeses are each cut into 10 pieces of 25 g. Ten of these pieces are immersed for 2 h 30 min in 0.75 liter of brine containing 100 g of NaCl and the other ten in 0.75 liter of a brine containing 100 g of NaCl and 30 g of α-ketoglutarate per liter.
The pH of all the brines is previously adjusted to 5.7 with lactic acid.
After salting, the cheeses are stored in a refrigerator overnight; the next day, they are coated with edible wax and placed in a cellar at 13° C.
Organoleptic Analyses
These analyses were carried out on 250 g cheeses.
The cheese with α-ketoglutarate and the control cheese were tasted after 14 and 28 days of ripening at 13° C. by a panel of 8 people. 13 characters were scored from 1 to 10 according to their intensity.
The characters evaluated are: the odour intensity, the overall cheese quality, the tastes: salty, sour, mild, sweet and bitter, and the flavour characters: fruity, floral, sulphur-like, maltol-like, milky, and foot. The results obtained for the cheese with α-ketoglutarate and the control cheese were compared by variance analysis.
Results
The results are illustrated by Table II below, which groups together the mean values of the marks given to each character by a panel of 8 people.
FIG. 1 represents the star-shaped profile of the marks given to the control cheese (—▴—) and the cheese with α-ketoglutarate () after 28 days of ripening.
TABLE II
Ripening time
14 days
28 days
Character
marked
Control
Test
Control
Test
Odour
2.08 ± 0.90
2.65 ± 1.95
1.68 ± 1.33
2.60 ± 1.7
intensity
Bitter
1.66 ± 0.97
2.13 ± 1.30
2.02 ± 1.27
1.33 ± 0.61
Mild-sweet
2.65 ± 1.41
2.31 ± 1.62
2.54 ± 1.35
3.53 ± 0.90
Salty
3.62 ± 1.33
4.22 ± 1˜09
4.05 ± 1.02
4.20 ± 0.96
[sic]
Sour
2.91 ± 1.49
3.68 ± 2.44
3.48 ± 2.11
3.20 ± 1.49
Foot
1.08 ± 1.37
2.16 ± 1.96
1.54 ± 1.53
2.11 ± 2.58
Sulphur-like
0.69 ± 0.56
0.94 ± 1.53
0.91 ± 0.91
1.08 ± 1.03
Fruity
2.00 ± 1.54
1.80 ± 1.11
2.02 ± 1.50
3.11 ± 1.66
Floral
0.96 ± 1.20
1.87 ± 1.81
1.14 ± 0.99
2.31 ± 1.99
Maltol-like
1.65 ± 1.28
1.43 ± 1.28
2.20 ± 1.74
2.94 ± 2.79
Milky
1.85 ± 2.04
1.54 ± 1.20
2.65 ± 1.65
2.48 ± 1.69
Degree of
4.62 ± 2.36
5.08 ± 2.42
4.22 ± 2.37
4.31 ± 2.21
ripening
Mark for
3.66 ± 2.04
2.83 ± 1.54
4.20 ± 1.71
5.25 ± 1.56
quality
After 14 days of ripening, the taste panels noted Little difference between the control cheese and the test. Only the mark for the floral character was significantly higher for the test.
After 28 days of ripening, the marks for the flavour characters: fruity, foot, floral, maltol-like; the odour intensity and the mark for quality are higher for the test. 6 judges out of 8 gave a mark for quality substantially higher for the test and 1 judge did not observe any difference. Overall, the panel emphasized “a more pronounced cheese flavour” and “a highly perfumed cheese” for the cheese with α-ketoglutarate.
It therefore appears that the increase in the degradation of phenylalanine, demonstrated by chemical analysis, impacts on the flavour of the cheeses, since the floral note, which is characteristic of the degradation compounds of aromatic amino acids, is significantly higher in the cheese with ketoglutarate tasted at 14 days.
After 28 days of ripening, the effect of the addition of α-ketoglutarate on the flavour is clearer than after 14 days of ripening. In particular, the odour intensity which is linked to the production of volatile molecules is significantly more intense.
In addition, the overall mark for quality shows that the intensification of the degradation of the amino acids does not generate taste defects but rather improves the organoleptic quality of the cheeses.
Sensory Analysis of the Flavours (Triangular Test).
This analysis was carried out on the 25 g pieces. The ketoglutarate concentration is close to zero for the control cheeses and close to 5 mg per g of cheese for the cheeses brined in the presence of ketoglutarate.
The odour of the cheeses with and without ketoglutarate was compared by a triangular test in which 24 judges participated.
This zest consists in presenting to the judges 3 samples, 2 of one of the cheeses, and 1 of the other cheese.
They are asked:
in a first instance, to indicate which sample is different from the other 2 and which one(s) is (are) the most odorous;
in a second instance, to mark the intensity of the difference perceived on a scale from 1 to 10, and if possible to characterize this difference.
The statistical interpretation consists in calculating the number of correct answers (which recognized the sample different from the other two) and in comparing the value obtained with that presented in the table of the binomial law for a probability of 1 over 3 to know if a significant difference exists.
Results:
The cheese ripened in the presence of ketoglutarate is significantly more odorous than the control cheese, at the 0.1% threshold (the difference was perceived by 18 judges out of 24). The intensity of the difference perceived was marked on average at 3.22/10 and this difference is frequently described as: “a more cheesy odour”. Thus, it appears that the addition of ketoglutarate really enhances the development of flavour in the cheeses.
EXAMPLE 4
Effect of the Addition of α-Ketoglutarate to Cheeses on the Degradation of Amino Acids
The free amino acids present in the cheeses used in Example 3 were assayed after 14 days of ripening.
Extraction and Analysis of Free Amino Acids
The free amino acids are extracted from the cheeses according to the protocol described for the extraction of the products of degradation of phenylalanine in Example 1. They are then analysed with the aid of an LC3000 automated amino acid analyser (BIOTRONIK) under the conditions recommended by the manufacturer of the apparatus.
Results
Table III below indicates the quantities of each amino acid (in nmol/g of cheese) in the control cheese and in the cheese with ketoglutarate. It also indicates the difference between these quantities, expressed, on the one hand, in nmol/g of cheese, and, on the other hand, in % of the quantity in the control cheese.
TABLE III
Quantity of amino acids in nmol/g of cheese
Control
+ ketoglu-
Difference
Difference
tarate
(nmol/g)
in %
Aspartate
543
511
−32
−5.8
Threonine
562
545
−17
−3
Serine
985
979
−6
−0.6
Asparagine
2838
2808
−30
−1
Glutamate
3275
3763
+488
+15
Glutamine
2220
2250
+3
+0.1
Proline
1899
1906
+7
+0.3
Glycine
396
384
−12
−3
Alanine
1144
1075
−69
−6
Citrulline
399
421
+21
+5
Valine
1730
1649
−81
−4.6
Methionine
462
413
−49
−10.6
Isoleucine
358
322
−37
−10.3
Leucine
4999
4514
−485
−9.7
Tyrosine
1062
1017
−46
−4.3
Phenylalanine
2919
2669
−250
−8.6
γ-Aminobutyrate
1887
2870
+982
+52
Ornithine
2354
2248
−106
−4.5
Lysine
2327
2328
+1
+0.04
These results show that the quantities of methionine, isoleucine, leucine and phenylalanine in the cheese ripened in the presence of ketoglutarate are about 10% lower than in the control cheese and the quantities of aspartate, alanine, valine, tyrosine and ornithine are about 5% lower. This demonstrates that the addition of α-ketoglutarate to the cheeses greatly intensifies the degradation of the branched acids and of the aromatic amino acids although in this case, the quantity of ketoglutarate incorporated is moderate (about 1 mg/g of drained curd).
Moreover, the quantities of glutamate and of γ-aminobutyrate (which comes from glutamate) are considerably higher in the cheese with ketoglutarate than in the control cheese. This confirms that the ketoglutarate added was indeed used for the transamination reaction and converted to glutamate (which is moreover a taste enhancer).
The other amino acids are in equivalent quantity in both cheeses.
EAXMPLE 5
Effect of the Addition of α-Ketoglutarate to Liquid Reaction Media and to Pseudocurds on the Degradation of the Amino Acids by Various Species of Lactic Acid Bacteria
This example demonstrates the influence of the addition of ketoglutarate on the catabolism of the amino acids by lactic acid bacteria other than lactococci. This study was carried out, on the one hard, in liquid media and, on the other hand, in a pseudocurd. The tests in pseudocurds represent an alternative to the tests in real cheeses which, on the one hand, are long and expensive and which, on the other hand, are difficult to carry out with pure strains of lactic acid bacteria other than lactococci. Indeed, in the cheeses, the lactic acid bacteria belonging to the genus Lactobacillus are always associated with lactococci or with streptococci. For example, the Lactobacillus delbrueckii and the Lactobacillus helveticus are associated with Streptococcus thermophilus in cooked pressed cheeses. The Lactobacillus of the paracasei or plantarum type develop for their part during a fairly long ripening of pressed cheeses manufactured either with lactococci or with streptococci. The latter are in fact called “non starter” lactic acid bacteria unlike the “starter” lactic acid bacteria which are responsible for the acidification. For this study, phenylalanine and leucine, which are the predominant free amino acids in cheeses, were chosen as marker amino acids, respectively for aromatic amino acids and for branched-chain amino acids.
Strains of Lactic Acid Bacteria and Preparation of the Cells.
The lactic acid bacteria chosen belong to the genera Lactobacillus and Streptococcus. They are the species most frequently encountered in dairy technology. Lactococcus lactis NCDO 763 serves as “control” in this study.
The seven strains used, which possess the characteristics of strains conventionally used in dairy technology, are obtained from the CNRZ collection (INRA, Jouy-en-Josas). They are: Lactococcus lactis ssp. cremoris (strain NCDO 763) Lactobacillus delbrueckii lactis (strain CNRZ 12) Lactobacillus delbrueckii bulgaricus (strain CNRSRZ 752)
Lactobacillus plantarum (strain CNRZ 1228)
Lactobacillus helveticus (strain CNRZ 32)
Lactobacllus paracasei (strain CNRZ 316)
Streptococcus thermophilus (strain CNRZ 302).
The lactobaccili are cultured in an MRS medium (DIFCO), the streptococcus in an M17 medium (DIFCO) containing 10 g/l of lactose and the lactococcus in M17 medium with glucose. The cultures are incubated at 37° C. except Lb. paracasei and Lb. plantarum which are cultured at 30° C.
The cells are recovered at the beginning of the stationary growth phase by centrifugation (8000 g, 10 min) and washed twice with 50 mM glycerophosphate buffer, pH 7.
Tests in Liquid Reaction Media.
The basal medium is composed of 100 mM Tris/HCl buffer pH8, with 2 mM of the non-labelled studied amino acid (phenylalanine or leucine) and 0.05 μM of the same amino acid which has been tritiated (126 mCl/μmol) (L-[2,3,4,5,6- 3 H]phenylalanine or L-[4,5- 3 H]leucine), and then 0.3% of glucose. For the tests with ketoglutarate, 10 mM of this compound are added to the basal medium.
The quantity of cells corresponding to an OD 480 of 10 is introduced into 500 μl of medium and 100 μl aliquots are collected at time 0 and then after 10 h, 20 h and 40 h of incubation at 37° C.
Tests in Pseudocurd.
The degradation of labelled (tritiated) amino acids was also studied in a pseudocurd whose composition is similar to that of a cheese.
This pseudocurd is prepared by mixing 4.5 ml of a solution of calcium phosphocaseinate at 10% sterile (115° C., 10 min) with 20 μl of a 10M solution of calcium chloride and 0.5 ml of a solution of amino acids simulating the free amino acid composition of a 4-week old St Paulin type cheese (cf. Table IV below) and containing 20 μCi of the tritium-labelled amino acid studied. For the tests with ketoglutarate, the latter is added in an amount of 4 mg/ml of medium. These two solutions are sterilized beforehand by filtration.
The cells obtained from a 5 ml culture are added to this mixture just before introducing thereto powdered gluconolactone at a final concentration of 15 g/l. Aliquots of 1 ml are then distributed into sterile tubes with a conical bottom, and 3 μl of rennet diluted {fraction (1/10)} and sterilized by filtration are finally added. The mixture is incubated at 30° C. until the curd sets and then the tubes are placed in an oven at 130°C. for “ripening” for 2 to 4 weeks.
TABLE IV
in μmol/g
in μg/g
Aspartate
0.8
110
Threonine
0.9
110
Serine
1.3
140
Asparagine
2.6
340
Glutamate
5
740
Glutamine
3.2
470
Proline
2.4
280
Glycine
0.5
40
Alanine
1.5
130
Valine
0.5
340
Cysteine
2.9
60
Methionine
1
150
Isoleucine
0.8
100
Leucine
6.4
840
Tyrosine
1.3
240
Phenylalanine
3.7
610
Histidine
0.6
90
Lysine
2.8
410
Extraction and Monitoring of the Degradation of Amino Acids.
In the liquid reaction media, the cells are removed by centrifugation (8000 g, 5 min) and the supernatants are directly analysed by HPLC with a continuous flow radioactivity detection, as described in example 1. This analysis allows the separation of the amino acid and of the various degradation products. The percentage degradation of the amino acid is estimated by the percentage of radioactivity present in the degradation product elution volume.
For the pseudocurds, the content of each tube (about 1 g) is homogenized with an ULTRA-TURAX in 2.5 ml of citrate buffer (0.2M sodium citrate, pH2.2, 0.2 g of EDTA and 0.1 ml of pentachlorophenol at 5% per liter). The mixture is then centrifuged for 5 min at 8000 g and the supernatant is precipitated in the presence of sulphosalicylic acid at a final concentration of 3%. After 10 min at 0° C., the precipitate is again removed by centrifugation (5 min at 18,000 g) and the supernatant is filtered on a 0.45 μm filter. The products of degradation of the amino acids are then separated, identified and quantified by HDLC as described above.
Results
1. The percentages of degradation of phenylalanine and of leucine in the liquid reaction media containing ketoglutarate or otherwise, after 10 h and 40 h of incubation at 37° C., are presented in Table V.
TABLE V
Phenylalanine
Leucine
without
with
without
with
ketoglu-
ketoglu-
ketoglu-
ketoglu-
tarate
tarate
tarate
tarate
Strains
10 h
40 h
10 h
40 h
10 h
40 h
10 h
40 h
Lc.lactis
7
13
71
98
20
—
30
—
Lb.d.bulgaricus
0
0
14
39
0
0
9
30
Lb.d.lactis
0
0
1
3
0
0
10
27
Lb.plantarum
9
11
38
73
6
10
23
42
Lb. helveticus
0
0
9
18
0
2
7
25
St.
7
15
25
48
9
10
38
67
thermophilus
Lb. paracasei
29
63
66
99
43
54
80
85
These results show that for all the strains studied, except Lb. paracasei, the degradation of the amino acids in the media not containing ketoglutarate is low: it remains less than 15% even after 40 hours of incubation at 37° C. The addition of ketoglutarate to the media considerably increases the degradation of the amino acids by all the strains studied. The percentage degradation is at least multiplied by 2. Similar results were obtained in media not containing glucose.
The degradation observed in the absence of ketoglutarate with Lb. paracasei indicates that for this bacterium, either the pyruvate obtained from the degradation of the glucose is an acceptor of the amine group in the transamination reaction, or that there is another route of degradation other than transamination. Nevertheless, with this strain as well, the addition of ketoglutarate substantially intensifies the degradation of the two amino acids tested.
2. The percentages of degradation of phenylalanine and of leucine in the pseudocurds after 2 and 4 weeks of ripening at 13° C. are represented in Table VI.
TABLE VI
Phenylalanine
Leucine
without
with
without
with
ketoglu-
ketoglu-
ketoglu-
ketoglu-
tarate
tarate
tarate
tarate
Strains
2 wk
4 wk
2 wk
4 wk
2 wk
4 wk
2 wk
4 wk
Lc.lactis
3
3
4
6
5
6
8
11
Lb.d.bulgaricus
0
0
18
22
1
1
7
10
Lb.d.lactis
0
0
11
7
0
0
3
4
Lb.plantarum
1
2
7
13
—
—
—
—
Lb. helveticus
0
0
6
10
0
0
0
2
St.
0
1
2
3
0
0
5
9
thermophilus
Lb. paracasei
0
0
7
3
0
0
10
10
As in the liquid media, for most of the strains of lactic acid bacteria studied, the degradation of the amino acids in the pseudocurds without ketoglutarate is practically zero. On the other hand, in the presence of keroglutarate, all the strains degrade phenylalanine ar,d leucine, and the degradation after 4 weeks varies between 2% and 22% depending on the strains and the amino acid considered. It should be noted that the percentages of degradation observed in these pseudocurds with Lactococcus lactis after 4 weeks are of the same order as those found in the St Paulin type cheeses manufactured with this strain and also ripened 4 weeks in the presence of ketoglutarate (9.8% and 12.8% respectively for phenylalanine and leucine in the cheeses, to be compared with 6% and 11% in the pseudocurds). Consequently, the results obtained with this model may be considered as being representative of what would be observed in cheeses.
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Process for enhancing the flavour of a cheese or of a cheese-flavoured food product whose preparation comprises a maturation step in the presence of lactic acid bacteria, characterized in that a preparation additive comprising at least one keto acid chosen from the group consisting of α-ketoglutaric acid, α-ketoisocaproic acid ketoisovaleric acid and phenylpyruvic acid is used to increase the catabolism of the amino acids in the cheese or food product by the said bacteria.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a color image forming apparatus having a plurality of photoconductive members wherein each of plural latent images is formed on a surface of a separate photoconductive member and is developed by utilizing liquid development for each of the color images.
2. Description of the Related Art
In a conventional color image forming apparatus, it is known that each latent image, which is developed by utilizing dry developer or liquid developer, is formed on the surface of a separate photoconductive member in accordance with information of each color resolution. The developed images are transferred onto a transfer sheet and fixed by a pair of fixing rollers. Toner for liquid development (WET-TYPE) has an advantage of producing a high quality copied image, since toner particles for liquid development are much smaller than those for dry development and since toner for liquid development has excellent transparency characteristics and produces fine image resolution. However, the liquid development, which has different characteristics than does dry developer, is difficult to use due to its fluidity, viscosity, etc., and such a color image forming apparatus using a plurality of color developers has many difficult problems.
An example of a color development system wherein a plurality of developing units are disposed below a drum type photoconductive member and the developing units are moved for developing each color image on the photoconductive member corresponding to each color resolution is disclosed in Japanese Laid-Open Publication No. 55-12758. In addition, in another example of a color development system, a color image forming apparatus uses a four color developer (yellow, cyan, magenta and black) having two developing units, wherein two color images are developed by each unit. Moreover, while one developing unit develops one color image, the developer in another developing unit is exchanged and the developing unit is cleaned. This is disclosed in Japanese Laid-Open Publication No. 3-186870.
In the prior art disclosed in Japanese Laid-Open Publication No. 55-127580, the liquid developer is liable to adhere to the photoconductive member portion where the liquid developer is not necessary, due to its fluidity and viscosity. This contaminates a transfer portion so that after transferring, the liquid developer gets mixed with other developer in the developing units disposed below the drum type photoconductive member. Such mixing causes a color mixture problem.
In order to prevent such problems, there is required an extra device or a complex structure, such as a device for preventing the liquid developer adhering to the photoconductive member portion where a developer is not necessary, a device for removal of the developer for cleaning or a device for reusing the developer for cleaning. The extra device or the complex structure increases the cost of the apparatus.
In the prior art disclosed in Japanese Laid-Open Publication No. 3-186870, it is difficult to avoid the color mixture problem and there is a limitation of image forming speed because two color images are developed by one developer unit.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a color image forming apparatus in which the above-mentioned conventional shortcomings are eliminated. More specifically, it is an object of the present invention to provide a color image forming apparatus having a plurality of photoconductive members arranged on the same plane and each corresponding to a color, and a casing with top opening which is provided below each photoconductive member, wherein one of latent images is formed on each of the photoconductive members by electrophotography and then a transfer sheet is transported to the transfer portion by a transfer belt, and the developed images on each of the photoconductive members is transferred to the transfer sheet.
It is another object of the present invention to provide a color image forming apparatus in which operation timing of each development roller and/or timing of each developer replenisher are/is staggered in turn.
It is another object of the present invention to provide a color image forming apparatus in which the widths of the photoconductive members and of cleaning portions disposed around the photoconductive members are greater than that of a transfer sheet, and the widths of the cleaning portions are different in accordance with vertical positions of the cleaning portions.
It is a further object of the present invention to provide a color image forming apparatus, in which the widths of the photoconductive members and of the cleaning portions disposed around the photoconductive members are greater than that of a transfer sheet, and the widths of the photoconductive members are different in accordance with vertical positions of the photoconductive members.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description taken with the accompanying drawings in which:
FIG. 1 is a sectional front elevational view showing a color image forming apparatus embodying the present invention;
FIG. 2 is a schematic view showing a development portion of the color image forming apparatus embodying the present invention;
FIG. 3 is a timing chart for a possible operational sequence for the color image forming apparatus embodying the present invention;
FIG. 4 is a side elevational view showing other color image forming apparatus embodying the present invention;
FIG. 5 is a side elevational view showing yet a further color image apparatus embodying the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A preferred embodiment of the present invention will hereinafter be described with reference to the drawings. FIG. 1 is a sectional front elevation view showing a color image forming apparatus embodying the present invention.
In the illustrated color image forming apparatus, there are formed a plurality of elongate photoconductive members 1, 2, 3 and 4, in which each color image is formed on a respective photoconductive member. The photoconductive member 1 is for the black toner image, the photoconductive member 2 is for the cyan toner image, the photoconductive member 3 is for the magenta toner image and the photoconductive member 4 is for the yellow toner image. The longitudinal axes of the photoconductive members 1 through 4 are arranged on substantially the same plane extending in the vertical direction--or a direction inclined by up to 45 degrees from the vertical direction. As can be seen from FIG. 1, for each of the elongate photoconductive members 2-4, a vertical plane passing through the longitudinal axis therefore intersects the elongate photoconductive member located immediately therebelow. The photoconductive members 1 through 4 are provided adjacent a transfer belt 7 and contact therewith. The transfer belt 7 is entrained on a driving roller 5 and a follower roller 6, in which the driving roller 5 and the follower roller 6 are respectively rotatably supported so as to be spaced from one another in a vertical plane parallel to that of the axes of the photoconductive members. The transfer belt 7 is made from a dielectric material such as polyethyleneterephthalate and is an endless belt which is polarized by transfer chargers 8 and electrostatically attracts a transfer sheet. A plurality of the transfer chargers 8 are provided to face to the photoconductive members 1 through 4 via the transfer belt 7.
An elongate exposure device 9 having writing portions arranged corresponding to each photoconductive member is provided to the right of the photoconductive members 1 through 4. In the exposure device 9, light beam signals corresponding to image information depending on color resolution by a scanner are outputted by a laser beam scanning device (not shown) and polygon mirrors 11 and 12 driven by a motor 10 rotate so as to scan the laser beam onto the photoconductive members 1 through 4. A correcting lens 13 for converging the laser beam and mirrors 14 for deviating the laser beam are disposed in each optical path.
At the circumference of each of the photoconductive members 1, 2, 3 and 4 are disposed respective chargers 15 for charging, developing units 16 for liquid development, cleaning blades 17 as a cleaning portion and discharging lamps 18. Taking the axial center of each of the photoconductive members 1 through 4 as the origin of a two dimensional coordinates axis on the plane of FIG. 1, the charger 15 for charging, the cleaning blade 17 and the discharging lamp 18 are located at the first (upper right) quadrant and the developing units 16 for liquid development are located at the third (lower right) quadrant and the fourth (lower left) quadrant.
Each of the developing units 16 provided below a respective photoconductive member comprises a casing 19 with an open top, a developing roller 20 and a reverse roller 20a. FIG. 2 shows more detail of the developing units 16. Each of the developing units 16 also includes a developer supply hole 35 wherein the liquid developer is supplied from a developer tank 33 by a supply pump 34 (as shown in FIG. 4). The developer flows from a supply nozzle portion 36 to a guiding film 20c touching the surface of the developing roller 20. The developing roller 20 rotates in the counterclockwise direction so as to supply the developer to a gap portion (about 150 μm) between the photoconductive member 1 and the developer roller 20.
A scraper blade 20b is held against the reverse roller 20a and a gap of about 50 μm is formed between the photoconductive member 1 and the reverse roller 20a. The reverse roller 20a rotates in the clockwise direction so as to scrape excess developer from the photoconductive member and form a uniform thickness of the developer film. The scraper blade 20b scrapes toner from the reverse roller 20a and the scraped toner in the casing 19 is circulated through a retrieval hole 19a and a retrieval pipe.
Below the photoconductive member 1, a feed roller 23 feeds transfer sheets 22 from a sheet supplying cassette 21 designed to hold transfer sheets of a predetermined width. The transfer sheets 22 are guided by a feeding path 24 and hold rollers 25, and are fed to the transfer belt 7. A cleaning unit 26 for supplying cleaning liquid is disposed around the follower roller 6 via the transfer belt 7. The cleaning unit 26 comprises a cleaning foam roller 27 contacting the transfer belt 7 and a cleaning blade 28 also contacting the transfer belt 7. A fixing roller 29 and a press roller 30 in contact with each other are pivotally provided above the driving roller 5. Discharging rollers 32 discharge the transfer sheet 22 passing the fixing roller 29 onto a discharge tray 31.
In the above-described construction, one of the color images is formed on each of the photoconductive member 1, 2, 3 and 4. Hereafter, an image forming process using the photoconductive member 1 will be described and detailed explanations of the image forming process concerning the other photoconductive members are omitted because they are substantially the same as that of the photoconductive member 1.
The photoconductive member 1 is rotated about its own axis in the direction of the arrow by a drive device (not shown) and is uniformly charged by the charger 15. The image information for the black color is modulated to a semiconductor laser device (not shown). The laser beams therefrom are deviated by the rotating polygon mirror 11 and form an electrostatic latent image on the photoconductive member 1. The electrostatic latent image is developed into a black toner image by the developing roller 20, wherein a predetermined bias voltage/current is applied to the developing roller 20 in the developing unit 16 for black developer so as that toner in the liquid developer is adhered to the latent image on the photoconductive member 1 by electrophoresis.
On the other hand, the tip portion of the transfer sheet 22 fed by the feed roller 23 is held at the nip portion of the hold rollers 25 so as to position it with respect with the toner image on the photoconductive member 1, and the transfer sheet 22 is fed by the rotation of the hold rollers 25 and the transfer belt 7, both of which are synchronized with the rotation of the photoconductive member 1. The black toner image on the photoconductive member 1 is transferred onto the transfer sheet 22 by the lowermost transfer charger 8. In the same way, the latent image for cyan toner is formed on the surface of the photoconductive member 2 and developed by the cyan developer, and a cyan toner image on the photoconductive member 2 is transferred onto the transfer sheet 22. Next, the latent image for magenta toner is formed on the surface of the photoconductive member 3 and developed by the magenta developer, and a magenta toner image on the photoconductive member 3 is transferred onto the transfer sheet 22. Furthermore, the latent image for yellow toner is formed on the surface of the photoconductive member 4 and developed by the yellow developer, and a yellow toner image on the photoconductive member 4 is transferred onto the transfer sheet 22. The final color image is thus formed on the transfer sheet 22.
A bias current/voltage applied to each transfer charger 8 corresponding to the photoconductive members 1 through 4 is raised gradually in accordance with the order of transferring in order to execute good transferring. For example, the bias currents of the transfer chargers 8 for the photoconductive members 1, 2, 3 and 4 are 300 μA, 500 μA, 700 μA and 1000 μA respectively.
The image transferred sheet 22 is then separated from the transfer belt 7, transported past the fixing roller 29 and the pressing roller 30 to fix the image, and driven out onto the discharge tray 31. The transfer belt 7 is cleaned by the cleaning foam roller 27 so as to remove the remaining developer thereon after the each image transfer.
The remaining developer on each photoconductive member is liable to flow along the surface of the photoconductive member and drop from it, especially if the photoconductive member is stopped and excess developer is supplied. In addition, the developer scraped by the cleaning blade 17 when the width of the cleaning blade 17 is greater than that of the photoconductive member, drops therefrom at the axial ends of the photoconductive member.
However, the developer dropping from each photoconductive member is effectively caught by the casing 19 of the developing unit 16. For this purpose, the width of the casing 19 is greater than that of the corresponding photoconductive member. Each of the casings 19 prevents the excess developer on the corresponding photoconductive member or developing unit, which is located thereabove, from dropping on the photoconductive member or the developing unit which is located below the respective casing.
In the color image forming apparatus having the above construction, the color mixing problem does not occur and high speed image forming is accomplished because each of the developing units 16 corresponds to only one of the photoconductive members 1 through 4 and so these units 16 need not exchange developer. Moreover, the axes of the photoconductive members 1 through 4 are arranged on substantially the same plane deviating from the vertical direction by up to 45 degrees, and the transfer belt 7 is also vertically disposed (plus or minus 45 degrees) in its longitudinal direction. Therefore, a minimum of space is required for installation.
A further sequence of operation of the present invention will hereinafter be described with reference to FIG. 3. This sequence is applicable to the above described embodiment and is directed only to the supply timing of each developer. Therefore, a detailed explanation of the image forming apparatus is omitted to avoid repetition.
In a conventional color image forming apparatus utilizing dry developer, a plurality of photoconductive members and developing units are simultaneously put into operation by a start signal, and the timing of each latent image written on each photoconductive member is staggered in turn. In this case, it is not necessary that the operation timing of applying a bias voltage on each developing unit is staggered in turn, because dry toner in a developing unit does not adhere on the surface of the photoconductive member when the latent image is not formed on it. But, in a color image forming apparatus utilizing liquid developer, toner particles are dispersed in a carrier material and moved in the carrier material by electrophoresis. The carrier material is made from an aliphatic hydrocarbon, for example. Isoper which is a Trademark of the Exxon Corporation.) Some liquid developer supplied on the developing roller 20 adheres on each surface of the photoconductive members 1 through 4 and the transfer belt 7 even if the latent image is not formed on it. Therefore, when a plurality of photoconductive members and developing units are simultaneously put into operation, the extra developer which does not contribute to forming a toner image is supplied and the developer consumption increases.
In this embodiment having a developing unit 16 around each of the photoconductive members 1 through 4, operation timing of the development roller 20 in each developing unit 16 is set up to be staggered in turn, i.e. sequential with respect to the first photoconductive member 1. For example, as shown in FIG. 3, after receiving the start signal for image forming, a latent image corresponding to black toner is written by the exposure device 9 and the electrostatic latent image is developed into a black toner image by the developing roller 20 for supplying black liquid developer. Next, the latent image for cyan toner is formed on the surface of the photoconductive member 2 and the electrostatic latent image is developed into a cyan toner image by the developing roller for supplying cyan liquid developer. Next, the latent image for magenta toner is formed on the surface of the photoconductive member 2 and the electrostatic latent image is developed into a magenta toner image by the developing roller for supplying magenta liquid developer. Finally, the latent image for yellow toner is formed on the surface of the photoconductive member 2 and the electrostatic latent image is developed into a yellow toner image by the developing roller for supplying yellow liquid developer.
In addition, operation timing of each developer replenisher is set up to be staggered in turn with respect to the first developing unit 16 for the photoconductive member 1 in order to reduce the carrier material adhering to each photoconductive member and the transfer belt 7. Timing of each developer replenisher, corresponding to timing of each latent image forming, to each photoconductive member or to each developing roller, is controlled by the pump for supplying developer or by rotating control of the developer roller 16. As a result, the developer consumption reduces.
Another embodiment of the present invention will hereinafter be described with reference to FIG. 4, wherein like reference numerals designate identical or corresponding parts. This embodiment is the same construction as the first described embodiment except for the width of a cleaning blade. Therefore, detailed explanation of the image forming apparatus is omitted to avoid repetition.
FIG. 4 shows a side view of the color image forming apparatus according to this embodiment. The widths of the photoconductive members and that of the cleaning blade 17 which is disposed around each photoconductive member is greater in axial the direction than that of the transfer sheet 22, and each such widths of the cleaning blades 17 is different in accordance with the vertical position of the cleaning portion, i.e., said widths of the cleaning blades 17 progressively increase from the highest cleaning blade to the lowest cleaning blade. A developing area of the developing unit 16 is greater than the width of the transfer paper 22, and the width of the casing 19 of the developing unit 16 in the axial direction is greater than the width of the photoconductive members 1 through 4 in the axial direction. The developer is supplied from the developer tank 33 to each developing unit 16 by the pump 34. In FIG. 4, W1 indicates the width of the transfer belt, W2 indicates the width of the transfer sheet, W3 indicates the width of the developing area, W4 indicates the minimum width of the cleaning blades, W5 indicates the maximum width of the cleaning blades and W6 indicates the width of the casing of the developing unit.
Some toner and carrier material remain on the photoconductive members 1 through 4 after the developed images on the photoconductive members 1 through 4 are transferred to the transfer sheet 22. It is necessary that the remaining developer on the photoconductive members 1 through 4 is scraped therefrom. The developer scraped by the cleaning blade 17 flows down from both ends of the cleaning blade 17 to the axial ends of the photoconductive members 1 through 4 and there gathers in a ring shape called a "liquid ring". The gathered developer on the photoconductive members 1 through 4 can undesirably adhere to the back surface of the transfer belt 7 and cause it to slip. Therefore, the widths of the cleaning blades 17 in the scanning direction progressively increases from the highest cleaning blade to the lowest blade so as that an adhering distribution of the developer which flows down from the ends of the cleaning blade 17 to the axial ends of the photoconductive members 1 through 4, and adheres to the developing belt 7, is dispersed. As a result, the phenomenon that the quantity of developer on the transfer belt 7 is sufficient that the developer is transported from the front surface to the back surface thereof is restrained and the transfer belt 7 slipping on the driving roller 5 is prevented.
The accurate transport of the transfer sheet 22 is thus accomplished.
A further embodiment of the present invention will now be described with reference to FIG. 5, wherein like reference numerals designate identical or corresponding parts.
This embodiment is the same construction as the first described embodiment except for the widths of the cleaning blade and photoconductive members. Therefore, a detailed explanation of the image forming apparatus is omitted to avoid repetition.
FIG. 5 shows a side view of a further color image forming apparatus according to this embodiment. The widths of the photoconductive members 1 through 4 and that of cleaning blades 17 which are disposed around each photoconductive member, is greater in the axial direction than that of the transfer sheet 22, and each width of the photoconductive members in said direction is different in accordance with the vertical positions of the photoconductive members; i.e., the widths of the photoconductive members 1 through 4 increase one after another from the photoconductive member 4 located in the highest position to the photoconductive member 1 located in the lowest position. The widths of the casings 19 in the developing unit 16 in said direction is greater than that of the photoconductive members 1 through 4 in said direction. In FIG. 5, W1 indicates the width of the transfer belt, W2 indicates the width of the transfer sheet, W3 indicates the width of the developing area, W4 indicates the width of the cleaning blade, W6 indicates the width of the casing of the developing unit, W7 indicates the minimum width of the photoconductive member and W8 indicates the maximum width of the photoconductive member.
In this construction, the developer on the photoconductive members 1 through 4 is scraped by each cleaning blade 17. The developer dropping from the photoconductive members 1 through 4 is almost entirely caught by each casing 19 having a broad area. Some developer on the photoconductive members 1 through 4 adheres to the transfer belt 7. However an adhering distribution of the developer which adheres to the transfer belt 7 is dispersed by using the different width photoconductive members in the axial direction. As a result, the phenomenon that the developer on the transfer belt 7 is transported from the front surface to the back surface thereof is restrained and the transfer belt 7 slipping on the driving roller 5 is prevented. The accurate transport of the transfer sheet 22 is thus accomplished.
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.
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A color image forming apparatus forms an image having a plurality of colors. It includes a plurality of elongate photoconductive members of a number corresponding to the plurality of colors. The axes of the photoconductive members are arranged on a plane extending by no more than 45° from the vertical direction. A plurality of developing units supply a liquid developer to each of the photoconductive members to develop latent images thereon. A movable transfer belt contacts the photoconductive members so that developed images may be transferred to the transfer belt. A plurality of cleaning portions are positioned for scraping liquid developer from the photoconductive members. The widths of the cleaning portions progressively increase from the highest to the lowest. An open topped casing is disposed below each of the photoconductive members for catching liquid toner dropping from the photoconductive members.
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This application is a continuation application of co-pending application Ser. No. 07/409,464, filed on Sep. 19, 1989, now U.S. Pat. No. 5,033,517, which is a continuation application of application Ser. No. 07/031,030, filed on Mar. 26, 1987, now U.S. Pat. No. 4,887,652.
BACKGROUND OF THE INVENTION
This invention relates to a system for controlling the release of fuel vapors into the atmosphere from the fuel filler pipe of a vehicle's fuel tank.
As currently designed, vehicle fuel tanks normally operate under a positive pressure. Accordingly, when the filler cap for such a tank is removed, fuel vapors are released into the atmosphere. Similarly, as the tank is filled with fuel, fuel vapors in the tank are forced out of the tank into the atmosphere by the incoming fuel. The release of fuel vapors into the atmosphere under these conditions is undesirable for both environmental and health reasons.
The present invention is directed to controlling the release of fuel vapors into the atmosphere under the foregoing conditions. Specifically, rather than allowing the vapors to escape, the invention routes them to a vehicle-mounted, vapor capture device, such as, a charcoal canister, from which the vapors can be later removed and safely burned in the vehicle's engine.
In addition to controlling vapor escape, the invention also prevents liquid fuel from flowing into the vapor capture device during filling of the fuel tank. Moreover, the invention provides automatic relief for over pressure conditions within the vehicle's fuel tank, is easy to construct, reliable, crash-worthy, and can be readily installed in place of conventional filler pipe assemblies.
SUMMARY OF THE INVENTION
To achieve the foregoing and other goals, the invention provides a fuel filler pipe assembly comprising an outer tube whose lower end is connected to the vehicle's fuel tank and whose upper end is attached, for example, to the sheet metal of the vehicle. The tube has a mouth at its upper end for receiving fuel, to which a cap is attached during use to seal closed the mouth. Preferably, the cap has a male screw thread which mates with a corresponding female screw thread formed in the mouth of tube.
The inside of the outer tube includes a partition which divides the interior of the tube into two conduits--a first conduit for carrying fuel from the mouth to the fuel tank and a second conduit, isolated from the mouth, for carrying fuel vapors out of the fuel tank to the vapor capture device. In certain preferred embodiments of the invention, the partition is in the form of an inner tube disposed within the outer tube. For this configuration, the bore of the inner tube carries fuel from the mouth to the fuel tank, and the space between the inner and outer tubes carries fuel vapors to the vapor capture device.
Attached to the second conduit is a third conduit for connecting the second conduit to the vapor capture device. Passage of fuel vapors through the third conduit is controlled by a valve assembly. The state of this assembly, i.e., whether it is open or closed, is controlled by the attachment and detachment of the filler cap to the outer tube. Specifically, attachment of the cap causes the valve assembly to close so as to seal the fuel tank, while detachment causes the assembly to open so that fuel vapors are routed from the fuel tank to the vapor capture device.
In this way, the fuel tank can be pressurized during normal operation of the vehicle with the cap in place. As the cap is removed, the valve assembly opens thus venting substantially all of the pressurized fuel vapors within the tank to the vapor capture device, rather than allowing these vapors to escape into the atmosphere. Similarly, as fuel is introduced into the tank through the mouth of the tube, substantially all of the fuel vapors which are displaced by the entering fuel leave the tank through the second and third conduits and the open valve assembly, rather than through the mouth of the tube. To further ensure that the displaced fuel vapors leave the tank through the second and third conduits, a seal is preferably formed between the fuel filler nozzle and the first conduit.
In certain preferred embodiments of the invention, wherein a male screw thread is used on the cap and a female screw thread is formed in the mouth of the outer tube, the coordination between the opening and closing of the valve assembly and the detachment and attachment of the cap is achieved by the movement of the male screw thread within the female screw thread. In connection with these embodiments, it is further preferred to use a valve assembly which includes a normally-closed valve connected to a mechanical linkage which is activated by contact with the male screw thread as that thread rotates within the female screw thread.
As discussed in detail below, a preferred form of such a mechanical linkage comprises a pivoted cam arm, a spring which urges the cam arm into contact with the normally-closed valve to open that valve, a second pivoted cam arm which is contacted by the male screw thread, and a rotatable post which connects the two cam arms so that contact of the male screw thread with the second cam arm causes that arm to rotate which, in turn, rotates the first cam arm, moving it away from the valve so that the valve can close. As also discussed below, it is further preferred to place a vapor barrier between the cam arms so as to prevent fuel vapors from reaching the mouth of the outer tube by following the path of the mechanical linkage.
In addition to the foregoing, it is also preferred that the valve assembly include a normally-closed valve which is designed to open when the pressure within the fuel tank exceeds a predetermined value. In this way, excess pressure which may develop within the tank is automatically vented to the vapor capture device.
In connection with other preferred embodiments, a second valve is provided which closes the second conduit when liquid fuel reaches a predetermined level within the second conduit. This valve prevents substantial amounts of liquid fuel from being pumped into the vapor capture device during filling of the fuel tank. When such a valve is used and when a seal between the first conduit and the fuel filler nozzle is also used, it is further preferred to provide an overpressure or relief valve between the second conduit and the mouth of the outer tube so as to provide a path for fuel to leave the fuel tank if the automatic shut-off of the fuel filler pump should malfunction and not shut off the pump once the fuel tank has been filled or if the user should continue to pump fuel into the tank after the tank is full.
As discussed below, a preferred form for the second valve comprises a ball and seat valve employing a ball having a lower density than the liquid fuel so that the ball rises into the seat and closes off the second conduit as the level of fuel rises in that conduit. As also discussed below, in connection with this valve configuration, it is also preferred to baffle the second conduit so as to minimize the chance that liquid fuel splashed up during the filling process will reach the ball and close the valve before the fuel tank has been completely filled. In addition, it is preferred to place a ball, e.g., a metal ball, having a higher density than the liquid fuel below the ball with the lower density so that if the vehicle should roll over, the second valve will automatically close by means of the higher density ball forcing the lower density ball into the valve seat.
An important feature of the invention is the fact that in terms of its relationship to the vehicle, the assembly of the invention has basically the same structure as conventional filler pipes. Thus, as with a conventional filler pipe, there is only one connection between the assembly and the vehicle's fuel tank. Similarly, the mouth of the assembly is mounted to the vehicle in the same manner as conventional filler pipes. Accordingly, the assembly of the invention can be used in place of conventional filler pipes with a minimum of changes to the manufacturing process. Also, because of the similar structure and attachment points, crashworthiness of the overall fuel supply system is not compromised by the substitution of the assembly of the invention for a conventional filler pipe.
The accompanying drawings, which are incorporated in and constitute part of the specification, illustrate the preferred embodiments of the invention, and together with the description, serve to further explain the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a fuel filler pipe assembly constructed in accordance with the present invention.
FIG. 2 is an exploded view of the assembly of FIG. 1.
FIG. 3 is a top view of the assembly of FIG. 1 with the fuel filler cap removed.
FIG. 4 is a side view of the assembly with the cover plate for the housing portion of the assembly removed.
FIG. 5 is a cross-sectional view along lines 5--5 in FIG. 3. FIG. 5 also illustrates the mating of the fuel tank's filler cap with the fuel filler pipe assembly.
FIG. 6 is a cross-sectional view along lines 6--6 in FIG. 4.
FIG. 7 is a cross-sectional view along lines 7--7 in FIG. 4.
FIGS. 8-11 illustrate the coordination between the opening and closing of the assembly's vapor control valve and the detachment and attachment of the fuel filler cap to the assembly. FIGS. 8 and 9 are cross-sectional views along lines 8--8 in FIG. 4. FIGS. 10 and 11 are cross-sectional views along lines 10--10 in FIG. 4.
FIG. 12 is a cross-sectional view along lines 6--6 in FIG. 4 illustrating the orientation of the filler pipe assembly when mounted to a vehicle.
FIG. 13 is a perspective view of a baffle assembly for use with the present invention.
FIG. 14 is a perspective view, partially in section, illustrating the fuel filler pipe assembly with the baffle assembly of FIG. 13 in place.
FIG. 15 is a cross-sectional view along lines 15--15 in FIG. 13.
FIG. 16 is a schematic diagram illustrating the attachment of the fuel filler pipe assembly of the present invention to a fuel tank and a vapor capture device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference now to the drawings, wherein like reference characters designate like or corresponding parts throughout the several views, there is shown in FIGS. 1 and 2 a perspective and an exploded view, respectively, of fuel filler pipe assembly 10 constructed in accordance with the present invention.
Assembly 10 includes outer tube 12 which is attached to outer hose 14 by hose clamp 16. Outer hose 14, in turn, is attached to the vehicle's fuel tank 150 by, for example, a further hose clamp 154. At its upper end, outer tube 12 forms mouth 18 for receiving fuel. The inside surface of mouth 18 includes female screw thread 20 which mates with male screw thread 22 carried by cap 24. Flange 26 is attached to outer tube 12 in the region of mouth 18 and is used to mount assembly 10 to the vehicle by means of, for example, sheet metal screws which pass through screw holes 28.
Within outer tube 12 is located inner tube 30 which is attached to inner hose 36 by hose clamp 38. Inner hose 36 lies within outer hose 14. Depending on the desired level to which the vehicle's fuel tank is to be filled, inner hose 36 will either extend beyond outer outer hose 14 into the vehicle's fuel tank or will end within the outer hose. In either case, inner hose 36 is not clamped to the fuel tank, but simply rides within the outer hose. For some tank configurations, inner hose 36 can be eliminated.
The upper end of inner tube 30 is sealed to the inner surface of outer tube 12 by means of flange 32 and grommet 34. During filling of the vehicle's fuel tank, grommet 34 forms a seal around the fuel filler nozzle so as to prevent substantial amounts of fuel vapors form passing out of the fuel tank by means of inner tube 30. Inner tube 30 includes slit 106 which provides a passageway for fuel to move from conduit 42 to conduit 40 as the fuel tank becomes full (see FIG. 12.) The presence of fuel in conduit 40 serves to trigger the automatic shut off sensor (aspirator) used on conventional fuel pump nozzles to shut off the fuel pump when the fuel tank is full. Inner tube 30 also includes aperture 100 which provides a vent path for fuel vapors within conduit 40 which are displaced by the incoming fuel, that is, aperture 100 vents conduit 40 so that slit 106 does not become vapor locked.
Outer tube 12 and inner tube 30 are preferably made of a plastic material, such as, for example, nylon or polyester, and can be fastened to each other by, for example, ultrasonic welding. Grommet 34 is preferably made of a fluoroelastomer.
Inner tube 30 functions as a partition and divides the interior of outer tube 12 into conduits 40 and 42. Conduit 40 extends from mouth 18 towards the fuel tank and serves to carry fuel from the mouth into the tank. Conduit 42 extends away from the fuel tank, is isolated from mouth 18, and serves to carry fuel vapors out of the fuel tank.
As can be seen most clearly in FIGS. 1-2, the upper portion of assembly 10 includes housing 46 and cover plate 48 which are attached together by screws 50 which pass through screw holes 52 in the cover plate and are received in screw holes 54 in the housing. Alternatively and preferably, the housing and outer tube 12 are molded as a single unit out of a plastic material, such as those discussed above, the cover plate is also made of plastic, and the housing and the cover plate are attached together by ultrasonic welding.
As shown in FIG. 1, hose 56 is attached to housing 46 at port 58 by means of hose clamp 60. Hose 56 leads to a vapor capture device 152, such as, a charcoal canister, which is mounted on the vehicle at a suitable location.
Housing 46 and cover plate 48 together form conduit 44 (see FIGS. 5-7) for connecting conduit 42 to the vapor capture device. Housing 46 and cover plate 48 also contain and form part of valve assembly 13 whereby conduit 44 is opened and closed in coordination with the detachment and attachment of cap 24 to mouth 18.
Valve assembly 13 includes: normally-closed valve 62; upper cam arm 64; lower cam arm 72; cylindrical post 66, which is journaled in cylindrical housing 68 formed in housing 46 and a corresponding cylindrical housing formed in cover 48 (not shown); O-ring 70, which is received on post 66 and forms a seal between the post and the wall of the cylindrical housing so as to create a vapor barrier between the upper and lower cam arms; and spring 74, which urges lower cam arm 72 into contact with valve 62 so as to move the valve into its open position. Cylindrical post 66 connects lower cam arm 72 to upper cam arm 64 so that rotation of the upper cam arm results in corresponding rotation of the lower cam arm.
As can be seen most clearly in FIG. 7, valve 62 includes piston 76, spring 78, and O-ring 80 which mates with surface 82 of housing 46 to close the valve. Spring 78 is preferably chosen so that valve 62 will automatically open at a predetermined pressure, e.g., a pressure on the order of 1-2 psi, so as to relieve excess pressure within the fuel tank such as can occur under hot environmental conditions.
The coordination between the opening and closing of valve 62 and the rotation of male thread 22 in female thread 20 is illustrated in FIGS. 8-11, where FIGS. 8 and 10 show the positions of upper cam arm 64, lower cam arm 72, spring 74, and valve 62 when the male thread is in engagement with upper cam arm 64, and FIGS. 9 and 11 show the positions of the same components when the male thread is out of engagement with the upper cam arm.
As shown in these figures, engagement causes lower arm 72 to rotate counterclockwise against the force of spring 74 thus allowing valve 62 to move into its normally closed position, while disengagement allows spring 74 to move lower arm 72 into contact with valve piston 76 so as to open the valve by disengaging O-ring 80 from surface 82. As shown in FIG. 6, upper arm 64 is preferably located towards the bottom of female screw thread 20 so that valve 62 opens at the beginning of the process of removing cap 24 from mouth 18. In particular, valve 62 opens before seal 25 carried by cap 24 disengages from mouth 18 of the assembly (see FIG. 5). In this way, any residual pressure which may be in the fuel tank is vented into the vapor capture device prior to removal of the cap, thus preventing the escape of fuel vapors into the atmosphere.
In addition to valve 62, assembly 10 also includes valve 84 which closes conduit 42 as liquid fuel reaches a predetermined height in that conduit. As shown in FIG. 6, ball 86 which seats in seal 88 can be used for this purpose. As shown in FIG. 12, assembly 10 is mounted on the vehicle so that ball 86 moves essentially vertically, i.e., the assembly is mounted so that housing 90 for ball 86 is oriented vertically. Ball 86, which must have a lower density than the fuel used in the vehicle, can be a hollow ball made out of polypropylene. Seal 88 includes flexible lip 89 which, along with the vertical movement of the ball, helps prevent the ball from hanging up on the seal.
FIGS. 13-15 illustrate the use of baffle assembly 92 for controlling splashing of liquid fuel onto ball 86. Because of the pumping rates used, the filling of a vehicle fuel tank by means of a conventional service station fuel pump results in substantial splashing of the liquid fuel within the fuel tank. This splashing can cause ball 86 to move upward in housing 90 and seat in seal 88 before the fuel tank has been completely filled. This seating, in turn, causes back pressure in conduits 40 and 42 which shuts off the service station fuel pump.
Moreover, if a grommet 34 has been used which forms a seal with the fuel pump's nozzle, as is preferred, ball 86 will remain seated in seal 88 even after the fuel pump has shut itself off, due to the internal pressure within the fuel tank produced by 1) the action of the fuel pump prior to shut off, and 2) the vapor pressure of the fuel in the fuel tank. Although this internal pressure will eventually bleed off through leakage around grommet 34, as a practical matter, to resume pumping in a reasonable amount of time, the user will need to remove the fuel pump nozzle from the filler pipe assembly in order to vent the internal pressure. Baffle assembly 92, by blocking the passage of splashed fuel to ball 86, minimizes the chances that such premature seating of ball 86 in seal 88 will occur before the fuel tank has been fully filled.
As shown in FIGS. 13-15, baffle assembly 92 can consist of a series of four transverse baffles 94 and a midline baffle 98. These baffles create the circuitous route illustrated by arrows 96 in FIG. 14 which fuel must follow to reach ball 86. In practice, it has been found that substantially no fuel splashes are large enough or have sufficient energy to traverse the full circuit and then move ball 86 up into seal 88 without first having entered slot 106 and contacted the aspirator on the nozzle of the service station fuel pump, thus shutting off that pump. Baffle assembly 92 also includes drain passages 102 and 104 which rapidly drain splashed fuel back into the tank so as to minimize the chance that multiple splashes will combine with one another to move the ball. Other baffle constructions besides the one illustrated in the figures can be used in the practice of the invention. For example, six baffles, rather than four baffles, can be used to provide even greater splash protection for ball 86.
As shown in the figures, baffle assembly 92 is conveniently formed on the outside surface of inner tube 30. In addition to the baffle assembly, guide members 108, 110 and 112, which control the movement of ball 86, are also formed on this surface. As shown in FIG. 14, valve 84 preferably includes a second ball 115. This ball is denser than the liquid fuel and thus remains in contact with top baffle 94 during normal operation of the vehicle. As such, it serves as an additional obstacle for splashed fuel. If a vehicle should roll over during accident, ball 115 serves the important function of forcing ball 86 into seal 88 thus preventing fuel from draining out of the fuel tank through conduits 42 and 44. Ball 115 can be made of, for example, stainless steel.
As also shown in FIG. 14, filler pipe assembly 10 preferably includes relief valve 114. This normally-closed valve is designed to open when the pressure in conduit 42 exceeds a predetermined value, such as 1-2 psi. Under normal conditions, this valve remains shut during filling of the fuel tank. However, if valve 84 should close during filling and if fuel should continue to be pumped into the tank, valve 114 will open allowing the excess fuel to pass out of conduit 42 and into mouth 18, thus relieving excess tank pressure and alerting the operator that the service station fuel pump has malfunctioned.
Inner tube 30 and its associated baffle assembly 92 can be attached to outer tube 12 by means of screws (not shown) and screw holes 116. Alternatively, the two tubes can be bonded together by, for example, ultrasonic welding. Grommet 34 forms a seal between the upper end of inner tube 30 and the body of outer tube 12. Grommet 34 also forms a seal about the fuel pump nozzle when the nozzle is inserted into conduit 40. As shown in FIG. 14, inner tube 30 is offset from the center line of outer tube 12. This permits the spring used on some fuel pump nozzles to engage threads 20 in mouth 18 of the filler pipe assembly. As further shown in FIG. 14, seal 88 can be held in place by retaining ring 118.
Based on the foregoing, the operation of the fuel filler pipe assembly of the present invention is as follows. When cap 24 is in place on outer tube 12, the assembly seals the vehicle's fuel tank by means of normally-closed valve 62 and seal 25 carried by the cap. Should excess pressure develop in the tank, valve 62 opens to vent the excess pressure into the vapor capture device through conduits 42 and 44 and hose 56.
When cap 24 is removed from outer tube 12, valve 62 automatically opens so that the fuel vapors within the tank are vented to the vapor capture device. During filling of the tank with fuel, valve 62 remains open so that the vapors displaced by the incoming fuel pass through the valve into the vapor capture device. As the tank becomes full, liquid fuel rises in conduit 42 causing ball 86 to seat in seal 88. This prevents substantial quantities of liquid fuel from flowing through conduits 42 and 44 into the vapor capture device. When cap 24 is replaced on outer tube 12, valve 62 closes and the fuel tank is once again sealed.
The components of the fuel filler pipe assembly of the present invention can be made of standard materials used in the automotive industry. For example, as discussed above, outer tube 12, inner tube 30, housing 46, and cover plate 48 can be made of nylon or polyester. Valve piston 76 can also be made out of these materials. O-rings 70 and 80, as well as seal 88 and grommet 34, can be made of a fluoroelastomer, while post 66 and cam arms 64 and 72 can be made of metal or high strength thermoplastic materials. Other suitable materials for the components making up the filler pipe assembly will be evident to persons skilled in the art in view of the present disclosure.
Although specific embodiments of the invention have been described and illustrated, it is to be understood that modifications can be made without departing from the invention's spirit and scope. For example, partitions other than inner tube 30 can be used to form two conduits within outer tube 12. Similarly, the components of the invention can be arranged relative to one another in a variety of configurations other than those shown.
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A fuel filler pipe assembly is provided which controls the release of fuel vapors from a vehicle fuel tank so as to limit the amount of fuel vapor released into the atmosphere. The assembly includes an outer tube which is partitioned into two conduits--one for carrying fuel to the vehicle's fuel tank and the other for carrying fuel vapors to an on board vapor capture device. Passage of fuel vapors to the vapor capture device is controlled by a valve which itself is controlled by the attachment and detachment of a fuel filler cap to the assembly such that attachment of the cap causes the valve to close while detachment causes it to open. In certain preferred embodiments, the assembly includes a second valve for preventing the passage of substantial quantities of liquid fuel to the vapor capture device.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an adapter for a self-programming printed circuit board tester.
2. Description of the Prior Art
Printed circuit board testers with which unassembled (i.e. prior to component insertion) printed circuit boards are inspected for insulation failures and contact faults between the separate conductor paths are known per se. With these instruments, an adapter is set up on a printed circuit board so that its contact pins are positioned on corresponding test points of the printed circuit board. An example of such an adapter is described in Luther, U.S. Pat. No. 3,996,516. These contact pins are connected with corresponding contacts of a connecting plug to which the tester itself is connected. During testing, the instrument determines with what other test points each individual test point is conductively connected. The results obtained are compared with reference or design results that correspond to results obtained from a faultless printed circuit board. If, for example, an extra contact is found, this indicates an insulation failure. If, on the other hand, the instrument detects a conductive connection less than the reference or design result, this signifies that a contact fault, such as a break in conducting path, exists.
"Automatic programming" printed circuit board testers have recently been developed. In these testers an adapter is set up on a fault-free master printed circuit board. By means of a suitable program the tester undergoes a learning cycle during which it interrogates separate contact pins of the adapter to ascertain whether a conductive connection exists with any other contact pins of the adapter. The results of each interrogation are stored in a memory of the printed circuit board tester and are retrieved for comparison purposes during the actual testing process. Thus, the electronics of the printed circuit board tester learns from the master board which points of such master board are insulated and between which test points conductive connections exist. Use of the tester for testing a given type of printed circuit board therefore begins with the learning of the testing program from a master board.
If the tester is to be used to test another type of printed circuit board which has a different conductor path layout, the electronics of the tester must learn a new testing program from a corresponding new master board on which a corresponding new adapter is set up. In the process, the testing program used for the type of board previously tested is erased and lost.
If later the tester is once again used for testing the first type of printed circuit board, the first testing program must be learned all over again, with the corresponding adapter again being set up on a master board and the learning program again run off. Here the following problems may occur:
If an adapter has for example lain on a shelf for some time and one of its test pins has become defective, for example by breaking off or by oxidizing or if the defect is not detected, when the adapter is set up on a master board considered to be good, the tester electronics will learn a defective program. In addition, the original master board originally used, which likewise had to be stored, may itself have sustained damage. If a new printed circuit board considered good is used as a master instead of the original master board, it may contain an undetected manufacturing defect. It is also possible that the connection of the adapter to the printed circuit board tester may be defective, so that this, too, may lead to a faulty testing program. The use of a faulty program, however, leads to faulty boards being found to be good and fault-free boards being erroneously found to be defective.
SUMMARY OF THE INVENTION
The present invention, in one aspect, provides novel arrangements for automatic programming of printed circuit board testers by which it is possible to detect, on automatic programming, a contact fault in the adapter, a fault in the master board or some other fault during self-programming, which has led to an error in the testing program.
These novel arrangements involve a special adapter having contact pins for electrical contact with test points of printed circuit boards, connecting plugs for electrical connections to a self-programming printed circuit board tester, conductors joining the contact pins to the connecting plugs, and a memory preset with stored information representative of the results of a test of a master printed circuit board, the memory being connected to be interrogated by the tester for comparison with results obtained from subsequent tests of the master printed circuit board.
The entire testing program, which is initially learned from the new faultless master board and the similarly new faultless adapter, can, in principle, be read into the memory of the inventive adapter. Then, if after testing other types of printed circuit boards, the tester is again used for this special type of board, the testing program can be read out of the adapter into the corresponding electronics of the tester and is again available.
A further aspect of the invention, however, involves not storing the entire originally-learned program in the adapter memory, but storing information derived from that program in a memory of substantially smaller scale. In relearning the testing program, this stored derivative information is used to make a comparison which serves to detect whether a contact fault or some other failure in the master board or adapter was present during the relearning process. This further aspect of the invention offers the particular advantage that a very simple and sturdily built memory may be utilized which is cost efficient and insensitive to external influences. If on the other hand, the entire learned program were to be stored in the adapter in the form of a magnetic card, for example, the adapter would have to be shielded from magnetic fields. Storage in the form of a punched strip would likewise possible, but would have the disadvantage that a special reading device would be necessary. In accordance with this further aspect of the invention, these difficulties are avoided.
In particular, it has been found to be advantageous to use a simple plug-in strip as the memory, wherein information storage is in the form of conductive connections established between the individual connecting contacts. This strip may be mounted on one of the connecting plugs of the adapter, so that the information is availble to the printed circuit board tester by way of this connecting plug during the self-programming procedure.
BRIEF DESCRIPTION OF THE DRAWINGS
By way of example of the many features and advantages of the invention, an illustrative embodiment adapter is described below and shown in the accompanying drawings in which:
FIG. 1 is a side view, partially in schematic outline, of a known printed circuit board tester;
FIG. 2 is a section view, also partially in schematic outline, taken along the line II--II through the tester of FIG. 1;
FIG. 3 is a perspective view of a new adapter used with the tester of FIG. 1, as seen from below;
FIG. 4 is a perspective view of the adapter of FIG. 3 as seen from above;
FIG. 5 is a section view taken along line V--V of FIG. 4;
FIG. 6 is an enlarged view of a segment represented by a phantom line circle VI of FIG. 5;
FIG. 7 is a perspective view of a preferred adapter memory used with the tester of FIG. 1, as seen from below; and
FIG. 8 of a perspective view of the adapter memory of FIG. 7 as seen from above.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The printed circuit board tester illustrated in FIGS. 1 and 2 is in the prior art and the example shown is a Luther & Maelzer Model LP 18-2030 PCB Test System which is availble from Luther & Maelzer Inc., 10 Dale Street, Waltham, Mass. 02154. As shown in FIG. 1, the printed circuit board tester is arranged on a mount 1 supporting an inclined table 2. On the upper side 3 of the table, there is located a magazine 4 for holding printed circuit boards 5 to be tested. The printed circuit boards 5 are ejected in cycles from the bottom of the magazine 4 by means of a slide (not shown). A pneumatic cylinder 6 serves to operate the slide. The printed circuit boards 5 are brought to a testing position beneath a testing assembly 7 which is adjacent the magazine 4. The testing assembly 7 includes electronic circuits for first learning a testing program and thereafter performing tests on the boards 5. The testing assembly 7 has a display window 10 for displaying information representative of the testing program and a display window 11 for displaying errors detected in the tested boards. In addition, the testing assembly 7 is provided with a keyboard 31 for entering in individual operating functions.
By means of a handle 32 (FIGS. 1 and 2), the testing assembly 7 is pivotable upwardly about a pivot axis 33 (see FIG. 2) which is parallel to the inclined plane of the table 3.
After testing, each printed circuit board slides, by force of gravity, along the inclined plane of the table 3 into a sorting device 8 shown in FIG. 1. The control of the sorting device 8 is responsive to the testing results obtained by the testing assembly 7 to sort the printed circuit boards into stacks: those having undesired conductor path connections, those having undesired conductor path breaks and those which are good. A stack of printed circuit boards which have been tested and found to be good is designated by the numeral 9 in FIG. 1.
The sorting device is the subject matter of commonly owned U.S. patent application Ser. No. 970,248, filed Dec. 18, 1978, now U.S. Pat. No. 4,245,940. The slide with the magazine is the subject matter of commonly owned U.S. patent application Ser. No. 970,484, filed Dec. 18, 1978, now U.S. Pat. No. 4,273,321.
In FIG. 2 a printed circuit board as positioned for testing on the upper side 3 of the table 2 in the area of the testing assembly 7, is represented by the reference numeral 12. An adapter 13 serves as an interface between electronic test circuits and test points located on the printed circuit boards. The testing assembly (represented by dot-and-dash lines) contains electronic interrogation circuits 18 to electronically interrogate the separate test points of the printed circuit board 12 in order to determine whether or not an electrical connection exists between any two given test points. The electrical connections detected between test points on the tested board are electronically compared with stored reference results obtained from a previous interrogation of the test points of a "faultless" master printed circuit board. A tested board is "good" if the test results match the stored reference results. If the test results indicate more electrical connections than the reference results, undesired conductor path connections exist; and if the test results indicate fewer electrical connections than the reference results, undesired conductor path breaks exist.
As may be seen from FIGS. 4 and 5, the electronic interrogation circuits 18 (FIG. 2) comprises a plurality of plug-in printed circuit cards 25 (sometimes called "switch cards") having electronic components and printed conducting connections. The plug-in cards 25 are provided with plug-in strips having contact receptacles 17 (FIG. 2) at an outside edge. Electrical connection is established between the tester electronics and the adapter 13 by means of connecting plugs 16 on the adapter 13 which are inserted into the contact receptacles 17.
Each type of printed circuit board 12 to be tested has an associated matching adapter 13. The underside of each adapter 13 has point contact pins 14 (FIG. 5) which are matched to the type of board being tested so that they press onto selected test points of the printed circuit board 12. The contact pins 14 are connected to the connecting plugs 16 via conductors, such as conducting wires 15, located within the adapter 13. To ensure reliable electrical contact between the contact pins 14 and the test points of the board to be tested, at the time when the printed circuit board 12 is brought to the testing position, the board is subjected to ultrasonic vibrations as described in Luther U.S. Pat. No. 3,996,516. The adapter 13 also includes a preset memory 19, which is described in more detail below.
The conductor path layout (and thus the positioning of the test points) is different for different types of printed circuit boards. Therefore, if a different type of printed circuit board is to be tested, the adapter 13 must be correspondingly exchanged. This can be done in a simple manner by tilting the testing assembly 7 about the pivot axis 33 (FIG. 2) and then withdrawing the adapter 13 from the recess within which it is received and replacing it with another adapter 13 which has been produced for the different type of circuit board. Likewise, each time a different type of circuit board is to be tested, the tester must be programmed with the "ideal" reference results obtained from an interrogation of a "faultless" master board of the different type.
Whenever the tester to be used for the first time to test a "new" type of printed circuit board, the new testing program must be learned. This is accomplished by placing the tester in the self-programming mode and electrically interrogating a freshly produced master board using an equally fresh adapter 13. For this purpose the adapter is mounted with its contact pins 14 on the master board.
FIG. 3 shows a view of the adapter from below with the points of the contact pins which are to be pressed against the test points of the conducting paths of the master printed circuit board shown schematically by crosses "x". The conducting wires 15 joining the connecting plugs 16 of the connecting blocks 23 to the pointed contact pins 14 are shown in FIG. 5. FIG. 6 shows an enlarged view of part of FIG. 5 which more clearly shows the contact strips 22 of the test point cards 25 which are mounted on the connecting plugs 16 of the connecting blocks 23. The adapter 13 is electrically connected to the electronic interrogation circuits 18 at connecting plugs 16 (FIG. 5) and the master board 12 is brought into the testing position on the tester (See FIG. 2) and is electrically interrogated to determine its test point interconnections as described below. A first one of the contact pins 14 is energized by the electric interrogation circuits 18 and the circuits 18 check to see what electrical contact is made with other contact pins 14 through the printed circuit board connector paths. When this is established, a next one of the contact pins 14 is energized and a corresponding interrogation is performed. This process is repeated for all of the contact pins 14 of the adapter 13. The interrogation results are stored in a tester memory 20 in the form of a table which indicates with what other test points each individual test point of the printed circuit board is connected. The table may, for example, be in matrix form with the energized test points listed as column headings and the respective conductively connected test points being indicated by entries in corresponding rows beneath them.
When this table of "ideal" interrogation results has been completed, the learning process is terminated. The results of the testing undertaken by the interrogation of a master board are thus stored in the tester memory 20 (FIG. 2) which now contains the reference data as to which test points of a "faultless" printed circuit board are electrically interconnected and which are electronically insulated.
When the tester has been programmed in the manner described, the tester is ready to test the conductor paths of other (i.e. production line) printed circuit boards of the same type. The electronic interrogation circuits of the tester will compare each set of interrogation test results with the stored results obtained from the initial interrogation of the master printed circuit board. The electrical comparison is done by means of a comparator 21 (FIG. 2). The results of the comparison by comparator 21 are displayed on the display panel 11 (FIGS. 1 and 2) which reads either "good", "insulation fault" or "break fault". For insulation faults and break faults, the locations of the faults (i.e. between which test points) are displayed. In addition, the results of the comparison made by comparator 21 are communicated to the control circuit of the sorting member 8, which sorts the printed circuit boards as they leave the testing assembly 7, as already described.
When another type of printed circuit board is to be tested, the former contents of the memory 20 are erased and the learning is performed anew with entry of new reference test results into memory 20 in the same manner, as described above.
A different master board 12 and corresponding different adapter 13 are produced for each type of printed circuit board to be tested. When a particular type of board is being tested for the first time, the master board and corresponding adapter are freshly produced. Thus, one may be fairly sure that they are indeed "faultless." However, when tests on a type of board have been previously done and the master board and the adapter are "old", having been stored for a prolonged period while other types of printed circuit boards have been tested by the tester, such assurance does not exist. During the time of storage, faults may have arisen through mechanical damage to the adapter contact pins 14, through scratch damage to the master board's conductor paths, etc. Thus, if such a damaged master board or adapter is used to generate reference interrogation results for testing, the testing assembly 7 will learn a false testing program. This may result in faulty printed circuit boards being found to be good and faultless printed circuit boards being erroneously found to be faulty.
To provide a check as to whether a master board or its corresponding adapter for a given type of printed circuit board has suffered any damage during non-usage and storage between tests the adapter 13 of the present invention is provided for subsequent use with a memory 19 that is preset with stored information representative of the original test of the freshly produced master plate. This stored information serves to verify the continuing accuracy of the testing program each time it is relearned. When a new master printed circuit board and a new adapter are put into operation for the first time, information representative of the reference results obtained by the first interrogation of the master board by the electronic interrogation circuits 18 is derived from those results by a verification data forming circuit 34 (FIG. 2). This information is also displayed on a verification data display 10.
The perspective view of the adapter 13 in FIGS. 3 and 4 shows the pointed contact pins 14 at the bottom and the connecting plugs 16 at the top. FIG. 4 shows only one plug-in card 25 of the electronic interrogation circuits 18. FIG. 5 shows two plug-in cards 25. The plug-in cards 25 are provided at their underside with plug-in strips 22, the connecting plugs 16 of the adapter 13 being inserted in the contact receptacles of those strips. The connecting plugs 16, in turn, belong to plug-in strips 23 which are arranged side by side on the upper side of the adapter 13 (FIGS. 5 and 6). At the bottom of plug-in strips 23 there are located contact points which are connected to the contact pins 14 via conducting wires 15. A further plug-in strip 24, whose contact pins project downwardly, is soldered to the contact points of the lefthand plug-in strip 23 in FIGS. 5 and 6. The verification data memory 19, which is likewise in the form of a plug-in strip, is mounted on the contact pins of strip 23. This is shown in two views in FIGS. 7 and 8.
The verification data can, for instance, be a single representative number characteristic of the table reference test point interconnections stored in the memory 20 during the original learning process from the fresh master board and adapter. This number is stored in the adapter memory 19, which is preferably a fixed-value memory, as described further below in reference to FIGS. 7 and 8. When the tester is subsequently again programmed from the same master and adapter after a period of using the tester for testing other types of boards, the information in the adapter memory 19 provides a simple check on the accuracy of the relearned testing program and on whether the master board or adapter has suffered a contact fault or some other failure, during the interim storage period.
Once the initial test of the fresh master board and adapter is complete and verification data is stored in the memory 19, then for all subsequent tests the interrogation electronics 18 will query the data stored in the adapter memory 19. The queried verification data will be compared with the representative value formed during each subsequent interrogation of the master printed circuit board during the self-programming procedure by the verification data forming circuit 34 in a verification data comparator 35. If the comparator 35 determines coincidence, this indicates that the master printed circuit board and the adapter 13 have not undergone any change during interim storage. If, on the other hand, a discrepancy is detected, then there is an indication that either the master printed circuit board or the adapter 13 have meanwhile sustained damage. The fact of discrepancy will be indicated on the fault display 11 (FIG. 1).
The electronic circuits required for interrogating the contents of the memory 19 and the electronic circuits of the comparator 35 are the same as the electronic circuits conventionally used to interrogate the contact pins 14 and used for comparator 21. The structure of the verification data forming circuit 34 is dependent on the verification number selected for use in the adapter memory 19. The circuit 34 may comprise, for example, a conventional data processor programmed to manipulate the test results stored in the tester memory 20.
After understanding the teachings of this invention as will become apparent from this disclosure, those skilled in the art will appreciate the manner different types of verification data that can be selected for use in practicing the invention and selection will be a matter of personal preference.
A second example of suitable verification number is derived by multiplying the number of interconnected test points in the reference table by the number of insulated test points for any particular single energized point. A characteristic verification number is obtained by adding the code numbers of all the test points together to form an initial sum. Then the code numbers of all the test points appearing in the first column of the table are multiplied by a constant number and thereafter the individual products are added together to obtain a second sum. The first and second sums are added together to form a third sum. This third sum is a characteristic of the particular contents of the table and will produce a different number for different master boards and adapters corresponding to different type of printed circuit board to be tested.
It will be appreciated by those skilled in the art that verification data may be derived in many other ways. What is decisive, however, is that the representative value by characteristic of the interrogation results determined by the interrogation electronics 18 using a "faultless" adapter 13 in a test of a "faultless" master printed circuit board.
The representative value derived by the verification data forming circuit 34 and visually displayed on the verification data display 10 (FIGS. 1 and 2) may be represented in digital form and stored as testing program verification information in adapter memory 19. The memory 19 is located inside the adapter 13, as shown in FIGS. 5 and 6. Between the memory 19 and the connecting blocks 23 there is further found an intermediate block 24 which facilitates attachment and replacement of the memory 19.
The adapter memory 19 is especially valuable when the tester is again used to test a certain type of printed circuit board after a lengthy intervening period of use for testing other types of boards. To prepare for again testing the first type of board, the tester must relearn from the master board the table of reference results concerning interconnection of the test points. In this relearning process the verification data will be formed in the same way from the relearned table as it was in the original programming process. The derived verification number is then compared with the characteristic number fixed in the adapter memory 19 derived previously from the fresh master and fresh adapter. If the two characteristic numbers differ, this means that a fault (as, for example, a contact fault between an adapter pin 14 and the printed circuit board) has occurred in the second learning process. Thus, the self-programming can be monitored for accuracy and for the continued integrity of the master board and the adapter.
If a particular type of printed circuit board has a great many separate test points, the characteristic number could reach a relatively high value and thus the capacity of the adapter memory 19 would have to be more complex. This complexity can be avoided by reducing the value of the verification number while still maintaining enough information to reliably ascertain whether there has been a fault in the second learning process. The verification data could for example, be reduced by dividing it by a constant whole number and sorting only the remainder left over after the division as the characteristic number in the adapter memory. The verification data number obtained in this manner has only low storage location requirements, and can be represented in digital form, for example, in only sixteen bits.
A simple example for present adapter memory 19 is shown in FIGS. 7 and 8. The preferred adapter memory 19 consists of a plug-in strip. The stored verification data information is represented in the form of conducting connections between the individual plug contacts 30. These conducting connections are produced in simple fashion by means of a common electrically conducting wire 29 by soldering the corresponding soldering lugs 26 of the plug contacts 30 to this wire at soldering points 28. The soldering lugs may be considered as binary value carriers. A conducting connection made by soldering a lug 26 to the conduction wire 29 will result in a binary "1" being read from the corresponding plug contact 30. The absence of such a connection results in the reading of a binary "0" from the corresponding plug contact 30. This very simple memory construction in the form of a plug-in strip permits rapid examination, even visually, of the adapter memory to see whether the stored information has been altered during storage by some external influence, such as the breakage of a soldering point 12. The totality of soldering lugs (soldered and unsoldered) results in a binary number corresponding to the representative value. Thus, it is evident that such structure for memory 19 is a particularly inexpensive structural element which can be easily programmed.
This plug-in strip may be attached in simple fashion to the intermediate plug 24 (See FIGS. 5 and 6) so that it may be interrogated in the same manner as any other block 23 by the testing electronics 18.
As the verification data memory 19 contains only a representative value and not the complete results of the first interrogation of the master printed circuit board with the corresponding adapter 13, there is a possibility that faults, which arise on the master board and in the adapter, will cancel each other in such a way that on relearning the new verification data will have the same value as the original data, so that the faults in the testing program will go undetected. If desired, the probability of such complementary faults occurring can be reduced by storing more than one representative value in adapter memory 19.
From the foregoing it will be appreciated that with the adapter including a memory preset with stored information representative of the results of the original interrogation of a master printed circuit board, as described herein, self-programming of a printed circuit board tester can be achieved with verification of the continuing integrity of the master board and adapter associated with each type of printed circuit to be tested.
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A self-programming printed circuit board tester which receives and stores information corresponding to the conductive and insulative relationships between test points or master printed circuit boards and then compares that information to information received from boards to be tested and an adapter for connecting each master printed circuit board to the tester, the adapter having a memory which stores and supplies to the tester information corresponding to information supplied through the adapter to the tester from a perfect master printed circuit board.
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This is a continuation of application Ser. No. 756,203, filed Jan. 3, 1977, now U.S. Pat. No. 4,124,966 issued Nov. 14, 1978.
The present invention relates in general to the closing of bags and, in particular, to a method and apparatus for clamping a flexible poly-bag and preparing it for closure.
BACKGROUND OF THE INVENTION
Recently, in the dairy industry and in other industries dealing in consumer goods such as food products, there has been a growing trend to the use of thin-walled poly-bags for packaging purposes. Milk may be found in pouches and the pouches may be found in overbags. Potato chips, cereals, fertilizers, kitty litter, pet food and laundry detergents, are examples of other products found in poly-bags which are usually hermetically sealed as by heat sealing to preserve freshness. Vegetables and bakery products are often packaged in poly-bags which may be closed by pressure-sensitive adhesive tapes or reusable fastening devices. All of these products share the common steps of loading a predetermined weight, number or volume of a commodity into a bag and subsequently closing the bag hermetically or otherwise. The speed with which the filling and closing operations can be accomplished is governed by a number of factors, not the least of which is the capacity of the filling and closing apparatus itself. Other constraints are found in the feeding, weighing (or counting) and removal stages.
Many filling machines in the past have utilized gravity feed for the commodity to be packaged, the commodity passing downwardly through a hopper into a bag positioned therebeneath. Once the bag was properly filled it was removed from the filling location and passed, as by a conveyor to a closure station. In many instances, the hopper could double as a counting or weighing device to determine the exact amount of the commodity to be allowed to fall into the bag.
If the bag was to be hermetically sealed, or even if the opening was to be brought together to form a "pony tail," the machine designer was faced with the random location of the bag sides after the bag had fallen from the hopper. If the bag was to be sealed it was necessary to bring the bag sides together face to face for a bar sealer. If the bag sides were to be gathered for a "pony tail" configuration it was necessary to somehow circle the bag sides and bring them together into the "pony tail" for application of the appropriate fastener or closure member. Needless to say the equipment for this step preliminary to actual closure was, of necessity, sophisticated and expensive.
SUMMARY OF THE INVENTION
The present invention seeks to overcome the problems of the prior art by providing a filling and closing device wherein the bag opening is controlled at all times and hence the equipment required to grasp and close the bag becomes simple, effective and less expensive than prior art equipment. The present invention achieves this objective by grasping the end edges of an opened bag adjacent the opening and, once the bag has been filled, drawing those ends outwardly until the opposing faces come into close juxtaposition this without releasing the bag from its position below the filling hopper. Once the bag is this closed position it is clamped and removed laterally from below the hopper. If the bag is to be hermetically sealed a heat sealer within the clamping means will effect the heat seal during the lateral transfer. If the bag is to be formed into a "pony tail" a suitable ram may be used to bunch the sides together.
The present invention may, therefore, be described briefly as an apparatus for loading a bag with a commodity via a hopper having a retractable bottom closure member comprising; means for arranging at least one empty bag adjacent the hopper, the bag having an open end adjacent the closure member; means for opening the bag and essentially simultaneously retracting the closure member from below the hopper to permit the commodity to pass into the opened bag, the member serving to hold the bag open; means for gripping opposed end portions of the opened bag; means for moving the gripping means apart thereby bringing opposed faces of the bag into close juxtaposition; and means for clamping the opposed faces together and removing the clamped bag from below the hopper.
The present invention is also found in a packaging method described as a method for loading a bag with a commodity from a hopper provided with a movable bottom closure member comprising the steps of; essentially simultaneously opening the hopper by retracting the closure member, opening a bag below the hopper and gripping opposed end edges of the bag at the opening thereof; drawing the opening to an essentially closed condition by moving the opposed end edges away from each other thereby creating a pair of opposed and closely adjacent bag faces; and clamping the faces together over the length thereof to hold the bag firmly and laterally withdrawing the clamped bag from below said hopper.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the first embodiment of the apparatus of the present invention;
FIG. 2 is a view similar to that of FIG. 1 but showing the internal structure of the first embodiment of the present invention;
FIG. 3 is an enlarged view of the bag clamping mechanism
FIG. 4 is an enlarged view of the bag opening finger mechanism;
FIG. 5 is a perspective view of the hopper assembly used in the first embodiment;
FIG. 6 is an enlarged view of the bag clamping and carrying mechanism; and
FIG. 7 is a view similar to that of FIG. 2 but showing the internal structure of a second embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 broadly illustrates the bag loading and sealing apparatus of the present invention as it might be found in an industrial environment. The apparatus 10 thus includes a general framework or housing 12 provided with a hopper 14 which receives the commodity to be loaded, the commodity arriving at the hopper as a predetermined weight, volume of quantity, or being appropriately measured right at the hopper. The manner in which the correct amount of commodity to be loaded is determined does not form a part of this invention. Neither does the manner in which the commodity is fed to the hopper 14, although it is expected that an appropriate conveyor could be used. On the side of the framework carrying the hopper, means are provided for holding a plurality of empty bags (see FIG. 5) so that each bag may, in turn, be filled with the commodity from the hopper (see filled bag 16 (FIG. 1)). Also mounted in the framework are means for moving a filled bag laterally away from the hopper area and, if required, for simultaneously sealing the bag (see FIG. 6). The laterally shifted bag is then released to fall on a take-away conveyor 18 positioned so as to extend through the framework 12 and to receive the filled, and possibly sealed, bags. FIG. 1, by the way, shows the bag tops as being heat sealed as by a bar sealer.
FIGS. 2 and 7 illustrate the internal structure of the present invention in greater detail than does FIG. 1. As seen in FIG. 7, the framework 12 (applicable to both embodiments) includes a number of upright members 20, a number of longitudinal members 22, and a number of transverse members 24. The lowermost section 26 of the hopper 14 is shown as being mounted between a pair of the transverse members 24. Opposite the front and rear faces of hopper section 26 are a pair of cross-members 28,30 spanning the distance between the respective pairs of uprights 20 associated with the transverse members carrying hopper section 26.
Extending between the members 28 and 30 is a pair of guide rods 32,34 each rod being parallel to the transverse members 24 and being anchored securely to the members 28,30. Each rod carries a bearing block 36 reciprocally slidable thereon, the bearing blocks being elongated in the direction of the rods and being generally rectangular in cross-section. Rigidly affixed adjacent each end to a respective bearing block is a closure member or carrier plate 38, the plate spanning the distance between the blocks 36. The elevation of plate 38 within the framework is such that its upper surface makes sliding contact with the bottom edge of hopper section 26. Reciprocal movement of plate 38 is provided by a hydraulic or pneumatic cylinder 40 centrally affixed to member 30, the rod 42 of cylinder 40 extending through member 30 for attachment to plate 38 as at 44. If desired, carrier plate 38 may be of sufficient width to completely block the lower opening of hopper section 26 whereby the measured commodity or product may rest thereon prior to loading. In such an instance, the connection 44 between rod 42 and plate 38 would be on the underside of plate 38 rather than on the top as shown in FIG. 2. This latter configuration is more relevant to the embodiment shown in FIG. 7.
Affixed to the underside of carrier plate 38 is a pair of spaced apart bearing blocks 46 (FIG. 4), each carrying therein a rotatable shaft 48. At one end of each shaft 48 is a generally rectangular finger 50 and at the other end each shaft mounts a link 52. Each link is, in turn, pivotally connected to the rod 54 of a cylinder 56. Each cylinder is mounted to the short leg of an L-shaped bracket 58, the other leg of which is pivotally connected to a bracket 60, as at 62, the brackets 60 being affixed to the rear edge of plate 38. This bag opening assembly, the operation of which will be described hereinafter, is shown in detail in FIG. 4.
FIG. 3 illustrates a bag gripping or clamping mechanism 64 which includes a generally horizontal carrier plate 66 which is located by a link 68 pivotally connected to the plate 66 as at 70 and to a bracket 72 as at 74. Bracket 72 may be affixed to cross-member 28 as illustrated in FIG. 2 for the first embodiment, or to an upright 20 as illustrated in FIG. 7 for the second embodiment. As seen in FIG. 2 there are two such mechanisms 64, one at each end of carrier plate 38. Carrier plate 66 is further located by a pair of parallel links 76 each of which is pivotally connected to the carrier plate 66 as at 78 and to the carrier plate 38 as at 80. Links 76 along with the carrier plates 38 and 66 from a parallelogram.
Mounted to each carrier plate 66 are mounting blocks 82 and 84, these blocks carrying a support rod 86 extending parallel to the carrier plate 38. At the inboard end, each rod 86 mounts a vertical clamping block 88 which trunnionly mounts a bell-crank 90, one end of which carriers a short rod 92 of small diameter. The opposite end of bell-crank 90 is pivotally connected to the rod 94 of a cylinder 96 which, in turn, is affixed to an L-shaped bracket 98 in the same manner as cylinder 56. Bracket 98 is pivotally connected to the mounting block 82 as at 100.
Turning now to FIGS. 2 and 6, the bag clamping and carrying mechanism will be described. As seen in FIG. 2, this mechanism is laterally offset from the previously described structure and would usually be situated above the conveyor 18 of FIG. 1. This mechanism includes a generally U-shaped horizontal member 102 provided with two downwardly projecting legs 104,106 one leg being mounted at one end of one of the arms of the member, the other leg being mounted at the other end of the same arm. The other arm has a bevelled portion 108 at the entrance to the member. A pair of vertically spaced apart guide rods 110 pass through the legs 104,106 and extend to full length of the apparatus to be affixed to upright members 112 mounted in the framework 12. Affixed to the leg 106 and passing through the leg 104 is the rod 114 of a cylinder 116 which, in turn, is pivotally mounted to the upright member 112 at the opposite end of the framework to leg 106. Guide rods 110 and cylinder 114 are positioned behind the hopper section 26 to avoid interference with an opened bag.
Reciprocably mounted within the opening of member 102 is a clamping bar 118, supported by a pair of guide rods 120 extending through the adjacent member arm and driven by a pair of cylinders 122. Clamping bar 118 may carry in its inward face a heating element 124 of a conventional bar sealer.
FIG. 5 illustrates a hopper and bag holding assembly which is especially adapted for use in the first embodiment of the present invention. In this instance, reference number 126 denotes the top surface of the framework 12 and it is seen that lower hopper section 26 is positioned therebelow. A wicket assembly constituting a mounting plate 128 and a pair of wicket rods 130 is mounted to top surface 126 in front of the apparatus (deleted from FIG. 1 for clarity). The wicket rods 130 support a plurality of wicket bags 132 in their closed state, wicket bags being of the type that have an extension of one side projecting above the bag opening with the extension having a pair of holes for receiving the wicket rods 130. The bag opening its located just below the lower edges of the mounting plate 128.
As seen in FIG. 5 the hopper 14 extends above surface 126 and is provided with a reciprocable wall 134 which slides in suitable guides (not shown) so that it can fully close or fully open the hopper 14, drive for the wall 134 being provided by a cylinder 136 suitably mounted to the framework. Also mounted within the hopper 14 is a plurality, such as three, of nozzles 133 which point towards the opening of the next bag to be filled. With this configuration, the carrier plate 38 would only partially cover the opening of lower hopper section 126 so that there is a clear path between the nozzles and the bag opening.
Turning now to the second embodiment, as shown in FIG. 7, the movable wall 134 is omitted and carrier plate 38 constitutes the only closure for the hopper. Nozzles 138 in the instance could then be positioned on the underside of carrier plate 38 although they would still be directed towards the bag opening. The central zone of the plate 38, with nozzles attached could then be similar in configuration to the bottom plate or wall illustrated in Canadian Pat. No. 1,008,040 issued Apr. 5, 1977 and assigned to the assignee of the present invention. Also, as an alternative, the nozzles could be positioned on the outside wall of lower hopper section 26 if there is sufficient clearance provided adjacent the leading edge of plate 38, when in the closed position, to permit an air blast to reach the bag opening. The clearance could be very slight whereby there would be no deleterious effect on the load-carrying ability of the plate 38.
Another alternative construction is shown in FIG. 7 whereby the rods 32 are positioned inboard of the pivot points for the links 76 rather than outboard thereof as shown in FIG. 2. The positioning of the rods is not critical and the actual location would be determined on the basis of the dimensional limitations of the apparatus as required.
The operation of the present invention will now described in relation to the first embodiment. It is initially assumed that carrier plate 38 is positioned below hopper section 26 and that movable wall 134 closes the upper hopper section. It is further initially assumed that the correct amount of commodity to be loaded has been fed to the upper hopper section to rest on wall 134 and that a supply of wicket bags is positioned on the wicket rods 130. In this configuration, the sealing and carrying mechanism of FIG. 6 is positioned above conveyor 18.
Upon initiation of the apparatus cycle, air is caused to jet from the nozzles 138, the jet being directed towards the opening in the first unused wicketted bag thereby causing the bag to puff open. Cylinders 56 are then actuated in order to cause rotation of fingers 50 from their horizontal position to their vertical position extending downwardly into the bag opening. Essentially simultaneously cylinders 40 and 136 are actuated to retract the carrier plate 38 and wall 134 respectively whereby the commodity will descend through the hopper and into the opened bag. When the plate 38 has reached the end of its retractive motion the bag opening will be large and generally square as formed by the fingers 50.
During the retractive motion of plate 38 forces are applied to the two carrier plates 66 via the parallel links 76 tending to move the plates 66 in conjunction with the plate 38. Such motion, however, is constrained by the links 68 and hence the plates 66 actually follow an arcuate horizontal path from their rest position well outboard of hopper section 26 to a new position adjacent the hopper section 26. Links 76 and 68 along with the clamping mechanism mounted on plates 66 are dimensioned so that, in this new position, the mid-point of the adjacent end edges of the opened and loaded bag are very close to the adjacent side of the corresponding clamping block 88. When plates 66 reach this new position, cylinders 96 are actuated whereby rods 92 are caused to pivot into the bag opening and to clamp the adjacent end edge of the bag against the corresponding clamping block 88.
At this point in the cycle, fingers 50 are retracted from the interior of the bag opening and plate 38 as well as wall 134 return to their positions blocking their respective hopper sections. This movement of plate 38 causes retractive movement of plates 66 through the parallel links 76 as constrained by links 68 whereby plates 66 return to their rest positions. However, the rods 92 still clamp the bag sides and this returning movement of the plates 66 thereby causes the bag opening to close to a line between the opposed rods 92. The width of the bag opening now corresponds only to the diameter of the rods 92 and forms a slit with the opposed faces of the bag opening in close juxtaposition.
With the bag opening drawn taught by the rods 92, the clamping mechanism of FIG. 6 is then actuated via cylinder 116 whereby the U-shaped member 102 moves laterally and the arms thereof are positioned so that the bag opening is located therebetween. The bevelled edge 108 helps to guide the member 102 with respect to the bag opening and will prevent any jamming of the mechanism should the bag be positioned to one side or the other of its usual line. Once the member 102 is in position the clamping bar 118 is brought into registry with the bag side in order to clamp the opposed bag faces together against the arm having the bevelled entrance portion 108. The clamping action will take place below the lowermost end of the rods 92 to avoid any interference therewith and to permit the rods to be withdrawn following the clamping action.
The clamped bag is then withdrawn laterally by the mechanism as driven by cylinder 116 and this movement tears the bag from the wicket rods 130. During the lateral movement, the bag may be heat sealed via the bar sealer 124. Once the clamping and sealing mechanism has returned to its rest location, the clamping bar 118 retracts to release the bag to fall to the take-off conveyor 18.
The operation of the FIG. 7 embodiment is identical to that described hereinabove with the exception that the commodity to be loaded rests directly on the carrier plate 38 and drops into the opened bag upon retractive movement of the plate 38. The location of the parallel links 76 outboard of the bearing blocks 36 has no bearing on the operation of the invention.
It is thus seen that the present invention provides a compact and efficient loader for wicketted bags, the loader being fully automatic in operation. Proper quantities of a commodity may be loaded in a wicket bag and the bag sealed in a continuous operation which permits a loading operation to be taking place simultaneously with a sealing operation on a previously loaded bag. The invention could be used as well to merely transport a loaded bag laterally to subsequent closure equipment if heat sealing as illustrated is not desired or required.
Needless to say suitable microswitches, relays and timers would be used in the pneumatic and electric circuits as required to control or adjust the operating cycle. Such circuitry can be provided by a skilled practitioner and does not form a part of the present invention. Undoubtedly, variations in the present invention may occur to a skilled practitioner and hence the scope of protection afforded the invention should be determined from the appended claims.
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An automatic wicketted bag leader is suited to load one bag while simultaneously closing and sealing a preceding bag, each bag to contain a predetermined amount of a commodity. A hopper feeds the commodity when desired into a wicket bag which has been opened via mechanism connected to a retractable hopper-closing plate. A bag clamping mechanism simultaneously moves into position adjacent the sides of the opened bag and clamps the sides at about the midpoint thereof such that when the plate returns to its hopper-closing position the bag sides are drawn apart at the opening to bring the bag faces close together. The bag opening changes its configuration from generally square to a long rectangle. Clamping mechanism then moves laterally to encompass the bag opening and to clamp the two faces together and to then withdraw the clamped bag from below the hopper. The clamped bag may be heat sealed as it is withdrawn and then fed to an output conveyor. During withdrawal another bag may be loaded.
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