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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] Priority is claimed based on Federal Republic of Germany patent application no. 10 2009 009 420.2 filed Feb. 18, 2009, the entire application incorporated by reference herein.
TECHNICAL FIELD
[0002] The invention concerns a water separator, in particular for a fuel supply system of an internal combustion engine in motor vehicles.
BACKGROUND OF THE INVENTION
[0003] A water separator for a fuel supply system of an internal combustion engine in motor vehicle includes a separating chamber formed in a housing and a separating element arranged in the separating chamber as well as a collecting chamber arranged below the separating element for collecting water separated from the fuel. The housing has an inlet and an outlet for the fuel. The separating element comprises two separating stages wherein the first separating stage contains a hydrophilic filter medium.
[0004] Devices for separating water from fuel in fuel supply systems are frequently combined with a fuel filter. U.S. Pat. No. 4,740,299 discloses a fuel filter that has in its housing a collecting chamber for the water separated from the fuel. The fuel is supplied from above into the filter housing wherein it is assumed that the heavier water component in the fuel will sink to the bottom and collect in the collecting chamber. A portion of water emulsified in the fuel is however entrained by the fuel and transported through the filter material so that water is still present in the fuel at the outlet side of the filter.
[0005] EP 1 256 707 A2 discloses a fuel filter with water separating means. This fuel filter that is especially provided for diesel fuels of an internal combustion engine comprises two filter stages wherein the first filter stage is provided for particle filtration. This filter stage is comprised of a hydrophilic filter material that causes water that is finely distributed in the fuel to coalesce to larger water particle elements. A second filter stage of hydrophobic material is arranged downstream of the first filter stage and is positioned coaxially within the first filter stage. This arrangement is selected so that fuel that leaves the first filter stage and contains a water component will impact on the material of the last filter stage without being deflected. For this type of configuration of a fuel filter large surface areas of the hydrophilic material of the first stage as well as of the hydrophobic material of the second stage are required.
SUMMARY OF THE INVENTION
[0006] It is therefore an object of the present invention to provide a water separator of the aforementioned kind that has a simple configuration and enables generation of a defined droplet size at a separating stage.
[0007] In accordance with the present invention, this is achieved in that the hydrophilic filter material is surrounded by an element with a plurality of through openings that forms an outlet contour and generates drops of water, separated from the fuel, downstream of the filter medium and of the element.
[0008] The invention has the advantage that the coalesced water droplets are separated in a defined droplet size from the fuel; this is achieved by a plurality of through openings in the element that surrounds the filter medium. The element is preferably a perforated sheet metal, a perforated synthetic (plastic) material or ceramic material; alternatively, tight-mesh screens, synthetic grids or fabric are also conceivable.
[0009] In a further embodiment, the element that is present in the form of perforated sheet metal, perforated plastic material, ceramic material, tight-mesh screen or synthetic grid or fabric is embodied as liquid-permeable half shells wherein two half shells can be joined and in this way surround the filter element of the first separating stage. When joined, the half shells have the shape of a cylinder. The half shells are preferably connected to one another by lock connections or clip connections wherein a support element that is surrounded by the filter medium is clamped between edges of the half shells. In this way, a fixation of the first separating stage on the support element is provided.
[0010] The filter medium preferably comprises a single layer or multilayer filter material, wherein the filter material may be selected from in particular glass fibers or a synthetic foam or also a combination of the two. The filter material of the filter medium preferably has a thickness of at least 0.5 mm and maximally 30 mm. An especially suitable pore size of the filter material is in the range of 0.3 μm to 500 μm.
[0011] According to a further embodiment of the invention the hydrophilic filter medium is arranged on a support body that is provided with radial openings and the element with the plurality of through openings is resting immediately on the filter medium. The element that surrounds the filter medium has preferably a thickness of <5 mm. The through openings present in the element are expediently round, oval, polygonal, kidney-shaped, bone-shaped, of a circular or semi-circular shape. The configuration of the profile of the through openings in the direction of flow is preferably cylindrical, concave, convex or funnel-shaped. It is also advantageous that the surface of the through openings, as a result of the manufacturing process or a subsequent surface treatment, is smooth.
[0012] Moreover, with respect to the droplet formation, it is expedient that the through openings have a separating edge whose radius is <1 mm. The open surface area that is formed by the through openings is preferably <20 mm 2 . The through openings form expediently in the element a relative free surface area between 15% and 65%. It is also possible that the element with the through openings has a spacing between 0.1 mm and 5 mm relative to the filter medium.
[0013] The above features and advantages and other features and advantages of the present invention are readily apparent from the following detailed description of the best modes for carrying out the invention when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The accompanying Figures, where like reference numerals refer to identical or functionally similar elements throughout the separate views and which together with the detailed description below are incorporated in and form part of the specification, serve to further illustrate various embodiments and to explain various principles and advantages all in accordance with the present invention.
[0015] Features of the present invention, which are believed to be novel, are set forth in the drawings and more particularly in the appended claims. The invention, together with the further objects and advantages thereof, may be best understood with reference to the following description, taken in conjunction with the accompanying drawings. The drawings show a form of the invention that is presently preferred; however, the invention is not limited to the precise arrangement shown in the drawings.
[0016] FIG. 1 shows a longitudinal section of housing in the shape of a tubular body with separating chamber and collecting chamber, consistent with the present invention;
[0017] FIG. 2 is an illustration of several components of the separating element, partially in an exploded view, consistent with the present invention;
[0018] FIG. 3 is a variant of the embodiment of FIG. 2 , consistent with the present invention; and
[0019] FIG. 4 is a longitudinal section of a water separator, consistent with the present invention.
[0020] Skilled artisans will appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of embodiments of the present invention.
DETAILED DESCRIPTION
[0021] Before describing in detail embodiments that are in accordance with the present invention, it should be observed that the embodiments reside primarily in combinations of method steps and apparatus components related to a water separator as disclosed herein. Accordingly, the apparatus components have been represented where appropriate by conventional symbols in the drawings, showing only those specific details that are pertinent to understanding the embodiments of the present invention so as not to obscure the disclosure with details that will be readily apparent to those of ordinary skill in the art having the benefit of the description herein.
[0022] In this document, relational terms such as first and second, top and bottom, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. The terms “comprises,” “comprising,” or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. An element preceded by “comprises . . . a” does not, without more constraints, preclude the existence of additional identical elements in the process, method, article, or apparatus that comprises the element.
[0023] In FIG. 1 , a housing 2 is illustrated that is substantially embodied as a tubular body 3 that has a longitudinal direction LA and at the ends 4 , 5 is formed like a spherical segment, respectively. The housing 2 has transversely to the longitudinal direction LA a separating plane TE so that two housing parts 6 , 7 when joined together at the separating plane TE form the tubular body 3 . The separating plane TE is positioned adjacent to an inlet 8 so that the housing part 6 comprises approximately only the spherical segment of the end 4 while the housing part 7 comprises the main component of the tubular body 3 . At the inner side of the housing part 6 a socket 9 is formed that is substantially coaxial to the inlet 8 and is monolithic with the housing part 6 .
[0024] A partition 10 is attached to the other end 5 of the housing 2 and extends to the separating plane TE in the longitudinal direction LA at a level somewhat below the center. The partition 10 divides in this way the interior of the housing 2 into a separating chamber 11 and a collecting chamber 12 wherein only in the area of the housing part 6 an opening 13 is provided that realizes a connection between the separating chamber 11 and the collecting chamber 12 . At the end 5 an outlet 14 for the fuel is provided that extends in the same direction as the inlet 8 at the opposite end 4 . At the inner side of the housing part 7 a socket 15 is arranged that extends at least approximately coaxially to the outlet 14 . At the end 5 of the housing part 7 , a water drainage socket 17 is provided below the outlet 14 and immediately above the bottom 16 of the collecting chamber 12 . The housing part 7 is preferably a monolithic injection-molded part including the partition 10 , the outlet 14 , the socket 15 , and the water drainage socket 17 . The housing parts 6 , 7 are comprised preferably of plastic material and are welded or fused in the area of the partition plane TE so that a seal-tight connection is achieved that is fuel-resistant.
[0025] FIG. 2 shows a separating element 18 that is comprised of several components; for ease of understanding, the components are partially shown in an exploded view. The separating element 18 is embodied as a tubular element 19 conceived for a horizontal arrangement in the separating chamber 11 in the housing 2 , as shown in FIG. 1 . The tubular element 19 comprises a support body 20 provided with radial openings 21 in the form of longitudinal slots. The support body 20 is surrounded across the length of the longitudinal slots by a filter medium 22 that, in turn, is enveloped by an element 35 and forms together with it a first separating stage A 1 . The element 35 is, for example, a tight-mesh screen, a perforated sheet metal 36 , synthetic grid, or a fabric and is embodied as half shells 23 , 24 of a cylindrical shape.
[0026] The half shells 23 , 24 are comprised of a thin-wall material formed to a half cylinder 25 and a frame 26 that extends around the edges of the half cylinder 25 . The two frames 26 can be provided with clips or locking elements in order to connect the two half shells 23 , 24 with one another and to effect in this way an attachment on the support body 20 . The manufacture of the half shells 23 , 24 as two separate parts, i.e., the half cylinder 25 and the frame 26 , provides the possibility of using a material combination of synthetic (plastic) material and metal, but the half shells can also be made from the same material (monolithic).
[0027] Inside the support body 20 there is a partition 27 extending transversely to its longitudinal direction; it is positioned at a minimal spacing to the rearward end of the openings 21 when viewed in the flow direction S of the fuel. A guiding element 31 for guiding the flow is inserted into the interior of the support body 20 so far into the support body 20 that it contacts the partition 27 . The guiding element 31 is designed such that the flow cross-section within the support body 20 in the flow direction S becomes smaller. In this way, a uniform loading of the first separating stage A 1 across its entire length is provided.
[0028] Downstream of the support body 20 on the other side of the partition 27 a tubular section 28 adjoins the partition 27 . The tubular section 28 has radial cutouts 29 . The tubular section 28 is surrounded by a separating nonwoven 30 that covers the cutouts 29 . The separating nonwoven 30 is comprised of a hydrophobic material and forms in this way a second separating stage A 2 . The mesh width of the separating nonwoven 30 can be, for example, between 5 μm and 500 μm.
[0029] In FIG. 3 an embodiment variant of FIG. 2 is illustrated with a separating element 18 that differs from that of FIG. 2 in that the half cylinder 25 and frame 26 of the half shell 23 , on the one hand, and of the half shell 24 , on the other hand, are formed as a monolithic part and therefore are comprised of the same material, either synthetic (plastic) material or metal. All other features in FIG. 3 are the same as those of FIG. 2 so that for same parts the same reference numerals are used.
[0030] FIG. 4 shows a longitudinal section of a completely assembled water separator 1 . The housing 2 is comprised of housing parts 6 , 7 that form the tubular body 3 whose interior is separated by the partition 10 extending in the longitudinal direction LA of the housing 2 into the separating chamber 11 and the collecting chamber 12 . In the separating chamber 11 the separating element 18 in the form of tubular element 19 is arranged. The tubular element 19 comprises the support body 20 and the tubular section 28 that are positioned behind one another in the flow direction in an aligned arrangement. On the support body 20 the filter medium 22 is arranged as well as the element 35 with the plurality of through openings. On the left end of the support body 20 shown in FIG. 4 a sleeve 32 is integrally formed that is matched with its outer circumference to the inner size of the socket 9 at the inlet 8 and is received therein. The right end of the tubular section 28 is matched to the inner size of the socket 15 at the outlet 14 and is secured therein.
[0031] Mounting of the tubular element 19 in the housing 2 is possible in a simple way in that first the completed separating element 18 is inserted, with the free end of the tubular section 28 leading, into the separating chamber 11 and is pushed into the socket 15 . If required, measures for a radial sealing action between the socket 15 and the tubular section 28 are to be provided. Subsequently, the housing part 6 is guided in the direction toward the housing part 7 and the socket 9 at the inlet 8 is pushed onto the sleeve 32 wherein also measures for a radial sealing action may be provided. The housing part 6 is moved so far in the direction toward the housing part 7 that the leading edge 33 of the housing part 6 engages a groove 34 of the housing part 7 and is connected seal-tightly therewith. Between the first separating stage A 1 and the housing part 7 as well as the partition 10 there remains an annular chamber that ensures sufficient flow. In FIG. 4 all other reference numerals are the same as those in FIGS. 1 to 3 for same parts.
[0032] The fuel flows into the water separator 1 through inlet 8 in the direction of arrow S 1 and passes through the sleeve 32 into the interior of the support body 20 . Because of the partition 27 the fuel in accordance with arrow S 2 passes through the openings designed as slotted holes (compare FIGS. 2 and 3 ) and father in radial direction through the filter medium 22 and the half shells 23 , 24 into the annular chamber defined between the half shells 23 , 24 and the inner wall of the housing part 7 as well as the partition 10 . Uniform loading of the first separating stage A 1 is ensured by the guiding element 31 for guiding the flow in the interior of the support body 20 . When the fuel with the emulsified water component passes through the separating element 18 that has a coalescing effect, water droplets are formed that as a result of the horizontal arrangement of the housing 2 sink onto the partition 10 . The water droplets are guided along the partition 10 and reach through the opening 13 the collecting chamber 12 .
[0033] The fuel from which the water component has been substantially separated by the separating stage A 1 flows as a result of a vacuum effect at the outlet 14 into the tubular section 28 , namely through the second separating stage A 2 that is formed by the separating nonwoven 30 and the radial cutouts 29 , in accordance with arrow S 3 . Since the material of the separating nonwoven 30 has a hydrophobic effect, the water component that is still emulsified within the fuel, and also already formed water droplets that have been entrained by the flow, are retained by the separating nonwoven 30 so that exclusively fuel will reach the tubular section 28 and the outlet 14 . The water collected in the collecting chamber 12 can be removed by devices known in the art and connectable to the water drainage socket 17 .
[0034] In the foregoing specification, specific embodiments of the present invention have been described. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention. The benefits, advantages, solutions to problems, and any element(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential features or elements of any or all the claims. The invention is defined solely by the appended claims including any amendments made during the pendency of this application and all equivalents of those claims as issued.
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A water separator for a fuel supply system of an internal combustion engine has a housing with an inlet and an outlet for fuel and further has a separating chamber and a collecting chamber for collecting water. The separating chamber is arranged above the collecting chamber. A separating element is arranged in the separating chamber, wherein the separating element has a first separating stage and a second separating stage. The first separating stage has a hydrophilic filter medium. An element with a plurality of through openings surrounds the hydrophilic filter medium. The element forms an outlet contour and generates downstream of the hydrophilic filter medium and the element droplets of water separated from the fuel.
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TECHNICAL FILED OF THE INVENTION
[0001] The present invention is directed to a lamp hanger for entertainments, and particularly to an animal-like lamp hanger that can be enjoyable and entertaining.
BACKGROUND OF THE INVENTION
[0002] There have been many lamp hangers that are shaped to be like various animals in the art. A great number of small electric bulbs are attached to the outside of the lamp hanger and the animal profile can be showed by lighting the bulbs in the dark. However, the lamp hanger disclosed in the prior art is unmovable. As a result, the lamp hanger in the art looks stiff and is lacking in entertainments.
SUMMARY OF THE INVENTION
[0003] Accordingly, the present invention is to provide a movable animal-like lamp hanger that has a compact structure and a vivid shape when used.
[0004] According to the invention, the movable animal-like lamp hanger comprises a body including a first movable portion, a plurality of ornamental lights attached to the body, a motor disposed in the body, a transmission shaft connected to the motor, and a first drive rod pivotally connected to the transmission shaft and connected to the first movable portion of the body in such a manner that when the motor drives the transmission shaft to rotate, the first drive rod can direct the first movable portion to move like a desired animal.
[0005] In an embodiment of the present invention, the movable animal-like lamp hanger further comprises a second drive rod pivotally connected to the transmission shaft, and the body further comprises a second movable portion which is connected to the second drive rod in such a manner that when the motor drives the transmission shaft to rotate, the first drive rod and the second rod can respectively drive the first movable portion and the second movable portion to move like a desired animal.
[0006] In another embodiment of the present invention, the movable animal-like lamp hanger further includes a third drive rod pivotally connected to the transmission shaft, and the body further comprises a third drive rod which is connected to the third drive rod in such a manner that when the motor drives the transmission shaft to rotate, the first drive rod, the second rod and the third rod can respectively drive the first, the second and the third movable portions to move like a desired animal.
[0007] In accordance with an embodiment of the present invention, the first, second and third drive rods may be connected with the first, second and third movable portions by means of three gimbals respectively. In a further embodiment of the invention, the first drive rod is connected with the first movable portion with a connecting member having two annuluses perpendicular to each other.
[0008] The invention can apply for various shaped animals and insects such as bees, rabbits, cattle, frogs, deer and etc., even shaped soldiers. The body can be made of plastics and metal. Various ornamental bulbs in different colors can be used to attach the outside of the body or the inside thereof in case that the body is formed in a transparent form or a grid shape. In one embodiment of the invention, the lamp hanger is shaped with a grid configuration, and the ornamental lights are attached to the inside of the body.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 schematically shows the working principle of the lamp hanger in accordance with the invention;
[0010] FIG. 2 shows an embodiment of the movable frog-like lamp hanger of the invention;
[0011] FIG. 3 shows another embodiment of the movable deer-like lamp hanger of the invention;
[0012] FIG. 4 shows another embodiment of the frog-like lamp hanger of the invention, which includes an enlarged view of a connecting member used; and
[0013] FIG. 5 shows another embodiment of the deer-like lamp hanger of the invention, which includes an enlarged view of a connecting member used.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0014] The present invention will be described in detail with reference to the drawings.
Embodiment 1
[0015] FIG. 2 shows an embodiment of the movable lamp hanger of the invention, in which the lamp hanger is designed in the shape of a frog 10 .
[0016] The movable lamp hanger 10 in this embodiment includes a body 7 which has two movable portions, a head portion 100 and a tail (back) portion 400 disposed on a trunk 70 of the frog. A motor 5 that is connected with a power supply (not shown) is fixed to a support 6 mounted within the body 7 , a transmission shaft 4 connected to the motor 5 with a crank 9 . A first drive rod 1 is connected to the transmission shaft 4 with its one end, and another end thereof is connected with the head portion 100 by a first connecting bar 114 . The connecting bar 114 is connected to a lower jaw portion 1000 of the head portion 100 . As shown in FIG. 2 , the connecting bar 114 is connected to a frame 118 of the lower jaw portion 1000 , which can drive the lower jaw portion 1000 to open or close round a rotating axis 119 with respect to an upper jaw portion 2000 of the head portion 100 of the frog. A connecting member 101 is provided to connect the first drive rod 1 to the connecting bar 114 . The connecting member 101 is a gimbal in this embodiment.
[0017] A second drive rod 2 is provided to connect the transmission shaft 4 with the tail portion 400 . A second connecting bar 214 is fixed to the inside of the tail portion 400 , and is connected with the second drive rod 2 with a gimbal 201 that is connected to a frame 205 of the neck portion. In this embodiment, the body is made of plastic, and a plurality of ornamental bulbs 8 are attached to the outside of the body.
[0018] Thus, when the motor 5 is energized, the transmission shaft 4 is driven to move circumferentially round the output shaft of the motor 5 by the crank 9 . The first drive rod 1 and the second drive rod 2 are respectively driven to move. The first drive rod 1 drives the first connecting bar 114 to move and to hereby draw and pull the lower jaw portion 1000 upward and downward with respect to the upper jaw portion 2000 (in the direction of an arrow a as shown in FIG. 2 ). Meanwhile, the second drive rod 2 is driven to move circumferentially round the transmission shaft 4 and hereby to make the tail portion 400 move upward and downward with respect to a fixed frame 67 where the support 6 is mounted (in the direction of an arrow b as shown in FIG. 2 ). Because the first drive rod 1 can be designed with a different length from the second drive rod 2 , the movement of the tail portion 400 is not synchronous to that of the lower jaw portion 1000 . Therefore, the movable lamp hanger of the invention looks like a real frog.
[0019] In another embodiment of the frog-like lamp hanger of the invention as shown in FIG. 4 , a connecting member 101 includes two annuluses 11 , 14 perpendicular to each other. With such a structure, when the motor drives the first drive rod 1 to rotate, it will take a short time for the annulus 11 to contact the annulus 14 such that the lower jaw portion 1000 stays for the same time in the closed state or in the opened state with respect to the upper jaw portion 2000 . As a result, the lamp hanger looks very vivid.
Embodiment 2
[0020] As shown in FIG. 3 , a movable lamp hanger shaped like a deer 20 is provided in this embodiment. As those shown in the Embodiment 1, the lamp hanger 20 includes the hollowed body 7 which is shaped a grid configuration, a great number of small ornamental bulbs 8 are attached to the inside of the body, the motor 5 is fixed to the support 6 mounted within the body 7 , and the transmission shaft 4 is connected to the motor 5 by the crank 9 . In this embodiment, there are provided three movable portions. Besides the movable portions of the head portion and the tail portion, a movable neck portion is also provided.
[0021] The first drive rod 1 is connected to the head portion 100 by two connecting bars 112 and 123 . The connecting bar 123 is connected to the head portion 100 with a gimbal 103 .
[0022] The gimbal 103 is connected to a frame 105 mounted to the head portion 100 . The connecting bar 112 is respectively connected to the first drive rod 1 and the connecting bar 123 with two gimbals 101 and 102 . With such a structure, the head portion 100 of the deer can be driven to move in the direction of an arrow c as shown in FIG. 3 .
[0023] The second drive rod 2 is connected to the neck portion 200 of the deer with a gimbal 201 . The neck portion 200 connected to the head portion 100 of the deer can be driven to move forward and backward round a pivot 214 within the trunk 70 by the second drive rod 2 , (in the direction of an arrow d as shown in FIG. 3 ).
[0024] A third drive rod 3 connected to the tail portion 300 of the deer by a connecting bar 312 is provided in this embodiment. A connecting bar 312 is connected to the tail portion 300 with a pivot 302 and connected to the third drive rod 3 with a gimbal 301 disposed at the body 7 . The tail portion 300 of the deer can be driven to swing in the direction of an arrow e round the pivot 302 by the third drive rod 3 .
[0025] Also referring to FIG. 1 , when the motor 5 rotates, the three drive rods 1 , 2 , 3 are driven to direct the head portion 100 , the neck portion 200 and the tail portion 300 to move. Because the first drive rod 1 has a different length from the second drive rod 2 and the third rod 3 , the movement of the three movable portions in this embodiment is not synchronous.
[0026] Because the body of the deer is shaped in the grip configuration, and a great number of ornamental small bulbs 8 are attached to the inside of the body, when the lamp hanger is arranged on the grass and is powered in the evening, it looks like a real deer in browsing.
[0027] In another embodiment of the deer-like lamp hanger of the invention as shown in FIG. 5 , the connecting member 101 including two annuluses 11 , 12 perpendicular to each other which is similar to that shown in FIG. 4 is provided. With such a structure, when the motor drives the first drive rod 1 to rotate, it will take a short time for the annulus 11 to contact the annulus 12 such that the head portion 100 stays in the lowest state or at the highest state with respect to the ground for the same time. As a result, the lamp hanger looks much vivid.
[0028] It is appreciated that the above embodiments and description are merely used to illustrate the present invention. Those skilled in the art will understand that alternatives, modifications, varieties or equivalents to the present invention can be made without departing from the spirit of the invention. The full scope of the invention is all the subject matter defined by the appended claims, and equivalents thereof.
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The present invention is to provide a movable animal-like lamp hanger comprises a body including a first movable portion, a plurality of ornamental lights attached to the body, a motor disposed in the body, a transmission shaft connected to the motor, and a first drive rod pivotally connected to the transmission shaft and connected to the first movable portion of the body in such an manner that when the motor drives the transmission shaft to rotate, the first drive rod can direct the first movable portion to move like a desired animal. The movable animal-like lamp hanger of the invention is very vivid in the dark when used in a park and the like.
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BACKGROUND OF THE INVENTION
This invention relates to a heat-insulating layer in an internal combustion engine to prevent unwanted lowering of the temperature of combustion gas in combustion chambers or exhaust ports.
Regarding internal combustion engines, particularly automotive engines, the employment of a heat-insulating structure or a heat-insulating coating is effective not only for enhancement of thermal efficiency of the engine but also for decrease in the amount of unburned hydrocarbons (HC) emitted into the atmosphere as an undesirable component of the exhaust gas. Furthermore, when the exhaust system of the engine comprises either a thermal reactor or a catalytic converter to purify the exhaust gas thereby to meet current emission standards, it is desirable to minimize lowering of the exhaust gas temperature before the entrance of the exhaust gas into the reactor or the converter because such a device requires a certain minimum temperature to exhibit its oxidation or conversion ability and exhibits its full ability at considerably high temperatures.
For the purpose of maintaining high exhaust temperatures in internal combustion engines, it has been proposed and sometimes put into practice to cover the wall surfaces of combustion chambers, top face of each piston and/or wall surfaces of exhaust ports with a ceramic material low in heat conductivity, either by attachment of a ceramic plate directly to a surface to be covered or by a flame or plasma spraying technique. However, in practical applications this heat-insulating method involves a serious problem that a ceramic layer formed on a metal surface is liable to crack, break and even separate (at least fragmentarily) from the metal surface due to shocks and vibrations experienced during operation of the engine and a difference in thermal expansion characteristics between the ceramic and the metal. Of course this means an insufficient service life of the heat-insulating layer. As a matter of more seriousness, the service life of a combustion chamber is shortened significantly when fragments of the injured ceramic layer fall into the combustion chamber.
Accordingly there is an earnest desire for a method of producing a heat-insulating layer which can withstand severe environmental conditions in internal combustion engines, that is, a novel type of method for strong, reliable and durable bonding between a metal member and a ceramic material.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a heat-insulating layer which is firmly and reliably secured to a cast metal member of an internal combustion engine and is highly resistant to shocks, vibrations and thermal stresses produced during operation of the engine.
A heat-insulating layer according to the invention is secured to a cast metal member of an internal combustion engine in such an arrangement that the heat-insulating layer is exposed to a combustion gas produced in the engine and comprises a metal body which has a porous structure. Only a first surface portion of the metal body is impregnated with a heat-insulating ceramic material, which is fired in this portion of the metal body. A second surface portion of the metal body is cast-inserted into the cast metal member such that the metal of the cast metal member infiltrates into at least a part of the second surface portion and that the ceramic-impregnated surface portion is exposed to the combustion gas in the engine.
The aforementioned metal body having a "porous structure" includes a metal body having a multiplicity of interstices (not literally "pores" ).
It is preferable that the porous (or intersticed) metal body has a structure more yielding to compressional and tensional forces than the cast structure of the metal member.
The ceramic-impregnated portion may adjoin the second surface portion inserted into the cast metal member. Alternatively, the ceramic-impregnated portion may entirely be distant from the second surface portion such that the porous structure of the metal body remains unchanged in an intermediate portion interposed between the first and second portions.
Optionally, the outer surface of the ceramic-impregnated portion may be coated with either a protective metal layer or a heat-insulating ceramic layer.
A heat-insulating layer according to the invention can be embodied in a combustion chamber wall, exhaust port wall or a top portion of a piston in the engine.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic and sectional view of a heat-insulating layer according to the invention inserted into a cast metal member to constitute a surface region of the cast metal member;
FIGS. 2-5 show four kinds of modifications of the heat-insulating layer of FIG. 1, respectively;
FIG. 6 is a schematic and sectional view of a combustion chamber portion of an internal combustion engine, wherein heat-insulating layers according to the invention are arranged to provide combustion chamber wall surfaces;
FIG. 7 is a sectional view of a top portion of a piston for an internal combustion engine, wherein a heat-insulating layer according to the invention provides the top face of the piston; and
FIG. 8 is a schematic and sectional view of an exhaust port of an internal combustion engine, wherein heat-insulating layers according to the invention are arranged to provide the port wall surfaces.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, reference numeral 10 indicates a cast metal member such as a cylinder head constituting part of an engine block of an internal combustion engine. A platy block 20 having a thickness of t 1 , which is a heat-insulating layer according to the invention, is embeded in a surface region of the cast member 10 such that an outer surface 20a of this layer 20 is exposed to combustion gas when the engine comprising the cast member 10 is put into operation. Originally, the platy block 20 is of a metal such as a nickel-base corrosion resistant alloy and has a porous or intersticed structure over its entire thickness t 1 . It is preferable that the porous metal block has a structure more yielding to compressional and tensional forces than the cast structure of the metal member 10. (Such a structure of the porous metal block is herein called "soft structure" for the sake of convenience.) However, in the illustrated state, i.e. when finished as a heat-insulating layer according to the invention, an exterior portion 22 of this metal block 20 is impregnated with a ceramic material 24, which was fired in the porous matrix of this block 20, such that the resultant ceramic-impregnated (accordingly heat-insulating) layer 22 provides the outer surface 20a of the block 20. The remaining interior portion 26 of the block 20 is essentially free of the ceramic 24 and is entirely embedded in the cast member 10.
The embedment of the platy block 20 is accomplished at the stage of forming the engine block member 10 by casting. In advance of the casting operation, the exterior portion 22 of the porous metal block (20) is impregnated with the ceramic 24 (or a raw material for the ceramic 24) by a wet process, followed by firing of the partly ceramic-impregnated block to fix the ceramic 24 dispersed in the exterior portion 22. In most cases, the thickness t 2 of the ceramic-impregnated portion 22 is nearly equal to, or somewhat larger than the thickness t 3 of the remaining portion 26. The thus prepared (partly porous and partly ceramic-impregnated) platy block 20 is employed as an insert at casting of the engine block member 10. The casting is carried out with the partly ceramic-impregnated block 20 placed in a prescribed position in the mold so that the block 20 may occupy a prescribed surface portion of the product to serve as a thermal barrier between a combustion gas produced in the engine and the principal portion of the cast metal member 10 which is a good heat conductor. In this casting operation, there occurs infiltration of the molten metal into the porous metal structure of the interior portion 26 of the inserted block 20. Upon solidification of the molten metal poured into the mold, therefore, the interior portion 26 of the block or heat-insulating layer 20 is firmly and tightly bonded to the cast metal member 10. In the cast-inserted state, the interior portion 26 of the block or heat-insulating layer 20 according to the invention serves not only as a support for the ceramic-impregnated portion 22 but also as a bridging layer between the cast metal member 10 and the ceramic-impregnated layer 22. It is permissible that the ceramic-impregnated layer 22 partly protrudes or somewhat dents from the surface 10a of the cast metal member 10. Also it is permissible that the impregnation of the exterior portion 22 of the block 20 with the ceramic 24 is performed so as to leave a certain degree of porosity to the resultant ceramic-impregnated layer 22.
Essentially, the metal block 20 having a porous or intersticed structure may be a porously sintered body obtained either by a powder sintering technique or a fiber sintering technique, a sponge metal or a mat-like body consisting of densely and irregularly intertangled fine metal wire or filament. The lastly mentioned form is particularly favorable because of its sufficiently soft structure.
In an internal combustion engine, there is no possibility that the heat-insulating layer 20 as a whole separates from the cast metal member 10 or the ceramic-impregnated layer 22 separates from the entirely metallic layer 26 since the heat-insulating layer 20 is cast-inserted into the member 10 and the two layers 22, 26 are originally two continuous and inseparable portions of a single metal body (20). The ceramic 24 in the exterior portion 22 of the heat-insulating layer 20 takes the form of fine particles dispersed in and fixed (by firing) to the porous metal matrix of the exterior portion 22 of the heat-insulating layer 20 and, hence, hardly separates from the metal matrix even when the heat-insulating layer 20, particularly its ceramic-impregnated portion 22, is subjected to thermal and mechanical stresses during operation of the engine. Even when a very small portion of the ceramic particles 24 separate from the metal matrix and the separated particles fall into a combustion chamber of the engine, a detrimental effect of such particles on the engine will be far less material in comparison with detrimental effects of relatively large flakes separated from a conventional ceramic coating for the similar heat-insulating purpose. When the porous metal block (20) has a soft structure as is preferred herein, some strains possibly produced in the ceramic-impregnated portion 22 by thermal stresses during operation of the engine will be absorbed in the soft metal structure.
Preparing the ceramic-impregnated layer 22 so as to retain certain degree of porosity is effective for reducing the emission of HC because a portion of HC is caught in the pores of this layer 22 and readily undergoes afterburning.
Usually it is appropriate that the total thickness t 1 of the heat-insulating layer 20 of FIG. 1 is in the range from about 6 mm to about 8 mm and the thickness t 3 of the interior portion 26, where the cast metal has infiltrated into the porous structure of the original metal block (20), is made to range from about 2 mm to about 3 mm. Preferably the thickness t 2 of the ceramic-impregnated portion 22 is made to range from about 3 mm to about 4 mm.
However, as shown in FIG. 2, the thickness t 1 of the original metal block (20) and the manner of insertion of the partly ceramic-insulated block in the cast member 10 may be modified such that the finished heat-insulating layer 20 has a solely metallic and porous portion 28, as an intermediate portion between the ceramic-impregnated portion 22 and the interior portion 26 cast-inserted in the cast metal member 10, where the porous structure of the original metal block (20) remains unchanged, meaning that the molten metal has not infiltrated into this portion 28 during casting operation. Since the porous intermediate layer 28 is higher in strain-absorbing ability than the interior portion 26 impregnated with a cast metal, strains produced in the ceramic-impregnated portion 24, sometimes also in the interior portion 26, during operation of the engine are almost thoroughly absorbed in the porous portion 28. Accordingly the ceramic-impregnated portion 24 of the heat-insulating layer 20 of FIG. 2 is still less liable to suffer injuries such as cracking than the counterpart in FIG. 1. A thickness t 4 of about 3 to 4 mm is sufficient to the porous intermediate layer 28, so that the total thickness t 1 of the heat-insulating layer 20 of FIG. 2 will usually range from about 9 mm to about 12 mm. The boundary between the ceramic-impregnated portion 22 and the porous portion 28 may be in a plane outside of the surface 10a of the cast member 10.
Referring to FIG. 3, a metal coating layer 30 may optionally be formed on the outer surface of the ceramic-impregnated portion 22 of the heat-insulating layer 20. The metal coating 30 is formed before casting of the engine block member 10 together with the semifinished heat-insulating layer by flame or plasma spraying of a metal onto the surface of the ceramic-impregnated portion 22 or by dipping of a surface region of the ceramic-impregnated portion 22 in a molten metal bath. Even when a portion of the ceramic particles 24 separates from the metal matrix of the exterior portion 22, the metal coating 30 prevents actual separation of the ceramic particles 24 from the heat-insulating layer 20. FIG. 3 shows the addition of the metal coating 30 to the heat-insulating layer 20 of FIG. 2, but of course the same modification can be made also to the embodiment of FIG. 1.
When it is desired to especially enhance the thermal barrier characteristic of a heat-insulating layer 20 according to the invention, an entirely ceramic layer 40 shown in FIG. 4 may be formed on the outer surface of the ceramic-impregnated portion 22. FIG. 4 shows the addition of the ceramic layer 40 to the heat-insulating layer of FIG. 1, but it will be apparent that the ceramic layer 40 can be added in the same manner to the embodiment of FIG. 2, too. Referring to FIG. 5, also it is optional to employ the above described metal coating 30 together with the entirely ceramic layer 40. In this case, too, the metal coating 30 is formed as the outermost portion of the heat-insulating layer 20 as will be apparent from the role of the metal coating 30.
FIG. 6 illustrates the application of the invention to a combustion chamber, i.e. an assembly of a cylinder head 60 formed with a dent 64 in its bottom face and a cylinder block 62 formed with a cylinder bore 66. The dent 64 and an upper portion of the bore 66 constitute the combustion chamber. As is usual, both the cylinder head 60 and the cylinder block 62 are formed primarily by casting. The cylinder head 60 comprises a heat-insulating layer 20A, whose construction may be any one of the constructions described with reference to FIGS. 1-5, arranged such that this layer 20A provides the bottom face of the cylinder head 60 in its dented region. The cylinder block 62 comprises a cylindrically shaped heat-insulating layer 20B according to the invention such that the outer surface of this layer 20B serves as an uppermost portion of the cylindrical wall face of the bore 66.
Referring to FIG. 7, a cast-formed piston 72 to be received in an engine cylinder such as the one in FIG. 6 may comprise a disc-shaped heat-insulating layer 20C according to the invention as a top end portion of the piston 72. The construction of this heat-insulating layer 20C, too, may be any one of those described with reference to FIGS. 1-5.
FIG. 8 shows an exhaust port 74 formed in a cast-formed cylinder head 60A for an internal combustion engine as an exhaust passage connecting a combustion chamber 76 to an exhaust manifold (not shown). Indicated at 78 is a usual exhaust valve. The cylinder head 60A comprises a heat-insulating layer 20D (which may be constituted of several pieces of blocks) according to the invention such that the generally cylindrical wall face of the exhaust port 74 is substantially entirely given by the heat-insulating layer 20D. Also in this case, any one of the constructions of the heat-insulating layer 20 described with reference to FIGS. 1-5 may be employed. Since a major part of the production of a heat-insulating layer according to the invention 20 is completed before casting of the cylinder head 60A which the insertion of the partly ceramic-impregnated block by utilizing a desirably shaped block (20) of a porous metal, there is no difficulty in the application of the heat-insulating layer 20D to the exhaust port 74. Of course, the heat-insulating layer 20D for the exhaust port 74 may be employed in combination with at least one of the heat-insulating layers 20A, 20B, 20C for the combustion chamber and the piston.
As will be understood from the description of the illustrated embodiments, a heat-insulating layer (or layers) according to the invention in an internal combustion engine is highly effective for prevention of unwanted lowering of the exhaust gas temperature either in combustion chambers or in exhaust ports. Therefore, the oxidation of HC and CO in the exhaust gas proceeds during passage of the exhaust gas through the exhaust ports, and the exhaust gas arrives at a thermal reactor or a catalytic converter at temperature high enough to a sufficiently effective function of the reactor or the converter. When the invention is applied to the combustion chambers, it brings about an improvement in the thermal efficiency of the engine as an additional effect.
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A heat-insulating layer secured to a cast metal member of an internal combustion engine so as to be exposed to combustion gas in the engine. A porous or intersticed metal body, preferably having a soft structure, is used as a fundamental material of this layer. A surface portion of the porous metal body is impregnated with a ceramic material, and then the metal body is cast-inserted into the metal member such that the molten metal infiltrates into another surface portion of the porous metal body and that the ceramic-impregnated portion is exposed to combustion gas in the engine. This heat-insulating layer is excellent in toughness, durability and bonding strength and can be embodied in a combustion chamber wall, exhaust port wall or a top portion of a piston.
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FIELD OF THE INVENTION
[0001] The present invention relates to the field of semiconductor device manufacturing. In particular, it relates to the engineering of channel strain in field-effect-transistors through gate replacement and/or selective use of gate material.
BACKGROUND OF THE INVENTION
[0002] In the field of semiconductor device manufacturing, active semiconductor devices such as, for example, transistors are normally manufactured or fabricated by front end of line (FEOL) technologies. A transistor may include, for example, a field-effect-transistor (FET) such as a complementary metal-oxide-semiconductor (CMOS) FET. Among FET transistors may be a p-type doped FET (PFET) or an n-type doped FET (NFET). Different types of FET transistors may be formed or manufactured on a common substrate of semiconductor chip or a common semiconductor structure.
[0003] In order to improve device performance such as operational speed by enhancing carrier mobility in the channel of a FET, following forming the gate structure of the FET, stresses are normally induced into the channel region of the FET through, for example, applying stress liners. A compressive stress liner is normally applied to a PFET transistor and a tensile stress liner applied to an NFET transistor due to different types of carriers. Both stress liners may be formed by following a conventional dual stress liner (DSL) process, or more recently a self-aligned dual stress liner process (SADSL). Other techniques for engineering strain in the channel of a FET may include, for example, embedding silicon germanium (SiGe) in the source/drain regions of a PFET transistor so as to more effectively apply stress towards the channel of the PFET transistor.
[0004] With the continued pursuing for high-performance semiconductor devices, there is a need to further improve the engineering of strain in the channel region of field-effect-transistors. This may include, for example, improving the effectiveness of stress liners and in some instances even in the absence of such stress liners.
SUMMARY OF THE INVENTION
[0005] Embodiments of the present invention provide a method of applying stress to a channel region underneath a gate of a field-effect-transistor, which includes the gate, a source region, and a drain region. The method includes embedding stressors in the source and drain regions; forming a stress liner covering the gate and the source and drain regions; removing a portion of the stress liner, the portion of the stress liner being located on top of the gate; removing at least a substantial portion of the gate of a first gate material and thus creating an opening therein; and filling the opening with a second gate material.
[0006] Embodiments of the present invention further provide a method of, after filling the opening with the second gate material, removing the stress liner that covers the source and drain regions; and a method of, after removing the stress liner covering the source and drain regions, forming a new stress liner covering the gate of the second gate material and the source and drain regions of the FET.
[0007] According to one embodiment, the first gate material may have a Young's modulus value being smaller than 130 GPa, preferably smaller than 115 GPa, and more preferably smaller than 100 GPa. The first gate material may be selected from the group consisting of Si 0.8 Ge 0.2 , SiO 0.5 Ge 0.5 , Ge, GaP, GaAs, Al 0.5 Ga 0.5 As, AlAs, InP, InAs, ZnO, ZnS, ZnSe, CdS, and CdTe. According to another embodiment, the second gate material may have a Young's modulus value being equal to or larger than 130 GPa.
[0008] Embodiments of the present invention provide a method of applying stress to a channel region underneath a gate of a field-effect-transistor, which includes the gate, a source region, and a drain region. The method includes forming the gate of the FET with a gate material, the gate material having a Young's modulus value being smaller than 130 GPa, preferably smaller than 115 GPa, and more preferably smaller than 100 GPa; and forming a stress liner covering the gate and the source and drain regions of the FET.
[0009] Embodiments of the present invention provide a method applying stress to a channel region underneath a gate of a field-effect-transistor. The method includes embedding stressors in a source and drain regions of the FET; forming a stress liner covering a gate of the FET and the source and drain regions; removing a portion of the stress liner that is located on top of the gate; removing the gate of a first gate material and a layer of a first gate oxide underneath, thus creating an opening therein; filling the opening with a layer of a second gate oxide; and filling a second gate material on the layer of said second gate oxide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention will be understood and appreciated more fully from the following detailed description of the invention, taken in conjunction with the accompanying drawings of which:
[0011] FIGS. 1-8 are demonstrative illustrations of a method of forming a field-effect-transistor with gate replacement according to embodiments of the present invention; and
[0012] FIGS. 9-13 are demonstrative illustrations of alternative steps in methods of forming a field-effect-transistor according to embodiments of the present invention.
[0013] It will be appreciated that for the purpose of simplicity and clarity of illustration, elements in the drawings have not necessarily been drawn to scale. For example, dimensions of some of the elements may be exaggerated relative to other elements for clarity purpose.
DETAILED DESCRIPTION OF THE INVENTION
[0014] In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of embodiments of the invention. However, it will be understood by those of ordinary skill in the art that embodiments of the invention may be practiced without these specific details. In the interest of not obscuring presentation of essences and/or embodiments of the present invention, in the following detailed description, processing steps and/or operations that are well known in the art may have been combined together for presentation and/or for illustration purpose and in some instances may not have been described in detail. In other instances, processing steps and/or operations that are well known in the art may not be described at all. A person skilled in the art will appreciate that the following descriptions have rather focused on distinctive features and/or elements of embodiments of the present invention.
[0015] In semiconductor manufacturing industry, various types of active semiconductor devices such as transistors, including CMOS FET of n-type (NFETs) and p-type (PFETs), may be created or formed on a single substrate of semiconductor by applying well-known FEOL processing technologies. The well-known FEOL technologies may include processing steps and/or operations of, inter alia, cap deposition, photo-resist-mask formation, photolithography, hard-mask formation, wet etching, reactive-ion etching (RIE), ion-implantation, and chemical-mechanical polishing (CMP), to list a few. During and/or after the formation of transistors, stress liners of the same or different types may be applied to the transistors, i.e., NFETs and PFETs, for device performance improvement. Improvement in device performance may come from improved mobility of electrons in the channel region of NFETs and/or holes in the channel region of PFETs brought by strains induced by the stress liners.
[0016] In the following detailed description, well-known device processing techniques and/or steps may not be described in detail and, in some instances, may be referred to other published articles or patent applications in order not to obscure the description of the essence of presented invention as further detailed herein below.
[0017] FIGS. 1-8 are demonstrative illustrations of a method of forming a field-effect-transistor with gate replacement according to embodiments of the present invention. For example, FIG. 1 illustrates a step of forming a field-effect-transistor (FET) 100 on a semiconductor substrate 101 . FET 100 may be electrically separated from other FETs or semiconductor devices by shallow trench isolation (STI), e.g., STI 102 , embedded in substrate 101 . The formation of FET 100 may include forming or depositing a dielectric layer 103 , e.g., oxide, on a top surface of substrate 101 ; patterning gate conductor 201 , e.g., polysilicon, on top of dielectric layer 103 ; and embedding stressors 104 , e.g., silicon-germanium (SiGe) or silicon-carbon (SiC), in the source and drain regions next to gate conductor 201 .
[0018] Although not specifically illustrated in FIG. 1 , according to some embodiments of the present invention, the formation of FET 100 may also include other well known steps such as, for example, forming spacers on the two sides of gate conductor 201 , forming source and drain defined by the spacers, forming silicide at the top surfaces of source, drain, and gate for contact, et al. According to some other embodiments, the formation of spacers, source and drain, and/or silicide may be performed at a later stage after the gate replacement process as described below in more details. In any case, in order not to obscure the essence of the present invention, a person skilled in the art may refer to other published articles and/or patents for details of these steps of forming a FET.
[0019] FIG. 2 illustrates a step of forming FET 100 following the step shown in FIG. 1 . Specifically, a stress liner 202 may be subsequently formed on top of FET 100 , which may apply stress toward the channel region of FET 100 underneath gate conductor 201 . Stress liner 202 may be a compressive stress liner, a tensile stress liner, or a dual stress liner. In the case of a p-type doped FET (PFET) 100 , a compressive stress may be applied by stress liner 202 , which may be formed on top of PFET 100 through deposition in a, for example, plasma-enhanced chemical vapor deposition (PECVD) process. Other well-known methods other than PECVD may be used in forming stress liner 202 as well. Stress liner 202 may be a compressive nitride liner or compressive oxide liner. However, a person skilled in the art will appreciate that compressive stress liner may not be limited to nitride liner or oxide liner and other compressive liner materials may be used as well.
[0020] According to one embodiment, in the case of an n-type doped FET (NFET), a tensile stress may be applied by stress liner 202 . According to yet another embodiment, stress liner 202 may have a stress substantially close to zero. In other words, a non-stress liner 202 may be used as well in the process of gate replacement as described below in more detail.
[0021] Assuming FET 100 is a PFET without losing generality, in order to enhance the effectiveness of compressive stress liner 202 in exerting stress in the channel region of FET 100 , according to some embodiment of the present invention, in the previous step ( FIG. 1 ) of forming gate conductor 201 , which may be referred to as a replacement gate or dummy gate, conductive materials with low Young's modulus may be used. For example, polysilicon (Si) is well known as suitable for gate conductor and has a nominal value of Young's modulus around 130 GPa. However, gate conductor material made of a compound of silicon (Si) and germanium (Ge) may have a Young's modulus smaller than that of Si, typically between 103 and 130 GPa. For example, Young's modulus of Si 0.8 Ge 0.2 is around 124 and Si 0.5 Ge 0.5 is around 116, while germanium (Ge) has a Young's modulus value around 103.
[0022] Table 1 lists some of possible candidates for gate conductor. Along with their Young's modulus values, table 1 also provides the respective melting point, mobility factor, and band gap values for each of the candidates.
[0000]
TABLE 1
Candidate material for gate conductor
Young's
Melting
Mobility
Material
modulus (GPa)
point (C.)
factor
Band gap (eV)
Si
130
1412
1
1.12
Si 0.8 Ge 0.2
124
1275
1.05
1.03
Si 0.5 Ge 0.5
116
1109
1.12
0.891
Ge
103
938
1.26
0.661
GaP
103
1457
1.26
2.26
GaAs
85.3
1240
1.52
1.424
Al0.5Ga0.5As
84.4
1351
1.54
1.8
AlAs
83.5
1740
1.56
2.168
InP
61.1
1062
2.13
1.344
InAs
51.4
942
2.53
0.354
ZnO
108
1975
1.20
3.2
ZnS
74.4
1718
1.75
3.54
ZnSe
70
1525
1.86
3.10
CdS
50
1750
2.6
2.42
CdTe
52
1041
2.5
1.56
[0023] A person skilled in the art will appreciate that most of the materials listed in Table 1 have a Young's modulus smaller than that of silicon of 130 GPa. In particular, the listed materials include Si 0.8 Ge 0.2 , Si 0.5 Ge 0.5 , Ge, GaP, GaAs, Al 0.5 Ga 0.5 As, AlAs, InP, InAs, ZnO, ZnS, ZnSe, CdS, and CdTe. Materials with smaller Young's modulus, once used for replacement gate 201 , may exhibit relatively smaller resistance to an external force being applied thereupon, and thus the compressive stress applied by stress liner 202 may be more effectively transferred to the channel region of FET 100 .
[0024] FIG. 3 illustrates a step of forming FET 100 following the step shown in FIG. 2 in order to further strengthen the strain effect brought by stress liner 202 . More specifically, a top portion of stress liner 202 may be removed to expose gate conductor or replacement gate 201 underneath. The removal of stress liner 202 at the top of gate conductor 201 may be through well-known processes such as a chemical-mechanical-polishing (CMP) process, which may create a co-planar surface 202 a, 202 b at the top of stress liner 202 and 201 a at the top of gate conductor 201 . The selective removal of stress liner 202 at the top of replacement gate 201 may cause at least partial relaxation of stresses by stress liner 202 in the direction to enhance the strain effect in the channel region underneath replacement gate 201 . Further relaxation may be obtained in a gate replacement process as described below in more detail, according to embodiments of the present invention.
[0025] FIG. 4 illustrates a step of forming FET 100 following the step shown in FIG. 3 after the top of gate conductor 201 is exposed. The exposed gate conductor 201 may be subsequently removed through, for example, a RIE etching process in which the etchant or etchants used may be selected such that the etching process is selective to the gate conductor material. In other words, the etching of gate conductor 201 may leave nitride stress liner 202 a and 202 b substantially intact. The selection of etchants for performing selective RIE etching is well-known in the art and will not be described in further details. Following the removal of gate conductor 201 , portion of dielectric oxide 103 exposed by the removal of gate conductor 201 may be selectively removed as well to expose the underneath channel region of FET 100 , leaving only layer 103 a under liner 202 a and layer 103 b under liner 202 b. However, embodiments of the present invention are not limited in this respect. For example, according to some embodiments, dielectric oxide layer 103 underneath gate conductor 201 may be left intact or substantially intact, in which case the re-growth of a dielectric oxide layer in the opened gate region (as described below in detail) may not be necessary. In one embodiment, layers 103 a and 103 b may be silicide over source and drain regions 104 as electrical contact for FET 100 .
[0026] According to one embodiment, the removal of gate conductor or replacement gate 201 allows stress liner 202 to further relax, resulting in a more effective transfer of stresses from the two sides of the channel, including those from stress liner 202 and stressor 104 and any other possible sources, to the channel region of FET 100 . Even in the case of a non-stress liner 202 , the removal of replacement gate 201 will still allow stresses from stressor 104 to be transferred to the channel region. It shall be noted that a person skilled in the art will appreciate that stressor 104 may include embedded SiGe, embedded SiC, or any other types of stressors which may be formed by any future technologies.
[0027] FIG. 5 illustrates a step of forming FET 100 following the step shown in FIG. 4 after both gate conductor 201 and dielectric layer 103 underneath have been removed. A new dielectric layer 211 may be formed in the opening directly on top of the channel region. Dielectric layer 211 may be a gate oxide layer.
[0028] FIG. 6 illustrates a step of forming FET 100 following the step shown in FIG. 5 after gate oxide layer 211 is formed. Directly on top of gate oxide layer 211 , a new gate 212 may be formed through for example deposition in the opening between stress liner 202 . Deposition of gate 212 may be followed by a planarization process such as a CMP process to form a surface which may be coplanar with surface 202 a and 202 b. Gate 212 may be a relaxed gate conductor of material such as, for example, polysilicon, tungsten (W), or metal silicide. However, the present invention is not limited in this respect and other type of gate materials may be used as well, including any suitable thin layer being placed between the gate and the gate oxide layer 211 underneath in order to protect the gate oxide.
[0029] FIG. 7 illustrates a step of forming FET 100 following the step shown in FIG. 6 after forming gate 212 . A relaxed nitride diffusion barrier layer 213 may be optionally formed on top of stress liner 202 and gate 212 , thereupon an inter-level dielectric (ILD) layer 214 may be formed as is well known in the art. Diffusion barrier layer 213 may protect ILD layer 214 from contamination from nitride stress liner 202 . In a next step as shown in FIG. 8 , metal contacts 215 and 216 may be formed through well-known etching and deposition process. For example, metal contact 215 may be formed to contact gate 212 and metal contact 216 may be formed to contact source/drain in the embedded SiGe region 104 , possibly through silicide 103 a and 103 b.
[0030] According to an alternative embodiment of the present invention, the gate replacement process as described in FIGS. 2-6 may be applied early in the stage in forming FET 100 , and may be applied in situations where no embedded silicon-germanium is formed in the source/drain regions. For example, as illustrated in FIG. 9 , processing steps as described above may be applied after replacement gate 201 is formed on top of semiconductor substrate 101 via gate dielectric layer 103 . According to this embodiment, after material of replacement gate 201 is removed to form an opening inside stress liner 202 (as shown in FIG. 4 ), stress from stress liner 202 may be transferred effectively to the channel regions in the substrate underneath the opening. However, the present invention is not limited in this respect and any other types of stresses applied by stressors (e.g., stress liner, eSiGe, etc.) from the two sides of replacement gate 201 may be effectively transferred to the channel region of FET 100 after the gate material 201 is removed.
[0031] In FIG. 2 as part of the gate replacement process, stress liner 202 is formed on top of gate 201 (dummy gate or replacement gate), which step is then followed by a planarization (CMP) step to open the top of gate 201 in preparation for the removal of the dummy gate 201 . However, the present invention is not limited in this respect. For example, as illustrated in FIG. 10 , in the case that the thickness of nitride stress liner 202 is less than the height of gate 201 , additional layer or layers, such as an oxide layer 203 , may be formed until the top of gate 201 is covered such that a CMP process may be subsequently applied. Here, a person skilled will appreciate that stress liner 202 may not be limited to nitride stress liner and, so long as stressors (e.g., eSiGe 104 in FIG. 10 ) have been formed at the two sides of replacement gate 201 , stress liner 202 may not be even a stress liner and may be a regular non-stress liner. According to one embodiment, the formation of stress liner 202 may be optional.
[0032] According to one embodiment, following the removal of replacement gate 201 as in FIG. 4 and depending on the stage of forming FET 100 , spacers 204 a and 204 b may be formed on the sidewalls of stress liner 202 in the opening as illustrated in FIG. 11 . Spacers 204 a and 204 b may be tailored to define the width of gate conductor formed therein and away from the source/drain and their extension regions. Following the formation of spacers 204 a and 204 b, dielectric oxide layer 211 and gate conductor 212 may be formed as described in FIGS. 5-6 in between spacers 204 a and 204 b.
[0033] According to another embodiment, following the step as shown in FIG. 6 , the at least partially relaxed (due to the opening) stress liner 202 may be removed selectively, as illustrated in FIG. 12 . In this case, material used in forming gate conductor 212 in step of FIG. 6 may be selected to have a relatively high Young's modulus (for example, equal to or higher than that of polysilicon) such that gate conductor 212 may be able to hold or retain (to certain extent) the strain, which may be caused by the compressive stress of stress liner 202 , in the channel region underneath gate conductor 212 . In other words, the stress in the channel region of FET 100 may be relaxed, if any, to a lesser extent upon the removal of stress liner 202 . Upon forming source/drain and silicide at the source/drain regions, if necessary and not formed previously, a new stress liner 205 may be formed on top of FET 100 as illustrated in FIG. 13 according to yet another embodiment. Stress liner 205 may further strengthen the strain applied to the channel region underneath gate conductor 212 and gate dielectric 211 .
[0034] While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents will now occur to those of ordinary skill in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the spirit of the invention.
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There is disclosed a method of applying stress to a channel region underneath a gate of a field-effect-transistor, which includes the gate, a source region, and a drain region. The method includes steps of embedding stressors in the source and drain regions of the FET; forming a stress liner covering the gate and the source and drain regions; removing a portion of the stress liner, the portion of the stress liner being located on top of the gate of the FET; removing at least a substantial portion of the gate of a first gate material and thus creating an opening therein; and filling the opening with a second gate material.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. patent application Ser. No. 61/657,259, filed Jun. 8, 2012, entitled, “Nanofibrillated cellulose foam containing one or more active ingredients for wound dressing, catalysis, active filtration, and/or other applications,” which is herein incorporated by reference in its entirety.
GOVERNMENT INTEREST
[0002] Governmental Interest—The invention described herein may be manufactured, used and licensed by or for the U.S. Government.
FIELD OF INVENTION
[0003] Embodiments of the present invention generally relate to nanocellulose and, more particularly, to methods of preparing nanocellulose foam containing one or more active ingredients.
BACKGROUND OF THE INVENTION
[0004] Wound dressings may be comprised of films, gels, hydrocolloids and foams. Foam wound dressings may include polyurethane foams, foams of cellulose derivatives and bacterial foams and gels. The inventors have deduced that incorporating one or more active ingredients, such as antibacterial agents and antimicrobial agents, into nanocellulose foams, also referred to as cellulose nanofibril foams, should help promote wound healing.
[0005] Therefore, the inventors have provided improved nanocellulose foams containing one or more active ingredients and methods of preparing such nanocellulose foams containing one or more active ingredients.
BRIEF SUMMARY OF THE INVENTION
[0006] Embodiments of the present invention relate to methods of preparing nanocellulose foam containing one or more active ingredients. In some embodiments, a method of forming a nanocellulose structure may include forming a liquid mixture of nanocellulose, wherein the nanocellulose is dispersed, suspended and/or gelled in the liquid mixture; drying the liquid mixture of nanocellulose to form a nanocellulose foam; and mixing one or more active ingredients into at least one of the liquid mixture of nanocellulose or the nanocellulose foam.
[0007] In some embodiments, a nanocellulose structure may include a nanocellulose foam comprising at least one of a carboxylate group, a hydroxyl group, or a sulfate group bonded to an active ingredient.
[0008] Other and further embodiments of the invention are described in more detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0010] FIG. 1 depicts a flow diagram of a method of preparing nanocellulose foam containing one or more active ingredients in accordance with some embodiments of the present invention.
[0011] FIGS. 2A-2B depicts an illustrative view of a method of preparing nanocellulose foam containing one or more active ingredients in accordance with some embodiments of the present invention.
[0012] FIGS. 3A-3B depict a scanning electron micrograph of nanocellulose foam with silver nanoparticles in accordance with some embodiments of the present invention.
[0013] FIG. 4 depicts FESEM images illustrating the porous network structures of nanocellulose hydrogels.
[0014] FIGS. 5 a through 5 d depict the results of zone of inhibition antimicrobial tests of the nanocellulose hydrogel (a and c) and nanocellulose-Ag hydrogel (b and d) against (a-b) Escherichia coli and (c-d) Staphylococcus aureus.
DETAILED DESCRIPTION OF THE INVENTION
[0015] Embodiments of the present invention include nanocellulose foams containing one or more active ingredients as well as methods of preparing such nanocellulose foams containing one or more active ingredients. Nanocellulose foams in accordance with embodiments of the present invention may advantageously have high surface area, porosity, and absorption and adsorption properties, as well, as biocompatibility and flexible mechanical properties.
[0016] FIG. 1 depicts a flow diagram of a method 100 of preparing a nanocellulose foam containing one or more active ingredients in accordance with some embodiments of the present invention. The method 100 starts at 102 by forming a liquid mixture of nanocellulose by at least one of dispersing, suspending or gelling the nanocellulose in a liquid mixture. Nanocellulose refers to cellulosic fibrils or crystals or whiskers having a diameter of less than 1 micron, preferably less than 100 nm. The length of the nanocellulose may vary from about 10 nm to about 10 microns. The mixture of nanocellulose is formed through mechanical or chemical treatment of a cellulose containing material. In some embodiments the cellulose containing material is oxidized using 2,2,6,6-tetramethylpiperidine-1-oxyl radical (“TEMPO”). In some embodiments, acid hydrolysis, for example sulfuric acid hydrolysis, is used to produce the nanocellulose mixture. In some embodiments, the mechanical treatment is imparted by a mechanical homogenization process with or without enzymatic fractionation. In some embodiments, the cellulose containing material is one or more of wood pulp fibers, plant fibers, tunicate, algae, or ramie. Controlling the concentration of cellulose containing material in the mixture advantageously controls properties of the nanocellulose foam, such as porosity, absorption capacity, flexibility, and active ingredient release rate.
[0017] The nanocellulose produced by TEMPO oxidation is surface functionalized with carboxylate groups. The nanocellulose produced by sulfuric acid hydrolysis is surface functionalized with sulfate groups. The carboxylate groups or sulfate groups or hydroxyl groups of cellulose advantageously allow for the incorporation of a variety of active ingredients to provide a variety of functionalities, as discussed below.
[0018] At 104 , the liquid mixture of nanocellulose is dried to form a nanocellulose foam. In some embodiments, the liquid mixture of nanocellulose is dried using a freeze drying process. For example, in some embodiments, the liquid mixture is frozen in an ethanol/dry ice bath then freeze dried at a pressure of 0.1 mbar. The freeze dried nanocellulose foam has an average pore size diameter of about 1 μm to about 100 μm. The pore sizes may vary from one side of the foam to another side of the foam (e.g., opposing sides). For example, a foam may be formed to have an average pore size of about 50 μm on one side and about 10 μm on another side. Alternatively, the mixture of nanocellulose can be dried using one of a super-critical carbon dioxide (CO 2 ) drying process or a liquid carbon dioxide (CO 2 ) drying process. The nanocellulose foam prepared by super-critical or liquid carbon dioxide drying comprises a pore size in the sub-micron range and a high surface area of about 200 m 2 /g to about 400 m 2 /g.
[0019] At 106 , one or more active ingredients may be added to the nanocellulose. The active ingredient may be mixed into at least one of the liquid mixture of nanocellulose prior to drying 104 (discussed above) or into the nanocellulose foam after drying at 104 . As used herein, an active ingredient is any chemical element, compound or other substance that can be coupled to the nanocellulose to provide additional activity that the bulk nanocellulose does not normally provide, for example pharmaceutical activity or antimicrobial activity. Some suggested active ingredients are described below in detail. In some embodiments, the active ingredient is coupled to the nanocellulose by a physical interaction, such as adhesion, or by a chemical interaction, such as covalent bonding, ionic bonding, or hydrogen bonding, or by a self-assembly process or a by vapor deposition process, or by a layer by layer process.
[0020] In some embodiments, additional materials, such as binders, proteins, surfactants, preservatives, fillers or colorants, may be added to the nanocellulose foam. Such materials can be added to the liquid mixture of nanocellulose prior to drying or to the dried nanocellulose foam. These materials can be coupled to the nanocellulose by physical or chemical interaction.
[0021] In some embodiments, as depicted in FIG. 2A , the active ingredient 202 is mixed into the liquid mixture of nanocellulose 200 to form a liquid mixture of functionalized nanocellulose 204 . The liquid mixture of functionalized nanocellulose 204 is freeze-dried to form functionalized nanocellulose foam 206 . The liquid mixture of functionalized nanocellulose can also be solvent-exchanged into an organic solvent, and then exposed to supercritical CO 2 or liquid CO 2 or freeze-dried to form a functionalized nanocellulose foam.
[0022] In some embodiments, the structure of nanocellulose foam is enhanced by hydrogelation of nanocellulose dispersion with cations before drying process. A few examples of these cations include, but are not limited to, Ca 2+ , Zn 2+ , Cu 2+ , Al 3+ and Fe 3+ , among which Ca 2+ and Fe 3+ are biocompatible. Nanocellulose hydrogels are produced by addition of a metal salt solution to the top of nanocellulose aqueous dispersion. The moduli of thus formed hydrogels correlate well with binding strength of cations with surface carboxylate groups on nanocellulose, as provided in Table 1. FIG. 4 shows interconnected porous networks after supercritical CO 2 drying of cation-induced hydrogels. which were prepared using a method described in example 3
[0023] To include the active ingredients in cation-induced hydrogels, active ingredients can be either added to the liquid dispersion prior to hydrogelation or added to hydrogels after gel formation. For example, proteins that promote wound healing are chemically attached or physically absorbed to the surface of cation-induced hydrogels.
[0024] In some embodiments, nanocellulose gels can be functionalized with chitosan. In one example, nanocellulose beads with chitosan are generated by dropping nanocellulose dispersion into CaCl 2 or other aqueous salt solution, followed by hardening and rinsing with water. Then the nanocellulose beads were incubated with chitosan. In another example, nanocellulose dispersion was dropped into chitosan/CaCl 2 or other aqueous salt solution to form nanocellulose/chitosan beads.
[0025] In some embodiments, the liquid mixture of nanocellulose can be functionalized with silver (Ag) to form a hydrogel. For example, in some embodiments, the hydrogel is generated by adding silver nitrate (AgNO 3 ) to the liquid mixture of nanocellulose. In an exemplary embodiment, a sufficient amount of silver nitrate (AgNO 3 ) is added to the liquid mixture of nanocellulose to ensure complete saturation of carboxylate groups with silver ions. The addition of silver nitrate (AgNO 3 ) results in the gelation of the liquid mixture of nanocellulose. The hydrogel is allowed to sit for a desired period of time in order to promote the slow reduction from silver ions (Ag + ) to silver (Ag) nanoparticles. The hydrogel may be immersed in water to rinse off any unattached silver (Ag) species.
[0026] In some embodiments, to form an aerogel, silver nitrate (AgNO 3 ) is introduced to the liquid mixture of nanocellulose in quantities to remain below the gelation threshold. The functionalized liquid mixture of nanocellulose is then degassed under vacuum to remove air bubbles and freeze dried as described above. To reduce silver ions (Ag + ) to silver (Ag) nanoparticles, the top and bottom sides of the dried aerogels are exposed under a UV lamp for 30 minutes each. FIGS. 3A and 3B depict a scanning electron micrograph of functionalized nanocellulose foam 206 with silver nanoparticles 302 , which shows the pores 300 of freeze-dried foam. The functionalized foam was prepared using a method described in example 2.
[0027] In other embodiments, as depicted in FIG. 2B , the liquid mixture of cellulose nanofibrils 200 is dried prior to adding any active ingredients, in order to form non-functionalized nanocellulose foam 208 . The non-functionalized nanocellulose foam 208 is immersed in an active ingredient 202 -containing solution 210 and dried to form a functionalized nanocellulose foam 206 A.
[0028] For example, in some embodiments, a nanocellulose foam is prepared by adding an acid, such as hydrochloric acid (HCl), to a liquid mixture of nanocellulose resulting in the gelation of the liquid mixture. The non-functionalized nanocellulose hydrogel is removed from the hydrochloric acid (HCl) solution and washed with water several times. The hydrogel can then be dipped in a liquid solution containing an active ingredient, such as silver, and dried as described above to form a functionalized nanocellulose foam 206 A.
[0029] Alternatively, for example, the nanocellulose foam is an aerogel formed by degassing the liquid mixture of nanocellulose under vacuum to remove air bubbles. The liquid mixture of nanocellulose is then freeze dried as described above. The freeze dried nanocellulose aerogel can then be loaded with an active ingredient such as silver ions or silver nanoparticles. In some embodiments, the foam can be particle or bead shapes or in sheet forms.
[0030] In some embodiments, the nanocellulose foam is used as a wound dressing and the selected active ingredient has at least one of antimicrobial properties, antiviral properties, or hemostatic properties. In some embodiments, the nanocellulose foam can have a high porosity, for example, greater than about 99%, such that upon application to the wound, the nanocellulose foam can absorb large amounts of wound fluid exudates. As the nanocellulose foam absorbs fluid, it releases the active ingredient to the wound. For example, in some embodiments, the active ingredient is at least one of a silver species, a copper species, chitosan, an antimicrobial drug, an antibiotic, a pharmaceutical, a vitamin, a mineral, or a diagnostic agent. FIG. 4 demonstrates antimicrobial properties of nanocellulose-Ag hydrogels against tested bacteria. Nanocellulose-Ag hydrogels were prepared using a method illustrated in example 1.
[0031] A variety of active ingredients can be added to the liquid mixture of nanocellulose suitable for use in a variety of industries, such as biomedical, cosmetic, and pharmaceutical. In some embodiments, the active ingredient is advantageously selected to promote a variety of properties, such as adsorption of external materials, permeability of matter or energy, conductivity, catalysis, biological activity, reactivity, electrochemical reactions, or mechanical properties.
[0032] For example, in some embodiments, the nanocellulose foam is a tissue scaffold and the active ingredient is selected to provide stability and attachment for cell growth. In such embodiments, the active ingredient is at least one of collagen, chitosan, hyaluronic acid, or proteins.
[0033] In some embodiments, the active ingredient has high adsorption or absorption properties, which can be useful in applications such as wound dressings or diapers.
[0034] In some embodiments, the active ingredient is selected to bind, trap, or filter target materials in liquid or gas phase effluent, which is useful in applications such as air purification, water sanitization or wastewater treatment.
[0035] In some embodiments, the active ingredient has a high electrical conductivity, which is useful in a variety of applications including but not limited to electronics or protection against stray current (e.g., lightning strike). In such embodiments, the active ingredient is, for example, a metal species such as copper, silver, gold, or platinum, or an electrically conducting polymer, such as polypyrrole, polyaniline, or poly(3,4-ethylenedioxythiophene). In some embodiments, the active ingredient has high electrical resistivity, which is useful in a variety of applications including but not limited to electrical shielding or electronics.
[0036] In some embodiments, the active ingredient has either thermally conductive properties, such as silver, copper or aluminum oxide, or has thermal insulation properties, such as rubber, silica, or polyethylene. Such properties are useful in a variety of applications including but not limited to insulation or thermoelectrics.
[0037] In some embodiments, the active ingredient provides acoustic dampening properties which are useful in a variety of applications including but not limited to sound insulation in buildings.
[0038] In some embodiments, the active ingredient is a non-linear optical material, such as lead pthalocyanine and related derivatives.
[0039] In some embodiments, the active ingredient interacts with electromagnetic waves. In some embodiments, the active ingredient reflects energy in the form of electromagnetic waves, sound, or heat so as to provide a waveguide through the nanostructure, which is useful in a variety of applications.
[0040] In some embodiments, the active ingredient can store energy, which is useful in a variety of applications including but not limited to electrochemical batteries or capacitors. In some embodiments, the active ingredient can undergo oxidative or reductive changes to store ionic or electric charge. In such embodiments, the active ingredient is at least one of a redox-active polymer, such as polyaniline or polypyrrole, a transition metal, such as lithium, cobalt oxide, lithium manganese oxide, or lithium iron phosphate, carbon, such as graphite or carbon nanotubes, silicon, tin, lithium, sodium, lead, or other electrode materials.
[0041] In some embodiments, the active ingredient has chemically active properties. In some embodiments, the active ingredient has catalytic properties. In some embodiments, the active ingredient is a gas-phase catalyst and is selected from a group consisting of a noble metal or a metal alloy catalyst. In some embodiments, the active ingredient is a liquid-phase catalyst and is selected from a group consisting of a noble metal or a metal alloy catalyst.
[0042] In some embodiments, the active ingredient reacts with chemical or biological agents to render them inert, for example, titanium oxide.
[0043] In some embodiments, the active ingredient can react with an external stimulus, such as increased temperature or an applied voltage to generate a detectable chemical, mechanical, or electrical signal, which is useful in a variety of sensor applications.
[0044] In some embodiments, the active ingredient has mechanical properties that change based on external stimuli.
[0045] In some embodiments, the active ingredient has magnetic properties, which is useful in a variety of applications including but not limited to electric generators or data recording. In such embodiments, the active ingredient is, for example, at least one of a ferrite or a rare-earth-element-based complex such as samarium-cobalt or an alloy of neodymium, iron and boron.
EXAMPLE 1
[0046] Nanocellulose-Ag hydrogels were generated by addition of AgNO 3 aqueous solution to an aqueous dispersion of carboxylated nanocellulose followed by reduction. Typically, nanocellulose dispersion was put into a container. An equal volume of 50 mM AgNO 3 solution was added dropwise along the sidewall into the 1 wt % nanocellulose dispersion without stirring. Gelation occurred rapidly upon the addition of AgNO 3 . The gel sat for five days to allow for slow reduction of Ag + to Ag nanoparticles. UV reduction as an alternative method could also be used to convert Ag + to Ag nanoparticles. A brown gel thus formed was removed from the AgNO 3 solution, and immersed into water several times to rinse off the unattached Ag species.
EXAMPLE 2
[0047] A freeze-drying method was used to prepare nanocellulose-Ag aerogels. The molar amount of AgNO 3 added to the 1 wt % nanocellulose dispersion was calculated on the basis of the dried nanocellulose weight. Low quantities were desired to remain below the gelation threshold. To 40 g of nanocellulose aqueous dispersion, the calculated amount of AgNO 3 corresponding to 0.2 mmol or 0.5 mmol Ag + per gram of dried nanocellulose was dissolved in 1 mL of H 2 O and added dropwise under vigorous stirring. After continuously stirring for 30 min, the aqueous dispersion was degassed quickly under vacuum. 8 grams of each sample were put in a glass freeze-drying vial and immersed in an ethanol/dry ice bath. An ethanol/dry ice bath was preferred over liquid N 2 for freezing the NFC dispersion as it was found to generate fewer cracks in the aerogel structures. The frozen dispersion was then freeze-dried at a pressure of 0.1 mbar in a FreeZone freeze dry system. The drying was typically finished within 12-24 h. To reduce Ag + to Ag nanoparticles, the dried aerogels were exposed under a UV lamp (λ=320-395 nm) 30 min each for the top side and the bottom side.
EXAMPLE 3
[0048] Nanocellulose hydrogels were produced by addition of a metal salt solution to the top of aqueous dispersion of carboxylated nanocellulose. A certain weight of 1 wt % nanocellulose dispersion was put in a container. An equal weight of a 50 mM aqueous solution of metal salt, such as CaCl 2 or FeCl 3 , was added dropwise along the wall of the container into the CNF dispersion without stirring. Gelation occurs upon the addition of the metal salt solution. After standing for overnight, the metal salt solution was decanted, the resulting hydrogel was soaked and rinsed with water several times to remove unbounded metal ions. For the hydrogel generated with FeCl 3 , a yellow gel formed after addition of 50 mM FeCl 3 . t, the gel of CNF—Fe 3+ was rinsed with water of pH 3 before rinsing with neutral water.
[0049] The hydrogels in example 1 and 3 were dried either by freeze-drying using similar conditions as described in example 2 or by sc-CO 2 drying after solvent exchanged with acetone.
EXAMPLE 4
[0050] 1 wt % nanocellulose dispersion was pumped through a syringe into a gelling bath that contained an aqueous solution of 50 mM CaCl 2 solution. The gel beads were allowed to harden in the gelling bath for 1 hour, and then rinsed with water. The gel beads were then incubated with buffered chitosan solution for overnight.
[0051] Other details and/or embodiments may be described in a journal article titled” Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles” Carbohydrate Polymers 95 (2013 760-767) which is hereby incorporated by reference.
[0052] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof.
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Nanocellulose foams containing at least one active ingredient and methods of preparing such nanocellulose foams containing one or more active ingredients are provided herein. In some embodiments, a method for preparing nanocellulose foam containing active ingredients may include forming a liquid mixture of nanocellulose, wherein the nanocellulose is at least one of dispersed, suspended or gelled in the liquid mixture; drying the liquid mixture of nanocellulose to form a nanocellulose foam; and mixing at least one active ingredient into at least one of the liquid mixture of nanocellulose or the nanocellulose foam. In some embodiments, a nanocellulose structure may include a nanocellulose foam comprising at least one of a carboxylate group, a hydroxyl group, or a sulfate group bonded to an active ingredient. In some embodiments, the nanocellulose structures are enhanced or crosslinked with metal cations.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to liquid crystal displays (LCDs), and particularly to an LCD with in-plane switching (IPS) mode and providing a highly precise alignment of liquid crystal molecules therein.
[0003] 2. General Background
[0004] Conventional chip packages such as leadframe-based Chip Scale Packages (CSPs) are soldered onto PCBs using solder paste. Leadframe-based CSPs are CSPs having no peripheral leads that typically extend out from chip packages. A conventional leadframe-based CSP includes a leadframe divided into a die attach. pad centrally located therein and a plurality of wire bonding pads peripherally located therein. The conventional leadframe-based CSP further includes one or more dies or chips mounted on the die attach pad, bonding wires for electrically connecting the dies to the wire bonding pads, and a mold compound for encapsulating all these components in a package structure. A variety of different types of leadframe-based CSPs are available in the market, such as Micro-Lead Packages (MLPs), Micro-Lead-Frames (MLFs), Leadless Package Chip Carriers (LPCC), etc. Joint Electron Device Engineering Counsel (JEDEC), which is a committee for establishing industry standards and packaging outlines, has defined a package outline named “MO-220” for leadframe-based CSPS.
[0005] A typical PCB is made of conductive layers and dielectric layers stacked up in an alternating manner. The top conductive layer on the PCB is divided into a center pad centrally located therein and a plurality of I/O (input/output) pins peripherally located therein. Typically, solder paste is deposited on certain portions of the center pad and the I/O pins. An electronic package such as a leadframe-based CSP is then placed onto the PCB and fixedly mounted thereon by solder paste. During the mounting of the leadframe-based CSP, the die attach pad of the leadframe-based CSP is aligned with the center pad of the PCB and the wire bonding pads of the leadframe-based CSP are aligned with the I/O pins of the PCB.
[0006] As shown in FIG. 5 and FIG. 6 , a typical PCB is disclosed. The PCB 100 includes a substrate 110 , a circuit 130 centrally located thereon and a plurality of I/O pins 120 peripherally located thereon. The plurality I/O pins 120 are rectangular copper foil, which are parallel to each other, extending along a first extending direction. The plurality I/O pins 120 is connected to the circuit 130 for electrically connecting the circuit 130 with an outer PCB or other outer elements.
[0007] FIG. 6 is a partially enlarged, cross-sectional view of the PCB of FIG. 1 , taken along a line VI-VI. The plurality of pins 120 formed on the substrate 110 has a plurality of guiding textures 121 , and a soldering flux 122 covering an external surface of the pins 120 . The soldering flux 122 is generally made from tin or anisotropic conductive film. The guiding texture 121 extends along the first extending direction of the pins 120 , which is used to guide the flowing direction of the melting soldering flux 122 when an outer element is soldered on the pins 120 . The guiding texture 121 can prevent short circuit between two adjacent pins 120 , which is influenced by overflow of the melting soldering flux 122 from two sides of the pins 120 .
[0008] However, some superfluous melting soldering flux 122 flows to tail ends of the pins 120 or concentrates at the tail end to form a solder ball, under a pressure thereon produced in the process of bonding the outer elements on the PCB 100 . Thus, a short circuit is easy to produce when the soldering flux 122 is thicker or a pitch between two adjacent pins 120 is small (as shown in FIG. 7 ).
[0009] Thus, what is needed is an improved PCB which can overcome the above-mentioned disadvantages.
SUMMARY OF THE INVENTION
[0010] An exemplary printed circuit board has a substrate; a circuit on the substrate; and a plurality of pins peripherally located on the substrate, electrically connected to the circuit. The printed circuit board further has a plurality of accommodating spaces formed at the plurality of pins.
[0011] Another exemplary printed circuit board has a substrate; a circuit on the substrate; and a plurality of pins peripherally located on the substrate, electrically connected to the circuit. The printed circuit board further has at least one opening are formed at the plurality of pins.
[0012] Other objects, advantages and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a plane view of a PCB in accordance with a first preferred embodiment of the present invention;
[0014] FIG. 2 is a partially enlarged cross-sectional view of the PCB of FIG. 1 taken along a line II-II;
[0015] FIG. 3 is a plane view of a PCB in accordance with a second preferred embodiment of the present invention;
[0016] FIG. 4 is a plane view of a PCB in accordance with a third preferred embodiment of the present invention;
[0017] FIG. 5 is a plane view of a conventional PCB;
[0018] FIG. 6 is a partially enlarged cross-sectional view of the PCB of FIG. 5 . taken along a line VI-VI; and
[0019] FIG. 7 is plane view of the PCB of FIG. 5 , showing a short circuit phenomenon.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] Hereinafter, a preferred embodiment of the present invention will be explained in more detail with reference to the accompanying drawings.
[0021] Referring to FIG. 1 , a plane view of a PCB according to a preferred first embodiment of the present invention is shown. FIG. 2 is a partially enlarged, cross-sectional view of the PCB of FIG. 1 , taken along a line of II-II. The PCB 200 has a substrate 210 , a circuit 230 centrally located thereon and a plurality of I/O pins 220 peripherally located thereon. The plurality I/O pins 220 are rectangular copper foil, which are parallel to each other, extending along a first extending direction. Two adjacent pins 220 are insulated. The plurality I/O pins 220 are connected to the circuit 130 for electrically connecting the circuit 230 with an outer element.
[0022] The plurality of pins 220 formed on the substrate 210 has a plurality of guiding textures 221 formed at an external surface of the pins 220 , a soldering flux 222 covering the external surface, and an accommodating space 223 at a tail end of each pin 220 . The soldering flux 222 is generally made from tin or anisotropic conductive film. The guiding texture 221 extends along the first extending direction of the pins 220 , which is used to guide the flowing direction of the melting soldering flux 222 when an outer element is soldered on the pins 220 . The accommodating space 223 is a depressed portion at the tail end of the pins 220 , which has a deepness same to a thickness of the pins 220 .
[0023] In use, when an outer element is bonded on the pins 220 of the PCB 200 , the guiding textures 221 guide the melting soldering flux 222 flowing along the first extending direction of the guiding textures 221 . The guiding texture 221 can prevent overflow of the melting soldering flux 222 from two sides of the pins 220 , and avoid short circuit between two adjacent pins 220 or forming soldering ball or forming soldering joints. And, superfluous melting soldering flux 222 can flow in the accommodating space 223 . Thus, amount of the superfluous melting soldering flux 222 can be lessened, and the probability of producing the short circuit can be lowered.
[0024] FIG. 3 shows a PCB according to a second preferred embodiment of the present invention. The PCB 300 has a similar structure to that of the PCB 200 except that an accommodating space 323 is formed at a center region of pins 320 , which is a concave hole or a through hole. In use, when an outer element is bonded on the pins 320 of the PCB 300 , a plurality of guiding textures 321 of the pins 320 guide the melting soldering flux (not shown) flowing along the first extending direction of the guiding textures 321 . The guiding texture 321 can prevent overflow of the melting soldering flux from two sides of the pins 320 , and avoid short circuit between two adjacent pins 320 or forming solder ball. And, superfluous melting soldering flux can flow in the accommodating space 323 . Thus, amount of the superfluous melting soldering flux can be lessened, and the probability of producing the short circuit can be lowered.
[0025] FIG. 4 shows a PCB according to a third preferred embodiment of the present invention. The PCB 400 has a similar structure to that of the PCB 200 except that a first accommodating space 423 and a second accommodating space 424 are formed. The first accommodating space 423 is formed at a tail end of each pin 420 , which is a depressed portion, and the second accommodating space 424 is formed at a center region of each pin 420 , which is a concave hole. In use, when an outer element is bonded on the pins 420 of the PCB 400 , a plurality of guiding textures (not labeled) of the pins 420 guide the melting soldering flux (not shown) flowing along the extending direction of the guiding textures. The guiding texture can prevent overflow of the melting soldering flux from two sides of the pins 420 , and avoid short circuit between two adjacent pins 420 or forming solder ball. And, superfluous melting soldering flux can flow in the accommodating spaces 423 , 424 . Thus, amount of the superfluous melting soldering flux can be lessened, and the probability of producing the short circuit can be lowered.
[0026] In various alternate modifications, the accommodating space can be formed at other positions of the pins. Each pin can have one or two or more than three accommodating space. The deepness of each pin can be equal to or higher than or lower than the thickness of corresponding pin.
[0027] It is to be understood, however, that even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and function of the invention, the disclosure is illustrative only, and changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.
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An exemplary printed circuit board ( 200 ) has a substrate ( 210 ); a circuit ( 230 ) on the substrate; and a plurality of pins ( 220 ) peripherally located on the substrate, electrically connected to the circuit. The printed circuit board further has a plurality of accommodating spaces ( 223 ) formed at the plurality of pins.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is based upon and claims priority from prior Provisional Patent Application No. 60/532,208, filed on Dec. 22, 2003, the entire disclosure of which is herein incorporated by reference.
FIELD OF THE INVENTION
The present invention generally relates to the field of dish and food covers, and more particularly relates to a device for covering dishes and food during microwave cooking.
BACKGROUND OF THE INVENTION
When food is heated in a microwave, water molecules within the food become excited resulting in a build up of pressure. This pressure escapes from the food in the form of steam. Frequently, the release of steam is sudden, like an eruption, which causes food to splatter. Therefore, whenever food is heated in a microwave, it should be covered with a microwave transparent material to prevent splattering food particles from soiling the interior of the microwave.
U.S. Pat. No. 4,801,773 to Hanlon discloses a protective cover for a dish being heated in a microwave oven. The cover is formed of moisture-absorbent, microwave transparent material forming a top member and an encircling wall member depending downwardly form the periphery of the top member to completely cover the dish to protect the interior of the oven from any possible spattering of food particles during the heating. The cover is formed of absorbent material so that any escaping fluids and food particles may be captured or absorbed by the cover. The wall member is fluted to give the cover self-supporting rigidity, and an upper edge of each fluted portion coincides with a scalloped portion of the top member. The cover may be treated with a microwave safe resin to increase the rigidity of the cover.
U.S. Patent Publication No. 20030205575 discloses a device for preventing food splatter during microwave cooking which includes a sheet of material capable of maintaining a crease, and which has at least one crease that extends across the sheet. The device is positioned over food disposed on an open dish with the crease extending across the dish and with the crease being at an apex of the sheet while the food is heated in a microwave oven. The invention provides a convenient, easy to use and inexpensive device and method for preventing food splatter during microwave cooking of food in an open container such as a plate or bowl.
U.S. Pat. No. 5,126,520 to Nottingham et al discloses a shielded cover for a microwave container having upper and lower layers and a diamond-shaped metallic ring therebetween. The ring surrounds an upwardly extending multi-step truncated pyramid formed out of the center section of the upper and lower layers of the cover. The top surface of the truncated pyramid includes a series of openings to vent steam produced within the container. Microwave radiation produced by the microwave oven is reflected by the metallic ring and therefore only penetrates the cover to enter or exit the container at the corners and the center section of the cover. Microwaves are concentrated at the center section of the container and retained within the container, heating the center of the food therein proportionally more than the outer portion of the food, resulting in food having a uniform and consistent temperature throughout.
U.S. Pat. No. 4,748,303 to Drews discloses a microwave toaster including a rectangular block of microwave transparent material having a plurality of parallel and aligned slots therein for receiving cards of material which absorb microwave energy and subsequently dissipates heat therefrom. A piece of bread is positioned next to the material to absorb the heat dissipated therefrom for subsequently turning into browned toast.
Finally, WO 00/69222 to Davis discloses a fabric composite for microwave cooking. A composite of textile materials enhances both insulation and ventilation when formed as an enclosure or a cover for articles, and has particular utility for microwave cooking. The fabric composite includes multiple layers. One layer is a top insulative layer which has a multiplicity of pores therein, which may be voids which are present in a woven textile material. A mesh layer is attached to the insulative layer. The mesh layer has a multiplicity of pores which are formed therein. The mesh layer is formed of a non-porous fiber. One layer provides insulation to hold heat within the container or another article, while the mesh layer retards splattering. The composite allows steam ventilation from the container without the requirement of lifting a corner of the cover or enclosure from the container, or otherwise taking steps to provide ventilation. The fabric composite is machine washable.
Existing food covers do not provide consumers or users with a sanitary, easy-to-use product for microwave cooking. Many existing covers have a porous, mesh, or non-smooth surface facing the food which becomes contaminated with splattered food. If not properly and thoroughly cleaned, these non-smooth surfaces become havens for bacteria and germs. Also, many existing covers absorb liquid or moisture from steam which also creates an unsanitary condition as well as making the cover messy to handle. Furthermore, some existing covers are rigid and bulky making them difficult to wash in a dishwasher and inconvenient for storage.
Accordingly, there exists a need for overcoming the disadvantages of the prior art as discussed above.
SUMMARY OF THE INVENTION
According to an embodiment of the present invention, a device for covering food during microwave heating includes a microwavable flexible sheet having a substantially smooth, food-facing surface that is free of openings. The microwave sheet has a configuration and weight distribution for draping the sheet over food on a food-containing rigid structure such that the sheet contacts a portion of an outer perimeter of the food-containing rigid structure creating a partial enclosure around the food. During microwave heating, the partial enclosure around the food substantially contains food-splattering inside while allowing build-up of steam to escape through an opening between the sheet and the portion of the outer perimeter of the food-containing rigid structure.
In an exemplary embodiment, the microwave sheet is made of plastic material, such as polyethylene. The microwave sheet has a gauge in the range of about 1 mil to approximately 12 mil.
Further, according to another embodiment of the present invention, a device for covering food during microwave heating includes a microwavable flexible sheet having a substantially smooth, food-facing surface that is free of openings. The microwave sheet has a configuration and weight distribution for draping the sheet over food on a plate such that the sheet contacts an edge of the plate creating a cover over the food. During microwave heating, the cover substantially contains food-splattering while allowing build-up of steam to escape through an opening between the sheet and the edge of the plate.
In an exemplary embodiment, the microwave sheet has a perimeter portion. Optionally, the perimeter portion includes a fold or bevel. Also, optionally, the gauge or weight of the perimeter portion of the sheet is greater than a gauge or weight of an interior portion of the sheet. Alternatively, the perimeter portion includes microwaveable weights.
Moreover, according to another embodiment of the present invention, an apparatus for heating food in a microwave includes a microwavable container for containing food and a microwavable steam-impermeable sheet having a configuration and weight for draping the sheet over the microwavable container to form a cover over the food. During microwave heating, the cover substantially contains food-splattering while allowing build-up of steam to escape through an opening between the sheet and the container.
In an exemplary embodiment, the microwave sheet includes attachment means for connecting the sheet to a food container. Optionally, the sheet is removably attached to the container. Alternatively, the microwave sheet is rotationally attached to the food container.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying figures, where like reference numerals refer to identical or functionally similar elements throughout the separate views and which together with the detailed description below are incorporated in and form part of the specification, serve to further illustrate various embodiments and to explain various principles and advantages all in accordance with the present invention
FIG. 1 is a perspective view showing a microwave sheet according to an embodiment of the present invention;
FIG. 2 is a cross-sectional view showing a microwave sheet having a plurality of layers;
FIG. 3 is a cross-sectional view showing a microwave sheet in use within a microwave oven;
FIG. 4 is a cross-sectional view showing a microwave sheet in use having a heavier-weighted perimeter portion;
FIG. 5 is a cross-sectional view showing a microwave sheet in use having a perimeter portion with microwaveable weights;
FIG. 6 is a perspective view showing a microwave sheet having a folded perimeter portion; and
FIG. 7 is a cross-sectional view showing a microwave sheet in use having an attachment means.
DETAILED DESCRIPTION
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 can 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. Further, the terms and phrases used herein are not intended to be limiting; but rather, to provide an understandable description of the invention.
The terms “a” or “an”, as used herein, are defined as one or more than one. The term plurality, as used herein, is defined as two or more than two. The term another, as used herein, is defined as at least a second or more. The terms including and/or having, as used herein, are defined as comprising (i.e., open language). The term coupled, as used herein, is defined as connected, although not necessarily directly, and not necessarily mechanically.
According to an embodiment of the present invention, as shown in FIG. 1 , a microwave sheet 100 is flexible single sheet of microwaveable material. The microwave sheet 100 includes at least one substantially smooth, food-facing surface 102 which is free of openings. The sheet 100 has a configuration and sufficient weight to be draped over food and/or over a food-containing structure to create at least a partial enclosure around the food.
When placing the microwave sheet 100 over a dish, the substantially smooth surface 102 of the sheet faces the food so that any food or splattering food which contacts the smooth, food-facing surface 102 can be easily removed. Optionally, the smooth, food-facing surface 102 of the sheet 100 is non-porous for easier removal of food and other contaminants. In one embodiment, the microwave sheet 100 is reusable by cleaning the sheet in a dishwasher or by hand. Alternatively, the microwave sheet 100 is disposable.
According to one exemplary embodiment, the microwave sheet 100 includes a plastic material which is substantially microwave transparent. Such plastic material is polyester, polyethylene, or similar material. The thickness or gauge of the material is sufficiently light to allow the microwave sheet to be draped over food. Additionally, the material is sufficiently heavy to prevent the microwave sheet 100 from being blown off by steam and splattering food without the sheet clinging to or being attached to the food-containing dish. In an exemplary embodiment, the material of the microwave sheet 100 has a gauge in the range of approximately 1 mil to about 12 mil.
A variety of configurations of the microwave sheet 100 permits various food-containing dishes to be adequately covered during microwave use. Appropriate configurations for the microwave sheet 100 include circular, square, rectangular, triangular, octagonal, hexagonal, and similar configurations.
FIG. 2 illustrates another exemplary embodiment of a microwave sheet 200 . The microwave sheet includes two layers of material 202 and 204 . The bottom layer 202 of the microwave sheet 200 includes a plastic material and has at least one substantially smooth surface 206 for contacting or facing food. The top layer 204 also includes a material that is substantially microwave transparent. For example, the top layer 204 includes a fabric material to insulate the microwave sheet 200 . In another example, the top layer 204 includes a plastic, ceramic, or composite material.
Referring to FIG. 3 , an exemplary embodiment of a microwave sheet 300 is shown in use within a microwave oven 302 . The microwave sheet 300 is draped over food 306 on a rigid structure, such as a plate 304 . Other examples of a rigid structure include a bowl, a cup, a dish, a saucer, and other similar objects. Examples of food include liquid and solid foods. The substantially smooth surface 316 of the sheet 300 faces the food 306 . When draped over food 306 , the microwave sheet 300 contacts the outer edge of the plate 304 to form a partial enclosure over the food 306 . The microwave sheet 300 rests on the plate 304 such that at least one passage 310 is formed between the sheet 300 and plate 304 .
As the microwave 302 heats the food 306 , steam 312 is produced and rises from the food 306 . The steam 312 is prevented from passing through the microwave sheet 300 since the sheet 300 is free of openings. Instead, steam 312 exits from under the enclosure through at least one passage 310 formed between the microwave sheet 300 and outer edge of the plate 304 . Furthermore, the microwave sheet 300 prevents splattering food 308 from soiling the interior of the microwave 302 . The sufficient weight of the microwave sheet 300 prevents the sheet 300 from being blown off by the splattering food 308 and rising steam 312 .
According to another exemplary embodiment, as illustrated in FIG. 4 , a microwave sheet 400 of the present invention includes at least a portion of an outer perimeter 414 which is thicker or has a greater gauge than an inner portion of the sheet 400 . The increased-gauge or heavier outer perimeter 414 provides additional means for holding the microwave sheet 400 in place when splattering food 408 and steam 412 are rising from the food 406 being heated in the microwave. In one embodiment, the thicker or heavier outer perimeter 414 extends around the entire microwave sheet 400 .
In use, the microwave sheet 400 of FIG. 4 is draped over food 406 in a dish or bowl 404 . The microwave sheet 400 rests on the edges of the bowl 404 and forms passages 410 between the sheet 400 and bowl 404 . The heavier-gauged or thicker outer perimeter 414 of the microwave sheet 400 helps hold the sheet 400 over the food 406 . When the food 406 is being heated by the microwave, steam 412 rises from the food 406 and escapes from under the microwave sheet 400 through the passages 410 . Furthermore, splattering food 408 is caught or stopped by the smooth, food-facing surface 416 of the microwave sheet 400 .
According to another exemplary embodiment, as illustrated in FIG. 5 , a microwave sheet 500 of the present invention includes at least one weight 518 on the outer perimeter 514 of the sheet 500 . The at least one weight 518 provides additional means for holding the microwave sheet 500 in place when splattering food 508 and steam 512 are rising from the food 506 in the microwave. The weight 518 includes a substantially microwave transparent material, such as plastic, rubber, ceramic, composite, or similar material. In one embodiment, a plurality of weights 518 is disposed around the outer perimeter 514 of the sheet 500 . For example, the plurality of weights 518 is placed generally equidistant around the outer perimeter 514 .
In use, the microwave sheet 500 of FIG. 5 is draped over food 506 in a dish or bowl 504 . The microwave sheet 500 rests on the edges of the bowl 504 and forms passages 510 between the sheet 500 and bowl 504 . The weights 518 on the outer perimeter 514 of the microwave sheet 500 help hold the sheet 500 over the food 506 . When the food 506 is being heated by the microwave, steam 512 rises from the food 506 and escapes from under the microwave sheet 500 through the passages 510 . Furthermore, splattering food 508 is captured by the smooth, food-facing surface 516 of the microwave sheet 500 .
Referring to FIG. 6 , another exemplary embodiment of the present invention is illustrated. The microwave sheet 600 includes at least one fold 602 in the outer perimeter 614 of the sheet 600 . In one embodiment the fold 602 is disposed within the outer perimeter 614 during manufacturing of the sheet 600 . In another embodiment, the fold 602 is placed in the outer perimeter 614 by the consumer or user of the microwave sheet 600 . In an exemplary embodiment, a plurality of folds 602 is disposed in the outer perimeter 614 of the microwave sheet 600 . For example, the plurality of folds 602 is spaced equidistantly around the outer perimeter 614 to form a beveled perimeter.
In use, the microwave sheet 600 of FIG. 6 is draped over food in a dish or bowl 604 and rests on the edges of the bowl 604 . The folds 602 form passages 610 between the sheet 600 and bowl 604 . When the food is being heated by the microwave, steam 612 rises from the food and escapes from under the microwave sheet 600 through the passages 610 . Furthermore, splattering food is caught or stopped by the smooth, food-facing surface 616 of the microwave sheet 600 .
According to another exemplary embodiment, as illustrated in FIG. 7 , a microwave sheet 700 of the present invention includes at least one attachment means 718 for connecting the microwave sheet 700 to a plate, bowl, dish, or similar object 704 . Such an attachment means 718 includes a hinge, a clip, Velcro®, adhesive, a latch, or other suitable means. In one embodiment, the microwave sheet 700 is rotationally attached to a dish 704 . In another embodiment, the sheet 700 is removably connected with the dish 704 .
In use, the microwave sheet 700 with an attachment means 718 as described above is placed over food 706 in a dish 704 . An attachment means 718 connects one side of the microwave sheet 700 to the dish 704 . As the microwave sheet 700 rests on the edge of the dish 704 , a passage 710 is formed allowing steam 712 to escape from under the sheet 700 . The smooth, food-facing surface 716 of the microwave sheet 700 also prevents splattering food 708 from soiling the interior of the microwave.
Although specific embodiments of the invention have been disclosed, those having ordinary skill in the art will understand that changes can be made to the specific embodiments without departing from the spirit and scope of the invention. The scope of the invention is not to be restricted, therefore, to the specific embodiments, and it is intended that the appended claims cover any and all such applications, modifications, and embodiments within the scope of the present invention.
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A device for covering food ( 306 ) during microwave heating includes a microwavable flexible sheet ( 100 ) having a substantially smooth, food-facing surface ( 102 ) that is free of openings. The sheet ( 100 ) has a configuration including size, shape, and weight distribution for flexibly draping the sheet ( 100 ) over the food ( 306 ) on a rigid structure ( 304 ) such that the flexibly draped sheet ( 100 ) overhangs and folds loosely over an outer perimeter of the rigid structure thereby forming at least a partial enclosure around the food ( 306 ) when the sheet contacts at least a portion of an outer perimeter of the food-containing rigid structure ( 304 ). During microwave heating, the at least a partial enclosure around the food ( 306 ) substantially contains food-splattering ( 308 ) inside while allowing steam ( 312 ) to escape through an opening ( 310 ) formed between the flexibly draped sheet ( 100 ) and the outer perimeter of the rigid structure ( 304 ).
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BACKGROUND OF THE INVENTION
The present invention relates to a device for receiving a series of individual articles, placing those articles in a stack, and packaging the stack in a tray or container on a continuous basis. The device is further contemplated to be capable of varying the size of the stack.
SUMMARY OF THE INVENTION
The present invention relates to a device for stacking a series of articles, such as cookies, and packaging the stack in a tray or container. The invention is specifically contemplated to be capable of varying the size of the stack, as desired.
The contemplated invention is positioned at the end of a conveyer which consecutively feeds articles towards a stacking area. Within the stacking area is provided a stacking wheel which includes a series of dividers that project radially outwardly from the circumference thereof. As the articles move along the feed conveyer, they pass underneath a counter. The counter upon passage of each article, sends a signal to a drive motor that causes an incremental rotation of the stacking wheel. As each article is moved off of the conveyer belt, it is positioned on the top of the stack formed on one of the dividers. The incremental rotation of the wheel places the top of the stack in its proper position for receipt of the next article. The dividers are spaced equally from one another on the periphery of the stacking wheel such that a constant number of articles are provided within each stack. The stack, upon completion is moved to a packing area at the bottom of the wheel rotation.
Adjusting the size of the stack is accomplished by varying the spacing between the dividers projected from the stacking wheel. In a preferred embodiment, the stacking wheel is provided with a plurality of dividers located around the circumference having an equivalent spacing therebetween. Adjustment is accomplished by projecting only a preset group of dividers. The projection of the group is controlled by air actuated cylinders, magnetic means or the like. A multiple number of preset arrangements of dividers is contemplated in order to provide a multiple number of stacking relationships. The selection of one group of dividers, corresponding to the size of the stack, may be programmed along with an incremental adjustment of the drive motor for the stacking wheel.
Another feature contemplated by the present invention is a means for placing the stack of articles into its packaging. Upon rotation of the stack of articles to the bottom of the stacking wheel, the stack has been shifted approximately 90° in orientation. A first sliding plate moves out from under the stack and the stack falls into a retaining area. Upon passage of the stack into the retaining area, squeezing elements move slightly together to compress the stack and to realign the individual articles therein. Thereafter, a second sliding plate is moved out from under the retaining area and the articles fall into a container positioned therebelow.
It is contemplated that the stacking and packaging device will operate continuously. If it is desired to change the type or size of the articles being fed into the stacking area or if it is desired to change the size of the stack, the stacking wheel and packaging device may be adjusted to define the desired stack size and package orientation.
BRIEF DESCRIPTION OF THE DRAWINGS
For the purpose of illustrating the invention, there is shown in the drawings a form which is presently preferred; it being understood, however, that this invention is not limited to the precise arrangements and instrumentalities shown.
FIG. 1 shows a cross-sectional view of an apparatus in accordance with the present invention.
FIG. 2 shows a top plan view of the apparatus shown in FIG. 1.
FIG. 3 shows a cross-sectional view of the apparatus as taken along line 3--3 in FIG. 1.
FIG. 4 shows a partial cross-sectional view of the apparatus of the present invention.
FIG. 5 shows an alternate view of the portion of the invention shown in FIG. 4.
DETAILED DESCRIPTION OF THE INVENTION
In the figures where like numerals indicate like elements, there is shown a stacking and packaging apparatus as generally designated by the numeral 10. The apparatus 10, as generally illustrated in FIG. 1, comprises a stacking wheel portion 12 and a packaging portion 14. Operating in conjunction with the stacking wheel 12 and the package device 14 is a feed conveyer 16 and an exhaust conveyer 18. The feed conveyer 16 generally supplies a series of articles in succession towards the stacking wheel 12. The feed conveyer represents the output of a continuous production device (not shown) for articles 20, such as cookies. Positioned at the end of the feed conveyer 16 is the stacking area 22. The stacking area 22 generally comprises the end of feed conveyer 16, an electronic counter 24, and an extending projection or divider 26 located on the stacking wheel 12.
As the articles 20, positioned in a space relationship along the feed conveyer, are moved towards the stacking area 22, each passes under the counter 24. The counter 24 may be an optical type sensor which reacts to the presence of an article on the surface of a, preferably white, conveyor belt. The passage of an article 20 under the counter 24 causes a signal to be sent to a control means 32. The control means 32 in turn sends a signal to a drive motor 29, illustrated in FIG. 2. The drive motor 29 is contemplated to be a servo type motor which causes precise incremental rotation of the stacking wheel 12 in a counterclockwise direction (as seen in FIG. 1). The article 20 is then passed off of the end of the conveyor 16 and onto the divider 26 or, if articles have already been stacked thereon, onto the top of the stack resting on the divider 26. It is contemplated that the feed conveyer 16 will operate at such a rate that the articles 20 will move onto the stacking wheel without causing any substantial misalignment. A separate retaining and/or supporting means (not shown) may also be provided so as to maintain the stack in the proper alignment along the stacking wheel and on the top of divider 26. Means may also be provided adjacent the stacking wheel for continuously cleaning the stacking wheel 12 as in area 60 in FIG. 1.
The size of the stack formed by the stacking wheel 12 is determined by the distance between one divider 26 and its next adjacent divider 26a. Thus when the number of articles 20 in the stack depletes the spacing between adjacent dividers 26 and 26a, the incremental rotation is such that the new stack is started on divider 26a. As the stacking wheel 12 continues to incrementally rotate, a support guide 28 maintains the stack on the stacking wheel 12 and between the adjacent dividers 26, 26a. The wheel 12 rotates from the stacking area 22 towards the packaging device 14 and shifts the orientation of the stack approximately 90° . Thus, when the articles 20 reach the packaging area 30 at the bottom of the stacking wheel 12, the stack is generally longitudinally oriented.
The stacking wheel 12 includes a multiple number of dividers. As illustrated, the dividers are projected at equally spaced intervals around the circumference of the wheel 12. The distance between adjacent dividers defines the size of the stack. The number of articles within the stack will depend on the spacing between adjacent dividers and the thickness of each article. Each of these parameters can be programmed into the controller 32 so as to adjust the incremental rotation of the wheel 12. Furthermore, the relative spacing between the projected dividers can be adjusted by selecting various groups of dividers. The dividers 26 shown as projected in FIG. 1 represent only a portion of the number provided on wheel 12. Retracted dividers 34 and 36 may also be projected along with dividers 26 in various formats, as desired. Thus, by selecting any series or combination of dividers 26, 34 and 36, the relative spacing between adjacent dividers on the wheel 12 is varied, and thus the size of the stack can be varied.
As illustrated in FIG. 3, projection of the dividers is accomplished by air actuated cylinders 38. The actuators 38 control whether or not the dividers 26, 34 or 36 are projected from the support surface 40 of the stacking wheel 12. Upon selection of a specific size stack, corresponding to the number of articles desired and the size of the articles to be packaged, the selection of the specific group of dividers to be projected is determined. This calculation may be performed by the controller 32 along with the calculation of the incremental rotation of the wheel 12 by the drive motor 29. Equivalent means to control the projection of the dividers from the periphery of the wheel 12 may also be utilized and is contemplated by the present invention.
Upon orientation of the stack of articles to the packaging area 30, the stack is positioned on a first sliding plate 42. Positioned below the first sliding plate 42 is a retaining area 44. The retaining area 44 is defined by squeezing elements 46 and 48 and by stationary side walls (not shown). The bottom of the retaining area is defined by a second sliding plate 50. The second sliding plate 50 is positioned directly above the exhaust conveyor 18. A package or tray 52 is retained on conveyor 18 for receiving a stack. The tray 52 may be held in position on conveyer 18 by means of projecting stop 54.
In FIG. 1, a stack of articles has reached the position of the packaging area 30 and is ready to be inserted into tray 52 by means of the packaging device -4. The initial operation of the packaging device 14 is illustrated in FIG. 4. The first sliding plate 42 has been withdrawn from underneath the stack. The articles thus move (fall) into the retaining area 44. It is contemplated that the spacing between adjacent dividers 26 and 26a is slightly larger than the space provided within the tray 52. This relative spacing permits the articles in the stack to remain somewhat loose as they rotate along the support guide 28 to the packaging area 30. However, in order to properly align the stack for placement into the tray 52, squeezing elements 46 and 48 move relatively inward to slightly compress the stack and realign the articles therein. The initial position of the squeezing elements is generally contemplated to correspond to the distance between adjacent dividers on the wheel 12. The relative position between adjacent dividers on the divider, the initial position of the squeezing elements 46 and 48, and the amount of compression during squeezing is controlled by the controller 32. Movement of the squeezing elements 46 and 48 is accomplished by actuating cylinders 56 and 58, respectively.
As is illustrated in FIG. 5, upon compression of the stack between the squeezing elements 46 and 48, the second sliding plate 50 is retracted and the stack is permitted to fall into the tray 52. Substantially simultaneous with the retraction of the second sliding plate 50 is the release of the squeezing element 46 and 48. Upon the stack being positioned in the tray 52, stop 54 is withdrawn. The tray 52 is then permitted to move along the exhaust conveyer 18 to the next station in the production line.
The timing of the movement of the first sliding plate 42, the squeezing elements 46 and 48, the second sliding plate 50, and stop 54 is generally controlled by controller 32 and is a function of the size of the stack and the number of articles therein. The size of the stack is determined at the initiation of the operation by inputting the number of articles desired to be positioned within the stack and the size of each individual article.
It should be noted that the incremental movement of the stacking wheel 12 may result in a backlash at the end of the rotation thereof, due to the momentum of the stacking wheel 12. This backlash may be controlled by a brake (not shown), magnetic or otherwise, which is timed in conjunction with the incremental rotation of the wheel 12. Preferably, an anti-backlash type drive motor 29 is provided. Other means for controlling backlash are also contemplated. Furthermore, although pneumatic type actuated cylinders are contemplated for use with the moving parts of the apparatus 10, other means of actuation may also be utilized, including electronic cellanoids, mechanically controlled levers and the like.
A vibration means may be utilized within the packaging device 14 so as to assist in maintaining proper alignment of the articles by settling them within the retaining area 44 and/or the tray 52. Also, a number of stops 54 may be provided for trays having multiple slots therein for receiving multiple stacks of articles. Each stop would permit an incremental movement of the tray 52 along exhaust conveyer 18 to properly align the desired slot under the retaining area 44.
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 device for stacking and packaging a series of articles includes a rotating wheel having a multiple number of dividers thereon. The dividers being selectably projected from the periphery of the wheel in various space relationships for defining the size of a stack. The size of the stack is adjusted by varying the distance between adjacent dividers. The stacking wheel moves a stack to a packaging device that includes elements to align the stack for positioning into a package.
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BACKGROUND OF THE INVENTION
Illustrated in FIG. 1 is a typical software change management repository 100 of the prior art. In a software change management repository 100 , a set of objects 99 is maintained to capture the set of changes that have been requested by the developers and users of a software system. These change request objects 99 are known by a variety of names in different change management repositories, such as Modification-Requests, Enhancement-Requests, Work-Items, Defects, and Bugs. In this disclosure, the term “Change-Request” is used to refer to these types of objects 99 .
The information about a change request is captures in a set of properties of the Change-Request object 99 . The property is represented by either an atomic value (such as a string, an integer, or a date) or a reference to another object 99 as illustrated by the ‘XX’ and dotted line arrow, respectively, of object 99 a in FIG. 1 . Some properties are pre-defined and present on all Change-Request objects 99 , but most properties are determined by a customer, and can vary from project to project. The current state of a change request is summarized in a pre-defined State property 102 of the Change-Request object 99 . Although the State property 102 is pre-defined, the legal values of the State property are determined by a customer. The customer defines a set of allowed transitions from one State value to another, and defines the actions that perform those transitions.
Some key problems with maintaining the state of a Change-Request object 99 are as follows:
1. Different stake-holders in the change management process have different perspectives on what the current state of a given Change-Request should be. For example, a developer might believe that the Issue is resolved, while the submitter of the Issue believes the Issue requires further work. One approach to this problem is to introduce composite states such as “open-development-pending”, “open-development-complete” and, “closed-development-complete”. This approach results in a combinatorial explosion in the number of states as the number of stake-holders in the Change-Request management process increases, which makes it difficult to introduce new stake-holders to the change management process. 2. Multiple users of a software system might report similar problems. If each of these problems is entered as a separate Change-Request object 99 , it is error-prone and expensive to update the properties of each of these Change-Request objects as the problem is being resolved. If only a single Change-Request object 99 is used to track all of these problems, such as what release of the system was demonstrating the problem, and whether the problem has been resolved on the particular platform or product variant needed by a given user. 3. A given Change-Request might need to be resolved in different ways in multiple releases of variants of a given software system. It is important to be able to independently track how work is progressing in each of these releases or variants, but if there are separate Change-Request objects 99 for each release or variant, it is error-prone and expensive to update the problem description information on each of those change requests. 4. A given set of changes might be able to contribute to the completion of multiple tasks (especially when they are tasks to fix the same problem in different releases or variants of the software system). It is error-prone and expensive to be updating the multiple Change-Request objects 99 as work on that single activity progresses. 5. Different stake-holders in the change management process might be working at different sites with different replicas of the change management repository 100 , or working disconnected with a personal replica of a subset of the change management repository 100 . When multiple replicas are in use, different stake-holders can unwittingly modify the Change-Request object 99 in incompatible ways, resulting in difficult merge scenarios that require expensive manual merging or result in Joss of information from automated merging. A standard solution to this problem is to assign one replica of the repository 100 as the master of a given Change-Request, and only users accessing that replica of the repository 100 can make any modifications to that Change-Request object 99 . But this results in serious delays and loss of information as stake-holders wait for mastership to be transferred to their replica.
SUMMARY OF THE INVENTION
In the present invention, a Change-Request object is partitioned into a set of linked sub-object hierarchies: one Issue hierarchy, zero or more Task hierarchies, and zero or more Activity hierarchies. A given Task can be associated with multiple Issues (and therefore contribute to multiple Change-Requests), and a given Activity can be associated with multiple Tasks (and therefore contribute to multiple Change-Requests). Each Task, Issue and Activity is represented by a respective object which serves as a sub-object to the Change Request object. Each sub-object is owned by a single stake-holder (individual user) and has its own Status field that identifies the state of the Change-Request from the perspective of that individual. Each stake-holder then interacts with a single sub-object with a relatively simple set of Status values and Status transitions, while the State of the Change-Request is a composite value computed from the Status of each of the objects in the sub-object hierarchies of the Change-Request.
In a preferred embodiment, a computer method and apparatus for making changes to a given software system, comprise the steps of:
forming a change request object to represent a user's request to make a change to a given software system;
creating a root issue object for that change request object, the root issue object enabling a hierarchy of issue objects, each issue object representing a respective issue;
allowing a user or means to partition an issue object into issue sub-objects;
allowing a user or means to create a task object to define work needed to address an issue;
allowing a user or means to partition a task object into task sub-objects;
allowing a user or means to create an activity object to track work performed;
allowing a user or means to partition an activity object into activity sub-objects;
allowing a user or means to relate issue objects and issue sub-objects to task objects and task sub-objects;
allowing a user or means to relate task objects and task sub-objects to activity objects aid activity sub-objects;
determining the state of an object based on the status of each of its related objects and sub-objects.
The change request objects are stored in a repository and managed therein by a manager which computes the state of an object as a function of status of its related objects and sub-objects.
BRIEF DESCRIPTION OF THE DRAWINGS
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.
FIG. 1 is a block diagram of a change management repository of prior art.
FIGS. 2 a and 2 b are schematic and block diagrams, respectively, of computer network and digital processing environment in which embodiments of the present invention are deployed.
FIGS. 3 and 4 are schematic views of a change request object and corresponding object management system in embodiments of the invention.
FIG. 5 is a block diagram of one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
A description of preferred embodiments of the invention follows.
FIG. 2 a illustrates a computer network or similar digital processing environment in which the present invention may be implemented.
Client computer(s) 50 and server computers) 60 provide processing, storage, and input/output devices executing application programs and the like. Client computer(s) 50 can also be linked through communications network 70 to other computing devices, including other client devices/processes 50 and server computer(s) 60 . Communications network 70 can be part of a remote access network, a global network (e.g., the Internet), a worldwide collection of computers, Local area or Wide area networks, and gateways that currently use respective protocols (TCP/IP, Bluetooth, etc) to communicate with one another. Other electronic device/computer network architectures are suitable.
FIG. 2 b is a diagram of the internal structure of a computer (e.g., client processor 50 or server computers 60 ) in the computer system of FIG. 4 . Each computer 50 , 60 contains system bus 79 , where a bus is a set of hardware lines used for data transfer among the components of a computer or processing system. Bus 79 is essentially a shared conduit that connects different elements of a computer system (e.g., processor, disk storage, memory, input/output ports, network ports, etc.) that enables the transfer of information between the elements. Attached to system bus 79 is I/O device Interface 82 for connecting various Input and output devices (e.g., keyboard, mouse, displays, printers, speakers, etc.) to the computer 50 , 60 . Network interface 86 allows the computer to connect to various other devices attached to a network (e.g., network 70 of FIG. 2 a ). Memory 90 provides volatile storage for computer software instructions 92 and data 94 used to implement an embodiment of the present invention (e.g., change request objects 13 , change request object hierarchies 15 , 17 , 19 and change request manager code 11 detailed below). Disk storage 95 provides non-volatile storage for computer software instructions 92 and data 94 used to implement an embodiment of the present invention. Central processor unit 84 is also attached to system bus 79 and provides for the execution of computer instructions.
In one embodiment, the processor routines 92 and data 94 are a computer program product (generally referenced 92 ), including a computer readable medium (e.g., a removable storage medium such as one or more DVD-ROM's, CD-ROM's, diskettes, tapes, etc.) that provides at least a portion of the software instructions for the invention system. Computer program product 92 can be installed by any suitable software installation procedure, as is well, known in the art. In another embodiment, at least a portion of the software instructions may also be downloaded over a cable, communication and/or wireless connection. In other embodiments, the invention programs are a computer program propagated signal product 107 embodied on a propagated signal on a propagation medium (e.g., a radio wave, an infrared wave, a laser wave, a sound wave, or an electrical wave propagated over a global network such as the Internet, or other network(s)). Such carrier medium or signals provide at least a portion of the software instructions for the present invention routines/program 92 .
In alternate embodiments, the propagated signal is an analog carrier wave or digital signal carried on the propagated medium. For example, the propagated signal may be a digitized signal propagated over a global network (e.g., the Internet), a telecommunications network, or other network. In one embodiment, the propagated signal is a signal that is transmitted over the propagation medium over a period of time, such as the instructions for a software application sent in packets over a network over a period of milliseconds, seconds, minutes, or longer. In another embodiment, the computer readable medium of computer program product 92 is a propagation medium that the computer system 50 may receive and read, such as by receiving the propagation medium and identifying a propagated signal embodied in the propagation medium, as described above for computer program propagated signal product.
Generally speaking, the term “carrier medium” or transient carrier encompasses the foregoing transient signals, propagated signals, propagated medium, storage medium and the like.
Illustrated in FIG. 3 is a change request object 13 of the present invention. The change request object 13 is initiated in response to a given change request and stored in repositories 100 using similar first steps and technology of the prior art. Unlike prior art change request objects 99 , however, the invention change request object 13 is partitioned into a set of sub objects 21 , 23 , 25 , 27 , 31 , 33 . Each sub object is of one of the sub object hierarchies, namely an Issue hierarchy 15 , a Task hierarchy 17 , and an activity hierarchy 19 . Preferably, there is one Issue hierarchy 15 , and there may be zero or more Task hierarchies 17 and zero or more Activity hierarchies 19 . The subject hierarchies 15 , 17 , 19 are linked to each other such that a given. Task 27 can be associated with multiple Issues 21 (and therefore contribute to multiple Change-Requests), and a given Activity 31 can be associated with multiple Tasks 27 (and therefore contribute to multiple Change-Requests). Each sub-object 21 , 23 , 25 , 27 , 31 , 33 is owned by a single stake-holder (user) and has its own Status field that identifies the state of the subject Change-Request 13 from the perspective of that individual (user). Each stake-holder then interacts with a single sub-object with a relatively simple set of Status values and Status transitions, while the State of the Change-Request 13 is a composite value computed from the Status of each of the objects in the sub-object hierarchies 15 , 17 , 19 of the Change-Request 13 .
The Issue hierarchy 15 contains information about the motivation for a Change-Request 13 . This might be a problem report (a “defect”), or a change to the requirements of the software system (an “enhancement”). Each object 21 , 25 in the issue hierarchy 15 represents an issue. An Issue object 21 , 25 contains properties that specify requirements on how the Issue needs to be addressed (for example, if a system is released on multiple platforms, what platforms are required). When an Issue can be logically decomposed into multiple sub-Issues, respective sub-objects 23 of the Issue object 21 are created for each of those sub-Issues. This allows the State of a sub-Issue to be independently tracked; for example, the development organization may decide to only address one of the sub-Issues of a given issue.
The Task hierarchy 17 contains a description of the work that would address the Issue (at 21 , 25 generally) that motivates the Change-Request 13 . A Task (represented by a respective Task object 27 a , . . . 27 n ) is initially created by a triage team that is investigating an Issue 21 . If the triage team decides that the Issue 21 is to be addressed, the Status of the Task 27 is set to “Active”. Alternatively, the triage team could decide not to address the Issue 21 , in which case the Status of the Task 27 is set to “No-Plan-To-Fix”.
If a triage team decides that more than one Issue 21 b , 21 e , 25 can and should be addressed by the same Task 27 a , the same Task 27 a is linked to all of those Issues 21 (as shown by dashed arrows 29 in FIG. 3 ). For example, if the same defect is being reported by multiple stake-holders, the invention system 11 links the multiple stake holders versions of Change-Request 13 (as represented by respective issue objects 21 , 25 ) for the defect to the Task 27 for fixing that defect.
When there are several software releases or variants in which an Issue 21 is to be addressed, the system 11 creates a separate Task 27 for each release or variant, and links each Task 27 to the Issue 21 .
The Activity hierarchy 19 contains the changes made to perform a given Task 27 . If one activity (represented by a respective object 31 a for example) completes multiple tasks 27 a , . . . 27 n , system 11 associates the activity 31 a with each of those tasks 27 a , . . . 27 n (as illustrated at 35 in FIG. 3 ). If one sub-activity 33 contributes to multiple activities 31 , system 11 makes a sub-object 33 of each of those sub-activities.
With regard to state or status value of the change request object 13 , attention is turned to FIG. 4 . In general an object that has sub-objects is called a “composite object”. The Status of a composite object is computed from the Status values of its sub-objects. A composite object may have a Private-Status property 41 which is a Status value that is independent of the Status of its sub-objects, and which contributes to the Status of the composite object as if the private status 41 were the Status value of a sub-object of the composite object.
In the preferred embodiment, there are three pre-defined Status values: Active, Complete, or Cancelled. Each customer-defined Status value is classified as being Active, Complete, or Cancelled. Generally, an object, is Active if its predefined Status is Active or if its customer-defined Status value is classified as being Active. An object is Complete if its predefined Status is Complete or if its customer-defined Status value is classified as being Complete. An object is Cancelled if its predefined Status is Cancelled or if its customer-defined Status value is classified as being Cancelled. The invention system 11 sets the Status 45 of a composite object 21 , 25 , 27 , 31 in FIGS. 3 and 4 to;
“Cancelled” if all of Its sub-objects are Cancelled; otherwise
“Active” if any of its sub-objects are Active; otherwise
“Complete”.
System 11 then computes the State 42 of a Change-Request 13 from the Status of the objects 21 , 25 , 27 , 31 in the Issue, Task, and Activity hierarchies 15 , 17 , 19 associated with the Change-Request. The State 42 is preferably one of: Open, Cancelled, Partially-Scheduled, Scheduled, Partially-Developed, Developed, Complete, No-Plan-To-Fix, or Cancelled. In particular, invention system 11 defines the State 42 of a Change-Request object 13 with a given root Issue 25 as:
“Cancelled” if root Issue 25 is Cancelled; otherwise
“Open” If there is no Task 27 associated with the root Issue 25 ; otherwise
“Complete” if there is at least one Complete Task 27 that is associated with the root Issue 25 ; otherwise
“No-Plan-To-Fix” if all Tasks 27 associated with the root Issue 25 are Cancelled; otherwise
“Developed” if there is a Complete Activity 31 that is associated with an Active Task 27 that is associated with the root Issue 25 .
“Partially-Developed” if there is at least one Active Activity 31 or Complete Activity 31 that is associated with a non-Cancelled Task 27 that is associated with an Issue 21 in the Issue hierarchy 15 ; otherwise
“Scheduled” if there is at least one Active Task 27 associated with the root Issue 25 ; otherwise
“Partially-Scheduled”.
In the example illustrated in FIG. 4 , invention system 11 sets state 42 of Change Request object 13 to “Developed” because the activity 31 a has a status 45 a value of “Complete”, and this activity 31 a is associated with an active task 27 a (status 45 f value=“Active”) that is associated with the root issue 25 , illustrated by the dashed line arrows. Even though the activity 31 a has a private status 41 d value of “Cancelled”, not all of the activity sub-objects 33 are of status “Cancelled” and none are status “Active”. Thus system 11 sets status 45 n of composite activity object 31 a to “Complete”.
Likewise, task object 27 a has a private status 41 c set to “Active”. This follows the above rules that if any of task object's 27 a sub-object status 45 (including private status 41 c ) is “Active”, then system 11 sets task object 27 a status 45 f to “Active”,
Further, root issue 25 has a private status 41 b value of “Complete”. Issue objects 21 a and 21 c have respective status 45 b , 45 c of “Cancel” and “Active”. Issue object 21 c is of “Active” status 45 c because at least one of its sub-objects 23 d . . . 23 n has a respective status 45 d . . . 45 e of “Active”. Because root issue 25 is a composite object, its status 45 a value is set to “Active” where one of its sub-objects 21 c status 45 c is “Active”.
A sub-object 21 , 25 , 27 , 31 is mastered at the replica of the stake-holder that owns it. When a stake-holder transitions to a different replica (such as when he goes off-line), all sub-objects owned by that stake-holder are automatically transferred to that replica. Since each sub-object is owned and manipulated by a single stake-holder, this avoids delays and loss of information that result when two stake-holders at different sites attempt to update a shared object.
According to the foregoing, embodiments of the present invention employ a Change Request object creator 51 , partitioning means 53 and Change Request management means (manager system) 55 as shown in FIG. 5 . In response to user request to change a subject software system (program or the like), invention, system 11 through Change Request object creator 51 initiates a Change Request object 13 . Techniques known, in the art may be employed to implement Change Request object creator 51 . Creator 51 stores initiated Change Request objects 13 in a repository 101 similar to the change management repositories 100 of prior art.
Partitioning means 53 generates the issue hierarchy 15 , task hierarchy 17 and activity hierarchy 19 corresponding to a Change Request object 13 stored in repository 101 . Linked objects, tree structures and other data structures are employed.
Change Request management means 55 maintains associations between activity objects 31 , task objects 27 and issue/root objects 21 , 25 . Change Request management means 55 computes and maintains die status 45 values and private status 41 values of the objects 21 , 25 , 27 , 31 , 33 in the hierarchies 15 , 17 , 19 according to the above-described rules in FIGS. 3 and 4 . Likewise, manager 55 computes and maintains the respective state 42 values and private status 41 a values of Change Request objects 13 for each stake-holder at the replica of that stake-holder.
While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein, without departing from the scope of the invention encompassed by the appended claims.
For example, the present invention may be implemented in a variety of computer architectures. The computer network of FIGS. 2 a and 2 b are for purposes of illustration and not limitation of the present invention.
The invention can take the form of an entirely hardware embodiment, an entirely software embodiment or an embodiment containing both hardware and software elements. In a preferred embodiment, the invention is implemented in software, which includes but is not limited to firmware, resident software, microcode, etc.
Furthermore, the invention can take the form of a computer program product accessible from a computer-usable or computer-readable medium providing program code for use by or in connection with a computer or any instruction execution system. For the purposes of this description, a computer-usable or computer readable medium can be any apparatus that can contain, store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device.
The medium can be an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system (or apparatus or device) or a propagation medium. Examples of a computer-readable medium include a semiconductor or solid state memory, magnetic tape, a removable computer diskette, a random access memory (RAM), a read-only memory (ROM), a rigid magnetic disk and an optical, disk. Current examples of optical disks include compact disk-read only memory (CD-ROM), compact disk-read/write (CD-R/W) and DVD.
A data processing system suitable for storing and/or executing program code will include at least one processor coupled directly or indirectly to memory elements through a system bus. The memory elements can include local memory employed during actual execution of the program code, bulk storage, and cache memories which provide temporary storage of at least some program code in order to reduce the number of times code must be retrieved from bulk storage during execution.
Input/output or I/O devices (including but not limited to keyboards, displays, pointing devices, etc.) can be coupled to the system either directly or through intervening I/O controllers.
Network adapters may also be coupled to the system to enable the data processing system to become coupled to other data processing systems or remote printers or storage devices through intervening private or public networks. Modems, cable modem and Ethernet cards are just a few of the currently available types of network adapters.
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Computer method and apparatus manage requests to make changes to a given software system (e.g., application program or program portion). The invention method and apparatus form a change request object representing a user's request to make a change to the given software system. The invention method and apparatus form one or more hierarchies of objects and sub-objects to represent work to be performed and work performed in making the requested change. One embodiment creates a root issue object for each change request object and allows a user to partition an issue object into issue sub-objects. The embodiment (a) allows a user to create a task object to define the work needed to address an issue and allows a user to partition a task object into task sub-objects, and (b) allows a user to create an activity object to track work performed and allows a user to partition an activity object into activity sub-objects. Issue objects and issue sub-objects are relatable to task objects and task sub-objects. Task objects and task sub-objects are relatable to activity objects and activity sub-objects. State of an object is determined based on the status of each of its related objects and sub-objects.
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This is a continuation of application Ser. No. 07/211,948 filed on June 27, 1988, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to blends of acrylonitrile/butadiene/styrene copolymers (ABS) with certain copolyesters. These blends have been found to have an unexpectedly good balance of physical properties.
2. Discussion of the Background
Art of interest in connection with this invention includes U.S. Pat. No. 3,644,574, which discloses blends of poly(tetramethylene terephthalate) with polystyrene or with copolymers having a styrene content greater than 50%.
U.S. Pat. No. 3,564,077 discloses that the impact properties of poly(ethylene terephthalate) can be moderately improved by blending the poly(ethylene terephthalate) with small amounts, generally less than 10% by weight of a styrene-butadiene copolymer.
U.S. Pat. No. 4,117,034 discloses that the addition of certain graft polymers to amorphous aromatic polyesters of aliphatic diols provides an improvement in the impact strength characteristics and a concomitant reduction in the notch sensitivity of the composition. The polyesters disclosed by U.S. Pat. No. 4,117,034 can be amorphous polyesters derived from aromatic dicarboxylic acids and aliphatic diols, e.g., the phthalate copolyesters of aliphatic diols having three or more carbon atoms, such as copoly(1,4-cyclohexalene dimethylene iso/terephthalate) and the like.
U.S. Pat. No. 4,096,202 discloses that impact modifiers for poly(alkylene terephthalates) based on rubbers of polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, ethylene-propylene rubbers, polyisobutene and polyisoprene have been suggested, making reference to U.S. Pat. No. 3,919,353.
U.S. Pat. No. 4,496,202 also discloses blends of about 99% to 60% by weight of a poly(alkylene terephthalate) and about 1% to 40% by weight of a multi-phase composite interpolymer. The multi-phase composite interpolymer is made up of about 25 to 95 weight % of a first elastomeric phase polymerized from a monomer system, and about 75% to 5% by weight of a final, rigid thermoplastic phase form of epoxy groups polymerized in the presence of the elastomeric phase. The monomer system is made up of about 75% to 99.8% by weight of a C 1-6 alkyl acrylate, 0.1% to 5% by weight of a crosslinking monomer, and 0.1% to 5% by weight of a graft linking monomer. This blend is said to provide an impact modified poly(alkylene terephthalate) without significantly increasing melt viscosity.
DE No. 33 32 325 discloses blends of acrylonitrile/butadiene/styrene copolymers with polycarbonate. JP No. 53-71155 discloses three component blends of aromatic polyesters, acrylonitrile/butadiene/styrene copolymers and polycarbonate.
The present invention provides blends of ABS copolymers with certain copolyesters which possess a high notched Izod impact strength combined with a good balance of other properties, i.e., flexural modulus, tensile properties, heat deflection temperature, and hardness. These blends are useful in making automotive and appliance components.
BRIEF DESCRIPTION OF THE FIGURES
A more complete appreciation of this invention and many of its attendant advantages will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying figures, wherein:
FIGS. 1, 2 and 3 graph the notched Izod strength at 23° C. of various blends provided by the present invention as a function of the cyclohexanedimethanol content of the copolyester used in the blend.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The composition of the present invention is a blend of a copolyester component and an ABS copolymer component. The copolyester can be present in an amount of from 5% by weight to 95% by weight, and the copolymer can be present in an amount of from 95% by weight to 5% by weight, both weights being based on the combined weights of ABS and copolyester.
The copolyester component comprises repeating units from terephthalic acid, ethylene glycol, and cyclohexanedimethanol. This copolyester is made up of repeating units from an acid component of terephthalic acid and a glycol component of repeating units from about 85 to 10 mol % ethylene glycol, and about 15 to 90 mol % cyclohexanedimethanol.
As used herein, the term "terephthalic acid" includes substituted terephthalic acid such as 2-methyl-, 2-chloro-, 2,5-dimethyl-, or 2,5-dichloroterephthalic acid. The terephthalic acid portion also may be replaced with up to 20 mol % of other conventional aromatic dicarboxylic acids, such as 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, or isophthalic acid, or with aliphatic dicarboxylic acids containing 5-20 carbon atoms, such as glutaric, adipic, pimelic, suberic, azelaic, sebacic, cyclohexanedicarboxylic or dodecanedicarboxylic acids. Essentially 100 mol % terephthalic acid is preferred.
The ethylene glycol and cyclohexanedimethanol may be replaced with up to about 20 mol % of other aliphatic glycols, containing 2 to 10 carbon atoms such as ethylene glycol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol.
For many of these blends, the highest notched Izod impact strength characteristics are observed with copolyester containing repeat units from about 40 to 90 mol % cyclohexanedimethanol.
Generally the highest notched Izod impact strength characteristics are observed for compositions containing at least 50% by weight of the copolyester.
In a preferred embodiment of this invention, the copolyester component has an inherent viscosity of from about 0.5 to 1.0, preferably this inherent viscosity is from about 0.7 to 0.8.
In another preferred embodiment, the cyclohexanedimethanol component is a cis-/trans-mixture of 1,4-cyclohexanedimethanol.
In another preferred embodiment of this invention, the acrylonitrile/butadiene/styrene copolymer has a notched Izod impact strength of at least 2.5 ft-lb/in at 23° C. The ABS copolymers useful in this invention may have repeat units from the respective monomers in the following ranges:
acrylonitrile--about 15% to 30%
butadiene--about 6% to 30%
styrene--about 40% to 80%
Cycolac L is an acrylonitrile/butadiene/styrene copolymer (repeat unit weight percents of about 23, 27, and 50 respectively) having a notched Izod impact strength of 9.9 ft-lb/in and is represented in FIG. 1 as "ABS Copolymer A." As illustrated in FIG. 1, the highest Izod impact strength characteristic were observed for 20/80 ABS Copolymer A/polyester blends. For these blends, a notable increase in the notched Izod impact strength of the blend is observed at a 30% cyclohexanedimethanol content. The notched Izod impact strength of the blend increases as a function of the percentage of cyclohexanedimethanol in the copolyester to reach a maximum at a value of 65 mol % cyclohexanedimethanol, whereinafter the notched Izod impact strength characteristic of the blend decreased.
A 50/50 ABS Copolymer A/polyester blend behaves similarly, displaying a maximum notched Izod impact strength in the region of from 65 to 80 mol % cyclohexanedimethanol. The increase of the notched Izod impact strength of this blend is essentially continuous up to a 60% content of cyclohexanedimethanol, at which point the notched Izod impact strength levels to a value of about 80% cyclohexanedimethanol, whereinafter a decrease in notched Izod impact strength was noted.
An 80/20 ABS Copolymer A/polyester blend displays a more consistent notched Izod impact strength for values of up to approximately 65% cyclohexanedimethanol. With increasing content of cyclohexanedimethanol, the notched Izod impact strength of this blend decreases gently from 65 mol % cyclohexanedimethanol to a value of about 80 mol % cyclohexanedimethanol, whereupon it decreases more steadily.
FIG. 2 shows a different trend in the notched Izod impact strength of compositions provided by the present invention. FIG. 2 illustrates the notched Izod impact strength of Cycolac T/polyester compositions as a function of cyclohexanedimethanol content in the copolyester. Cyclolac T is an acrylonitrile/butadiene/styrene copolymer (repeat unit weight percents of about 27, 20, and 53 respectively) having a notched Izod characteristic of 6.7 ft-lb/in and is represented in FIG. 2 as ABS Copolyester B.
For these compositions, the highest notched Izod impact strength characteristics are displayed by an 80/20 ABS/copolyester blend at low cyclohexanedimethanol content. For this 80/20 blend, the notched Izod impact strength characteristic of the composition decreases continuously as a function of cyclohexanedimethanol content to reach a minimum value at 65 mol % cyclohexanedimethanol content, whereupon the notched Izod impact strength characteristics of the composition increases to reach a second maximum at 81 mol % cyclohexanedimethanol, whereupon the notched Izod impact strength characteristics again decreases.
By contrast, two other blends tested, a 50/50 ABS/copolyester blend and a 20/80 ABS/copolyester blend, both display an increase in notched Izod impact strength characteristics as a function of increasing cyclohexanedimethanol content. Both of these compositions display a maximum notched Izod impact strength at concentrations of from 65% to 85% cyclohexanedimethanol, whereupon the notched Izod impact strength characteristics decrease.
FIG. 3 provides the notched Izod impact strength for Cycolac DFA-R/polyester blends as a function of cyclohexanedimethanol content. Cycolac DFA-R is an acrylonitrile/butadiene/styrene copolymer (repeat unit weight percents of about 25, 13, and 62 respectively) material having a notched Izod characteristic of 2.6 ft-lb/in and is represented in FIG. 3 or ABS Copolymer C. For these compositions, a 20/80 ABS/copolyester blend displays the highest notched Izod impact strength characteristics. These characteristics increase as a function of cyclohexanedimethanol content to reach a maximum in the range of 65 to 85 mol % cyclohexanedimethanol, whereupon the notched Izod impact strength characteristics decrease. Two other blends tested, a 50/50 ABS/copolyester blend and a 20/80 ABS/copolyester blend, display maximal notched Izod impact strength characteristics in the neighborhood of 80 mol % cyclohexanedimethanol.
Other features of this invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
EXAMPLE 1
Blends of 80%, 50%, and 20% Cycolac L ABS (notched Izod of 9.9 ft-lb/in.) with 20%, 50%, and 80%, respectively, of each of PCT (a terephthalic acid/cyclohexanedimethanol polyester), Copolyester R (a terephthalic acid/cyclohexanedimethanol/ethylene glycol polyester from terephthalic acid, about 75-85 mol % cyclohexanemethanol, and about 15-25 mol % ethylene glycol), Copolyester S (a terephthalic acid cyclohexanedimethanol/ethylene glycol polyester from terephthalic acid, about 60-70 mol % cyclohexanedimethanol, and about 30-40 mol % ethylene glycol), Copolyester T (a terephthalic acid/cyclohexanedimethanol/ethylene glycol polyester from terephthalic acid, about 65-75 mol % cyclohexanedimethanol, and about 25-35 mol % ethylene glycol) and PET (a terephthalic acid/ethylene glycol polyester) were prepared. These blends are dried and melt compounded on a 1.5 inch single screw MPM extruder and chopped into pellets (conditions are provided in Table I). The samples are redried and molded on a 175 ton New Britain injection molding machine (conditions in Table I). Upon review of the data, an unusual trend is seen. Surprisingly, the notched Izod strength at 23° C. of the blends over a certain range of mol % CHDM (about 15% to about 90%) in the copolyesters is seen to be increased over blends made with the homopolymers PCT and PET or with low levels of ABS (see FIG. I).
EXAMPLE 2
Blends using Cycolac T ABS (notched Izod of 6.7 ft-lb/in.) are made as in Example 1. Again, the notched Izod impact strength at 23° C. of the blends made with the copolyesters containing about 15 to about 90 mol % CHDM is unexpectedly greater than those made with the homopolymers PCT and PET or with low levels of ABS (see FIG. II).
EXAMPLE 3
Blends using Cycloac DFA-R (notched Izod of 2.6 ft-lb/in.) are made following the procedure used in Example 1. The notched Izod impact strength at 23° C. of the blends over the same range of mol % CHDM in the copolyester is again surprisingly greater than those made with the homopolymers PCT and PET or with low levels of ABS (see FIG. III).
TABLE I______________________________________ Copolyester PCT R S T PET______________________________________% CHDM 100 81 66 31 0Extrusion with ABSDrying Temp (C) 90 90 90 90 90Drying Time (hr) 16 16 16 16 16Extrusion Temp (C) 270 250 250 250 260Molding with ABSDrying Temp (C) 90 90 90 90 90Drying Time (hr) 16 16 16 16 16Temp (°C.) 270 250 250 250 260Mold Temp (°C.) 23 23 23 23 23______________________________________
As used herein, the inherent viscosity (I.V.) is measured at 25° C. using 0.50 gram of polymer per 100 mL of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane.
Izod impact strengths are determined according to ASTM D256.
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 blend of a terephthalic acid/ethylene glycol/cyclohexanedimethanol copolyester and an acrylonitrile/butadiene/styrene copolymer is disclosed. This blend possesses high notched Izod impact strength while maintaining a good balance of flexural modulus properties, tensile properties, heat diffusion temperature properties and hardness properties. This blend is useful in making automotive and appliance components.
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CROSS-REFERENCE TO RELATED APPLICATION
This is a divisional application of U.S. Ser. No. 08/227,211, filed Apr. 13, 1994, U.S. Pat. No. 5,554,643; which is a divisional of U.S. Ser. No. 07/726,653, filed Jul. 12, 1991, now U.S. Pat. No. 5,340,825 dated Aug. 23, 1994; which is a CIP of U.S. Ser. No. 07/576,315, filed Aug. 31, 1990, now abandoned.
BACKGROUND OF THE INVENTION
Agents acting at central cholecystokinin (CCK) receptors may induce satiety (Schick, Yaksh and Go, Regulatory Peptides 14:277-291, 1986). They are also expected to act as analgesics (Hill, Hughes and Pittaway, Neuropharmacology 26:289-300, 1987), and as anticonvulsants (MacVicar, Kerrin and Davison, Brain Research 406:130-135, 1987).
Reduced levels of CCK-peptides have been found in the brains of schizophrenic patients compared with controls (Roberts, Ferrier, Lee, Crow, Johnstone, Owens, Bacarese-Hamilton, McGregor, O'Shaughnessey, Polak and Bloom. Brain Research 288:199-211, 1983). It has been proposed that changes in the activity of CCK neurones projecting to the nucleus accumbens may play a role in schizophrenic processes by influencing dopaminergic function (Totterdell and Smith, Neuroscience 19:181-192, 1986). This is consistent with numerous reports that CCK peptides modulate dopaminergic function in the basal ganglia and particularly the nucleus accumbens (Weiss, Tanzer, and Ettenberg, Pharmacology, Biochemistry and Behaviour 30:309-317, 1988; Schneider, Allpert and Iversen, Peptides 4:749-753, 1983). It may therefore be expected that agents modifying CCK receptor activity may have therapeutic value in conditions associated with disturbed function of central dopaminergic function such as schizophrenia and Parkinson's disease.
CCK and gastrin peptides share a common carboxy terminal pentapeptide sequence and CCK peptides can bind to the gastrin receptor of the stomach mucosa and elicit acid secretion in many species including human (Konturek, Gastrointestinal Hormones, Ch. 23, pp 529-564, 1980, ed. G. B. J. Glass, Raven Press, New York). Antagonists of the CCK-B receptor would also be expected to be antagonists at the stomach gastrin receptor and this would also be of value for conditions involving excessive acid secretion.
CCK and gastrin peptides have trophic effects on the pancreas and various tissues of the gastro-intestinal tract (Johnson, ibid., pp 507-527), actions which are associated with increased DNA and RNA synthesis. Moreover, gastrin secreting cells are associated with certain gastrointestinal tumors as in the Zollinger-Ellison syndrome (Stadil, ibid., pp 729-739), and some colorectal tumors may also be gastrin/CCK dependent (Singh, Walker, Townsend and Thompson, Cancer Research 46:1612, 1986, and Smith, J. P., Gastroenterology 95:1541, 1988). Antagonists of CCK/gastrin receptors could therefore be of therapeutic value as antitumor agents.
The CCK peptides are widely distributed in various organs of the body including the gastrointestinal tract, endocrine glands, and the nerves of the peripheral and central nervous systems. Various biologically active forms have been identified including a 33-amino acid hormone and various carboxyl-terminus fragments of this peptide (e.g., the octapeptide CCK26-33 and the tetrapeptide CCK30-33). (G. J. Dockray, Br. Med. Bull. 38(3):253-258, 1982).
The various CCK peptides are thought to be involved in the control of smooth muscle contractility, exocrine and endocrine gland secretion, sensory nerve transmission, and numerous brain functions. Administration of the native peptides cause gall bladder contraction, amylase secretion, excitation of central neurons, inhibition of feeding, anticonvulsive actions and other behavioral effects. ("Cholecystokinin: Isolation, Structure and Functions," G. B. J. Glass, Ed., Raven Press, New York, 1980, pp 169-221; J. E. Morley, Life Sciences 27:355-368, 1980; "Cholecystokinin in the Nervous System," J. de Belleroche and G. J. Dockray, Ed., Ellis Horwood, Chichester, England, 1984, pp 110-127.)
The high concentrations of CCK peptides in many brain areas also indicate major brain functions for these peptides (G. J. Dockray,
Br. Med. Bull. 38(3):253-258, 1982). The most abundant form of brain CCK found is CCK26-33, although small quantities of CCK30-33 exist (Rehfeld and Gotterman, J. Neurochem. 32:1339-1341, 1979). The role of central nervous system CCK is not known with certainty, but it has been implicated in the control of feeding (Della-Fera and Baile, Science 206:471-473, 1979).
Currently available appetite suppressant drugs either act peripherally, by increasing energy expenditure (such as thyroxine), or in some other manner (such as the biguanides), or act by exerting a central effect on appetite or satiety.
Centrally acting appetite suppressants either potentiate central catecholamine pathways and tend to be stimulants (for example, amphetamine), or influence serotonergic pathways (for example, fenfluramine). Other forms of drug therapy include bulking agents which act by filling the stomach, thereby inducing a "feeling" of satiety.
CCK is known to be present in some cortical interneurones which also contain gamma-aminobutyric acid (GABA) (H. Demeulemeester et al, J. Neuroscience 8:988-1000, 1988). Agents that modify GABA action may have utility as anxiolytic or hypnotic agents (S. C. Harvey, The Pharmacological Basis of Therapeutics (7th ed.) 1985, pp 339-371, MacMillan). Thus, agents which modify CCK action may have parallel anxiolytic or hypnotic activities. Aminoacylglycolic and -lactic esters are known as pro-drugs of amino acids (C. G. Wermuth, Chemistry and Industry, 433-435, 1980). Pro-drugs and soft drugs are known in the art (E. Palomino, Drugs of the Future 15(4) 361-368, 1990). The last two citations are hereby incorporated by reference.
The role of CCK in anxiety is disclosed in TIPS 11:271-273, 1990). Stella, V. J., et al, "Prodrugs", Drug Delivery Systems, pp. 112-176, 1985 and Drugs 29:455-73, 1985 disclose the concept of pro-drugs. J. Med. Chem. 33:344-347, 1990, disclosed pro-drug half esters. None of the foregoing references discloses pro-drugs of CCK antagonists.
SUMMARY OF THE INVENTION
The effectiveness of an orally administered drug is dependent upon the drug's efficient transport across the mucosal epithelium and its stability in entero-hepatic circulation. Drugs that are effective after parenteral administration but less effective orally, or whose plasma half-life is considered too short, may be chemically modified into a pro-drug form.
A pro-drug is a drug which has been chemically modified and may be biologically inactive at its site of action, but which may be degraded or modified by one or more enzymatic or other in vivo processes to the parent bioactive form.
This chemically modified drug, or pro-drug, should have a different pharmacokinetic profile to the parent, enabling easier absorption across the mucosal epithelium, better salt formulation and/or solubility, improved systemic stability (for an increase in plasma half-life, for example). These chemical modifications may be
1) ester or amide derivatives which may be cleaved by esterases or lipases, for example,
2) peptides which may be recognized by specific or nonspecific proteinases,
3) derivatives that accumulate at a site of action through membrane selection of a pro-drug form or modified prodrug form, or any combination of 1 to 3 above.
Current research in animal experiments has shown that the oral absorption of certain drugs may be increased by the preparation of "soft" quaternary salts. The quaternary salt is termed a "soft" quaternary salt since, unlike normal quaternary salts, e.g., R--N + (CH 3 ) 3 , it can release the active drug on hydrolysis.
"Soft" quaternary salts have useful physical properties compared with the basic drug or its salts. Water solubility may be increased compared with other salts, such as the hydrochloride, but more important there may be an increased absorption of the drug from the intestine. increased absorption is probably due to the fact that the "soft" quaternary salt has surfactant properties and is capable of forming micelles and unionized ion pairs with bile acids, etc., which are able to penetrate the intestinal epithelium more effectively. The pro-drug, after absorption, is rapidly hydrolyzed with release of the active parent drug.
The invention relates to novel compounds which are pro-drugs of the formula ##STR1## and the pharmaceutically acceptable salts thereof wherein R 1 , R 2 , R 3 , R 4 , R 9 , R 12 , R 13 , A and Ar are as defined hereinbelow. Commonly owned U.S. Pat. Nos. 5,331,006, 5,593,967, 5,244,915, 5,397,788, 5,523,306, 5,264,419, 5,574,013 and 5,244,905, by Horwell, et al, the disclosures in which are herein incorporated by reference, disclose CCK antagonists.
The invention also relates to a pharmaceutical composition containing an effective amount of a compound according to formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for appetite suppression.
The compounds are also useful as anxiolytics, antipsychotics, especially for treating schizophrenic behavior, as agents in treating disorders of the extrapyramidal motor system, as agents for blocking the trophic and growth stimulating actions of CCK and gastrin, and as agents for treating gastrointestinal motility.
Compounds of the invention are also useful as analgesics and potentiate the effect of morphine. They can be used as an adjunct to morphine and other opioids in the treatment of severe pain such as cancer pain and reduce the dose of morphine in treatment of pain where morphine is contraindicated.
An additional use for compounds such as the iodinated compound of Example 6 is that the suitable radiolabeled derivative such as iodine-131 or iodine-127 isotope gives an agent suitable for treatment of gastrin dependent tumors such as those found in colonic cancers. I-125 radiolabelled compound of Example 6 can also be used as a diagnostic agent by localization of gastrin and CCK-B receptors in both peripheral and central tissue.
The invention further relates to a method of appetite suppression in mammals which comprises administering an amount effective to suppress appetite of the composition described above to a mammal in need of such treatment.
The invention also relates to a pharmaceutical composition for reducing gastric acid secretion containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for reducing gastric acid secretion.
The invention also relates to a method for reducing gastric acid secretion in mammals which comprises administering an amount effective for gastric acid secretion reduction of the composition described above to a mammal in need of such treatment.
The invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for reducing anxiety.
The invention also relates to a method for reducing anxiety in mammals which comprises administering an amount effective for anxiety reduction of the composition described above to a mammal in need of such treatment.
The Invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for treating gastrointestinal ulcers.
The invention further relates to a method for treating gastrointestinal ulcers in meals which comprises administering an amount effective for gastrointestinal ulcer treatment of the composition as described above to a mammal in need of such treatment.
The invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for treating psychosis, i.e., schizophrenia.
The invention further relates to a method for treating psychosis in meals which comprises administering an amount effective for treating psychoses of a composition as described above to a mammal in need of such treatment.
The invention also relates to pharmaceutical compositions effective for stimulating or blocking CCK or gastrin receptors, for altering the activity of brain neurons, for schizophrenia, for treating disorders of the extrapyramidal motor system, for blocking the trophic and growth stimulating actions of CCK and gastrin, and for treating gastrointestinal motility.
The invention also relates to a pharmaceutical composition for preventing the withdrawal response produced by chronic treatment or abuse of drugs or alcohol.
The invention further relates to a method for treating the withdrawal response produced by withdrawal from chronic treatment or withdrawal from abuse of drugs or alcohol. Such drugs include benzodiazepines, especially diazepam, cocaine, caffeine, opioids, alcohol, and nicotine. Withdrawal symptoms are treated by administration of an effective withdrawal treating amount of a compound of the instant invention.
The invention also relates to a pharmaceutical composition containing an effective amount of a compound of formula I in combination with a pharmaceutically acceptable carrier in unit dosage form effective for treating and/or preventing panic.
The invention also relates to a method for treating and/or preventing panic in mammals which comprises administering an amount effective for panic treatment and/or prevention of the composition described above to a mammal in need of such treatment.
The invention further relates to the use of the compounds of formula I to prepare pharmaceutical and diagnostic compositions for the treatment and diagnosis of the conditions described above.
The invention further provides processes for the preparation of compounds of formula I.
The invention further provides novel intermediates useful in the preparation of compounds of formula I and also provides processes for the preparation of the intermediates.
DETAILED DESCRIPTION
The compounds of the present invention are pro-drugs of compounds of formula I which are formed by the condensation of two modified amino acids and are therefore not peptides. Rather they are "dipeptoids", synthetic peptide-related compounds differing from natural dipeptides in that the substituent group R 2 is not commonly over hydrogen. The compounds are disclosed in copending commonly owned U.S. Ser. No. 545,222, filed Jun. 28, 1990, the disclosure of which is hereby incorporated by reference.
The compounds of the present invention are represented by the formula ##STR2## or a pharmaceutically acceptable salt thereof wherein:
R 1 is a cycloalkyl or polycycloalkyl hydrocarbon of from three to twelve carbon atoms with from zero to four substituents each independently selected from the group consisting of a straight or branched alkyl of from one to about six carbon atoms, halogen, CN, OR*, SR*, CO 2 R*, CF 3 , NR 5 R 6 , and --(CH 2 ) n OR 5 wherein R* is hydrogen, straight or branched alkyl of from one to six carbon atoms, --(CH 2 ) n Ar, --COAr, --(CH 2 ) n OCOAr, or --(CH 2 ) n NR 5 COAr and R* may also independently be R** as defined below,
and R** must be present at least once in formula I and R** is attached to formula I through a carbonyl and can include ##STR3## R 5 and R 6 are each independently hydrogen or alkyl of from one to about six carbon atoms and n is an integer from zero to six;
and R** is --(CH 2 ) n NR 5 R 6 , --(CH 2 ) n --B--D* wherein D* is O--COR*, CO 2 Ar 2 , (CH 2 ) n Ar 2 , OCOAr 2 , NR 5 COAr 2 , COAr 2 , CO 2 CH(R)--CO 2 R*, CO 2 --(CH 2 ) n OCOR* where Ar 2 is independently taken from Ar and where m is as defined below, CONHCH(R)CO 2 R* where R is a side chain of a biologically significant amino acid, R is hydrogen only when B is not a bond, --CO 2 CH 2 CH 2 N + (R*) 3 X 1- when X 1- is a pharmaceutically acceptable counter anion,
A is --(CH 2 ) n CO--, --SO 2 --, --S(═O)--, --NHCO--, ##STR4## --O--(CH 2 ) n CO-- or --HC═CHCO-- wherein n is an integer from zero to six;
R 2 is a straight or branched alkyl of from one to about six carbon atoms, --HC═CH 2 , --C.tbd.CH, --(CH 2 ) n --CH═CH 2 , --(CH 2 ) n C.tbd.CH, --(CH 2 ) n Ar, --(CH 2 ) n OR*, --(CH 2 ) n OAr, --(CH 2 ) n CO 2 R*, or --(CH 2 ) n NR 5 R 6 wherein n, R*, R 5 and R 6 are as defined above and Ar is as defined below;
R 3 and R 4 are each independently selected from hydrogen, R 2 and --(CH 2 ) n' --B--D wherein:
n' is an integer of from zero to three;
B is a bond, ##STR5## wherein R 7 and R 8 are each independently selected from hydrogen and R 2 or together form a ring (CH 2 ) m wherein m is an integer of from 1 to 5 and n is as defined above;
D is hydrogen,
--COOR*,
--CH 2 NR 5 R*,
--CHR 2 NR 5 R*,
--CH 2 OR*,
--CHR 2 OR*,
--CH 2 SR*,
--CHR 2 SR*,
--CONR 5 R 6 ,
--CONR 5 R* ,
an acid replacement selected from ##STR6## wherein m is an integer of from 0 to 2 wherein R*, R 2 , R 5 , and R 6 are as defined above;
R 9 is hydrogen or a straight or branched alkyl of from one to about six carbon atoms, --(CH 2 ) n CO 2 R*, --(CH 2 ) n NR 5 R*, wherein n, R*, and R 5 are as defined above or taken from R 3 ;
R 12 and R 13 are each independently hydrogen or are each independently taken with R 3 and R 4 , respectively, to form a moiety doubly bonded to the carbon atom; and
Ar is a mono- or polycyclic unsubstituted or substituted carbo- or heteroaromatic or carbo- or heterohydroaromatic moiety.
Preferred Ar is 2- or 3-thienyl, 2- or 3-furanyl, 2-, 3-, or 4-pyridinyl or an unsubstituted or substituted benzene ring ##STR7## wherein E and F are each independently R 3 as defined above, hydrogen, fluorine, chlorine, bromine, iodine, methyl, methoxy, trifluoromethyl, or nitro.
Especially preferred Ar is from R 3 as defined as the ortho (2-) position of the ring, for example, ##STR8##
Preferred cycloalkyl or polycycloalkyl substituents have from six to ten carbon atoms.
Preferred compounds of the instant invention are those wherein cycloalkyl or polycycloalkyl is independently R*, F, Cl, Br, OR*, NR 5 R*, CF 3 , SR*.
Other preferred compounds of the instant invention are those wherein polycycloalkyl is selected from the group consisting of ##STR9## wherein W, X, Y, and Z are each independently hydrogen, a straight or branched alkyl of from one to six carbon atoms, CF 3 , NR 5 R 6 , --(CH 2 ) n CO 2 R*, CN, F, Cl, Br, OR*, SR*, wherein R*, R 5 and R 6 are as defined in Claim 1 and n is an integer of from 1 to 3.
Other preferred compounds of the instant invention are those wherein
R 1 is 2-adamantyl or 1-(S)-2-endobornyl;
A is --NHCO--, --OCO--, --SO 2 --, --S(═O)-- or --CH 2 CO--;
R 2 is --CH 3 , --CH 2 D* or --CH 2 C.tbd.CH;
R 3 is --(CH 2 ) n '--B--D or H;
R 4 is --(CH 2 ) n '--B--D or H; and
R 9 is hydrogen or methyl.
More preferred compounds of the instant invention are those wherein
R 1 is 2-adamantyl or 1-(S)-2-endobornyl, ##STR10## A is --O--C--, R 2 is --CH 3 ;
R 3 is H, --CH 2 OH, --CH 2 OCOCH 2 CH 2 D*, --CH 2 SCH 2 CH 2 D*, --CH 2 SCH 2 D, --CH 2 D*, --CH 2 OCOCH═CHD* or --CH 2 NHCOCH 2 CH 2 D*, or --CH 2 NHCOCH═CHD* and
R 4 is H, --NHCOCH 2 CH 2 D*, ( D! configuration or --NHCOCH═CHD* ( D! configuration).
The D and the L configurations are possible at the chiral centers and are included in the scope of the invention:
1. Preferred is when R 2 is --CH 3 D ! configuration;
2. Preferred is when R 3 is --CH 2 OCOCH 2 CH 2 D* or --CH 2 NHCOCH 2 CH 2 D* with the D! configuration at the Trp α-carbon atom and the L! configuration at the Phe-α-carbon atom; and
3. Preferred is when R 4 is --NHCOCH 2 CH 2 D* D! configuration or NHCOCH═CHD* D! configuration with the D! configuration at the Trp α-carbon atom.
Preferred compounds of the instant invention are pro-drugs of the following:
1S- 1α,2β S* S*(E)!!,4α!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo- 2.2.1!hept-2-yl)oxy!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid,
1S- 1α,2β S*(S*)!,4α!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo- 2.2.1!hept-2-yl)oxy!carbonyl!amino!propyl!methyl -amino!-1-phenylethyl!amino!-4-oxobutanoic acid,
1S- 1α,2β S*(S*)!,4α!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo- 2.2.1!hept-2-yl)amino!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid,
R-(R*,R*)!-4- 2- 3-(1H-indol-3yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-ylsulfonyl)amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid,
R-(R*,S*)!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-ylsulfonyl) amino!propyl!amino!-3-phenylpropyl!amino!-4-oxobutanoic acid,
1R- 1α R*(S*)!,2β!! and 1S- 1α!S*(R*)!,2β!!-4- 2- 2- (2-fluorocyclohexyl)oxy!carbonyl!amino!-3-(1H-indol-3-yl)-2-methyl-1-oxopropyl!amino!-3-phenylpropyl!amino!-4-oxobutanoic acid,
1R- 1α R*(S*)!,2β!! and 1S- 1α S*(R*)!,2β!!-4- 2- 2- (2-fluorocyclohexyl)oxy!carbonyl!amino!-3-(1H-indol-3-yl)-2-methyl-1-oxopropyl!methylamino!-3-phenylpropyl!amino!-4-oxobutanoic acid,
1R- 1α R*(S*)!,2β!! and 1S- 1α S*(R*)!,2β!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- 2-(trifluoromethyl)cyclohexyl!oxy!carbonyl!amino!propyl!-amino!3-phenylpropyl!-amino!-4-oxobutanoic acid,
1R- 1α R*(S*)!,2β!! and 1S- 1α S*(R*)!,2β!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- 2-(trifluoromethyl)-cyclohexyl!oxy!carbonyl!amino!-propyl!methylamino!-3-phenylpropyl!amino!-4-oxobutanoic acid,
R-(R*,S*)!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonly!-amino!propyl!methylamino!-3-phenylpropyl!amino!-4-oxobutanoic acid,
1S- 1α,2β S*(R*)!,4α!!- 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 1-oxo-3-(1H-tetrazol-5-yl)propyl!amino!-1-(phenylmethyl)ethyl!amino!ethyl!-carbamic acid, 1,7,7-trimethylbicyclo 2.2.1!hept-2-yl ester,
1S- 1α,2β S*(R*)!,4α!!- 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 1-oxo-3-(1H-tetrazol-5-yl)-propyl!amino!-2-phenylethyl!amino!ethyl!carbamic acid, 1,7,7-trimethyl-bicyclo 2.2.1!hept-2-yl ester,
N- 2-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanylglycine,
N- 2-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl-β-alanine.
In addition preferred compounds of the instant invention are pro-drugs of:
2-methylcyclohexyl 2- 1-(hydroxymethyl)-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!carbamate,
2- 2- (2-chlorocyclohexyl)oxy!carbonyl!amino!-3-(1H-indol-3-yl)-2-methyl-1-oxopropyl!amino!-3-phenylpropyl butanedioate,
2- 2- (2-methylcyclohexyl)oxy!carbonyl!amino!-3-(1H-indol-3-yl)-2-methyl-1-oxopropyl!amino!-3-phenylpropyl butanedioate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 2- 1-(hydroxymethyl)-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!carbamate,
2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-3-phenylpropyl butanedioate,
2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl butanedioate,
R-(R*,R*)!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid,
1S- 1α,2β S*(S*)!,4α!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo-2.2.1!hept-2-yl)oxy!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid,
R- R*,S*-(E)!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!amino!-4-oxo-2-butenoic acid,
R-(R*,S*)!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!amino!-4-oxobutanoic acid,
(R)-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2- methyl(2-phenylethyl)amino!-2-oxoethylcarbamate,
R-(R*,S*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-3-phenylpropyl!sulfinyl!acetic acid, ethyl ester,
R-(R*,S*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-3-phenylpropyl!sulfonyl!acetic acid, ethyl ester,
R-(R*,S*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-3-phenylpropyl!sulfinyl!acetic acid,
R- R*,R*-(E)!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid,
R-(R*,S*)!- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-3-phenylpropyl!thio!acetic acid,
1S- 1α,2β S* S*(E)!!,4α!!-4- 2- 3-(1H-indol-3yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo -2.2.1!hept-2-yl)oxy!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid, methyl ester, (Bicyclo system is 1S-endo),
1S- 1α,2β S* S*(E)!!,4α!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo 2.2.1!hept-2-yl)oxy!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid, (Bicyclo system is 1S-endo),
R-(R*,R*)!-3- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-3-oxo-propanoic acid,
R-(R*,S*)!-3-(1H-indol-3-ylmethyl)-3-methyl-4,10-dioxo-6-(phenylmethyl)-11-oxo-8-thia-2,5-diazatridecanoic acid, tricyclo 3.3.1.1 3 ,7 !dec-2-yl or ester,
R-(R*,S*)!-β- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!benzenebutanoic acid,
R-(R*,S*)!-N- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-4-phenylbutyl!glycine,
R- R*,S*-(E)!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (bicyclo 3.3.1!non-9-yloxy)carbonyl!amino!-1-oxopropyl!-amino!-3-phenylpropyl!amino!-4-oxo-2-butenoic acid,
mono R-(R*,R*)!-2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!-1-phenylethyl butanedioate,
3- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-1-oxo-2-phenylpropyl!amino!propanoic acid (TRP is R, other center is RS),
1R- 1α, R*(S*)!,2β!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!-amino!-3-phenylpropyl!amino!-4-oxo-2-butenoic acid, (-)-Isomer,
1R- 1α R*(S*)!,2β!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!-amino!-3-phenylpropyl!amino!-4-oxobutanoic acid, (-)-Isomer,
1R- 1α R*(S*)!,2β!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!-amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid, (-)-isomer,
1R- 1α R*(S*)!,2β!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!-amino!-1-phenylethyl!amino!-4-oxobutanoic acid, (-)-Isomer,
2-methylcyclohexyl- 1R- 1α R*(S*)!!,2β!- 2- 1-(hydroxymethyl)-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!carbamate,
R- R*,S*-(E,E)!!-6- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!-amino!-7-phenyl-2,4-heptadienoic acid,
R-(R*,R*)!- 2- 2- 1,4-dioxo-4-(1H-tetrazol-5-ylamino)-butyl!amino!-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!carbamic acid,
tricyclo- 3.3.1.1 3 ,7 !dec-2-yl- S- R*,S*-(E)!!-12-(1H-indol-3-ylmethyl)-12-methyl-3,11-dioxo-9-(phenylmethyl)-2-oxa-7,10,13-triazatetradec-4-en-14-oate,
R-(R*,S*)!-3- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!-amino!-3-phenylpropyl!amino!-3-oxopropanoic acid,
ethyl R-(R*,S*)!- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-3-phenylpropyl!thio!acetate,
R-(R*,S*)!-β- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-4-iodo-benzenebutanoic acid,
R-(R*,R*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1(tricyclo (3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-1-phenylethoxy!acetic acid,
3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo(3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-2-phenylpropyl!amino!acetic acid (TRP center is R, other center is RS),
(R)- 2- 3-(1H-indol-3-yl)-1-oxo-2-methyl-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethylidene!amino!oxy!acetic acid,
R-(R*,S*)!-β- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!-amino!benzenebutanoic acid,
R-(R*,S*)!-N- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!propyl!amino!-4-phenylbutyl!glycine,
2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!carbonyl!cyclopropanecarboxylic acid (cyclopropane ring is trans-(±) other centers are R),
carbamic acid, 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 1-oxo-3-(1H-tetrazol-5-yl)propyl!amino!-2-phenylethyl!-amino!ethyl!-,tricyclo 3.3.1.1 3 ,7 !dec-2-yl ester, R,(R*,S*!-,
benzeneheptanoic acid, α- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-, R-(R*,S*)!-,
methyl-(±)-β- (2-phenylethyl)amino!carbonyl!-1β- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-1H-indole-3-butanoate,
R-(R*,S*)!-4- 2-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo 3.3.1.1 3 ,7 !dec-2-yloxylcarbonyl!amino!propyl!-amino!-3-phenylpropyl!amino!-4-oxo-2-butenoic acid,
bicyclo 2.2.1!heptane-2-acetic acid, 3- 2- 1-(hydroxymethyl)-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!amino!carbonyl!oxy!-4,7,7-trimethyl-, 1R- 1α,2β,3α R*(S*)!,4α!!-,
butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!-amino!-1-oxopropyl!-amino!-1-phenylethyl!amino!-4-oxo- 1R- 1α R*(R*)!2β!!-((-)-isomer),
2-butenoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!-amino!-1-phenylethyl!amino!-4-oxo-, 1R- 1α R*(R*)!,2β!!-((-)-isomer),
butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!-amino!-3-phenylpropyl!amino!-4-oxo- 1R- 1α R*(S*)!,2β!!-((-)-isomer), and
2-butenoic acid, 4- 2- 3-)1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!-amino!-3-phenylpropyl!amino!-4-oxo- IR 1α R*(S*)!,2β!!-((-)-isomer).
Additionally preferred are the pro-drugs of the compounds:
3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo 3.3.1.1 3 ,7 !-dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-2-phenylpropyl!-amino!acetic acid, (TRP center is R, other center is RS),
R-(R*,R*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo 3.3.1.1.sup.3,7 !dec-yloxy)carbonyl!amino!propyl!amino!-1-phenylethoxy!acetic acid,
1R- 1α,2β R*(R*)!!!-2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!carbonyl!cyclopropane carboxylic acid,
1S- 1α-2β S*(S*)!!!-2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonylamino!propyl!amino!-1-phenylethyl!amino!carbonylcyclopropane carboxylic acid,
R-R*,R*)!-3- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethoxy!propanoic acid,
R-R*,R*)!-mono 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-1-phenylethyl butanedioic acid,
3- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-2-phenylpropyl!amino!propanoic acid, (TRP is R, other center is RS),
R-(R*,S*)!-β- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-4-iodobenzenebutanoic acid,
1R-1α R*(S*)!,2β!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!amino!-3-phenyl -propyl!amino!-4-oxo-2-butenoic acid, ((-)-isomer),
1R- 1α R*,(S*)!,2B!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!amino!-3-phenylpropyl!amino!-4-oxobutanoic acid, ((-)-isomer,
1R-1α R*(R*) ,2β!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!amino-1-phenylethyl!amino!-4-oxo-2-butenoic acid, ((-)-isomer),
1R- 1α R*(R*)!,2β!!-4- 2- 3-1H-indol-3-yl)-2-methyl-2- (2-methyl-1-cyclohexyl)oxy!carbonyl!amino!-1-oxopropyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid, ((-)-isomer),
R-(R*,S*)!-1g- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-benzeneheptanoic acid,
2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!carbonyl!cyclopropanecarboxylic acid, (cyclopropyl ring is trans-(±), other centers are R),
2-methylcyclohexyl 1R- 1α R*(S*)!!,2β!- 2- 1-hydroxymethyl)-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!-carbamate,((-)-isomer),
R- R*,S*-(E,E)!!-6- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-7-phenyl-2,4-heptadienoic acid,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 2- 1 (hydroxymethyl)-2-hydroxy-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methylethyl!carbamate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl R-(R*,R*)!- 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 1-oxo-3-(1H-tetrazol-5-yl)propyl!amino!-2-phenylethyl!amino!ethyl!carbamate,
R-(R*,S*)!-2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!sulfinyl!acetic acid,
R-(R*,S*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-3-phenylpropyl sulfonyl!acetic acid,
Ethyl R-(R*,S*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)!carbonyl!amino!propyl!amino!-3-phenylpropyl!sulfonyl!acetate
2-chlorocyclohexyl 2- 1-(hydroxymethyl)-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!carbamate, Isomer II, (ring centers are trans, trp center is D, other center is S), ((-) or (+) form),
R- R*,R*(E)!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-ylamino)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid,
R-(R*,R*)!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid,
R-(R*,S*)!-mono 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!butanediote,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl R-(R*,S*)- 2- 1-(hydroxymethyl)-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!-carbamate,
1S- 1α,2β S* S*(E)!!,4α-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo 2.2.1!hept -2-yl)oxy!carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid (bicyclo system is 1S-endo),
1S- 1α,2β S*(S*)!,4α!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (1,7,7-trimethylbicyclo 2.2.1.1!hept-2-yl)oxy!carbonyl!-amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid (bicyclo system is 1S-endo),
R- R*,S*-(E)!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!amino!-4-oxo-2-butenoic acid,
N- 2-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanylglycine,
R-(R*,S*)!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!amino!-4-oxobutanoic acid,
R-(R*,R*)!- 2- 2- 1,4-dioxo-4-(1H-tetrazol-5-ylamino)butyl!-amino!-2-phenylethyl!amino!-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl!carbamic acid,
R-(R*,R*)!-3- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sub.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-3-oxopropanoic acid,
R-(R*,S*)!-3- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!amino!-3-oxopropanoic acid,
R- R*,S*-(E)!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-2- (bicyclo 3.3.1.1!non-9-yloxy)carbonyl!amino!-1-oxopropyl!amino!-3-phenylpropyl!amino!-4-oxo-2-butenoic acid,
R-(R*,S*)!-5- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!amino!-5-oxopentenoic acid,
Ethyl R-(R*,S*)!- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!sulfinyl!acetate,
R- R*,R*-(E)!!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!4-oxo-2-butenoic acid,
R-(R*,S*)!-N- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-4-phenylbutyl!-β-alanine,
N- N- α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl!-L-alanine,
R-R*,S*)!-3- 2- 3-1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1.sup.3,7 !dec-2-yloxy)carbonyl!amino!propyl!aminoα-3-phenylpropyl!thio!propanoic acid,
R-(R*,S*)!- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl!thio!acetic acid,
R-(R*,S*)!-β- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-benzenebutanoic acid,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl R-(R*,S*)!-3-(1H-indol-3-ylmethyl)-3-methyl-4,10-dioxo-6-(phenylmethyl)-11-oxa-8-thia-2,5-diazatridecanoic acid,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3,17,17-trimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanoate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaeicosanedioate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3,17,17-trimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanedioate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 16-ethyl-3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12-trioxo-7-phenyl-13-oxa-2,5,8,16-tetraazaoctadecanoate,
bis(tricyclo 3.3.1.1 3 ,7 !dec-2-yl) 3,25-bis(1H-indol-3-ylmethyl)-3,25-dimethyl-4,9,12,16,19,24-hexaoxo-7,21-diphenyl-13,15-dioxa-2,5,8,20,23,26-hexaazaheptacosanedioate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaheptadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanoate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,6,11-trioxo-9-phenyl-13,15-dioxa-2,5,7,10-tetraazatetraadecandioate, 14-anhydride with 2-methylpropanoic acid,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaeicosanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7,16-diphenyl-13,15-dioxa-2,5,8-triazahexadecanoate,
2,3-dihydro-1H-inden-5-yl 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!-amino!-4-oxobutanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 14-(2,2-dimethyl-1,3-dioxolan-4-yl)-3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12-trioxo-7-phenyl-13-oxa-2,5,8-triazatetradecanoate,
1-ethyl 16-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 14-(1H-indol-3-ylmethyl)-3,14-dimethyl-5,8,13-trioxa-10-phenyl-2,4-dioxa-9,12,15-triaazahexadecanedioate,
1,3-dihydro-3-oxo-1-isobenzofuranyl 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo- 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 17-amino-3-(1H-indol-3-ylmethyl)-3,18-dimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanedioate,
19-methyl 1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 17-amino-3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanedioate,
N 5 - 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!-L-glutamine,
N 5 - 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!methyl!-L-glutamine,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 2- (propylamino)acetyl!amino!phenyl!ethyl!amino!ethyl!carbamate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 2- (propylamino)acetyl!amino!methyl!phenyl!ethyl!amino!ethyl!carbamate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2- 2- 2- (1-methyl-3-oxo-1-butenyl)amino!phenyl!ethyl!amino!-2-oxoethyl!carbamate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2- 2- 2- (1-methyl-3-oxo-1-butenyl) amino!methyl!phenyl!ethyl!amino!-2-oxoethyl!carbamate,
ethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!amino!-2-butenoate,
ethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!methyl!amino!-2-butenoate,
1,1-dimethylethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!amino!-2-butenoate, and
1,1-dimethylethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!methyl!amino!-2-butenoate.
Most especially preferred compounds of the instant invention are:
L-glutamic acid, N- N- α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl!-,
2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2 tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl(R-(R*,S*)!-1,4-dihydro-1-methyl-3-pyridinecarboxylate,
2- (3-(1H-indol-3-yl)-2-methyl-1-oxo-2 (tricyclo 3.3.1.1 3 .7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl R-(R*,S*)!-trigonelline iodide, and
2- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl R-(R*,S*)!-3-pyridinecarboxylate.
Also preferred compounds are:
1,2-dihydro-2-methyl-4-isoquinolinecarboxylic acid, 3-(1H-indol-3-ylmethyl)-3-methyl-1,4,9,12-tetraoxo-7-phenyl-1-(tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)-13-oxa-2,5,8-triazapentadec-15-yl ester,
4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid, 2- (1,4-dihydro-1-methyl-3-pyridinyl)carbonyl!amino!ethyl ester,
4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid, 2- (1,2-dihydro-2-methyl-4-isoquinolinyl)carbonyl!amino!ethyl ester,
1,2-dihydro-2-methyl-4-isoquinolinecarboxylic acid, 3-(1H-indol-3-ylmethyl)-3-methyl-1,4,9,12-tetraoxo-7-phenyl-1(tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)-13-oxa-2,5,8-triazapentadec-10-en-15-yl ester,
4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2-butenoic acid, 2- (1,4-dihydro-1-methyl-3-pyridinyl)carbonyl!amino!ethyl ester,
1,4-dihydro-1-methyl-3-pyridinecarboxylic acid, 2- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-4-phenylbutoxy!ethyl ester,
1,4-dihydro-1-methyl-3-pyridinecarboxylic acid, 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-3-phenylpropyl ester,
1,4-dihydro-1-methyl-3-pyridinecarboxylic acid, 3-(1H-indol-3-ylmethyl)-3-methyl-1,4,9,12-tetraoxo-7-phenyl-1-(tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)-13-oxa-2,5,8-triazapentadec-15-yl ester,
1,4-dihydro-1-methyl-3-pyridinecarboxylic acid, 3-(1H-indol-3-ylmethyl)-3-methyl-1,4,9,12-tetraoxo-7-phenyl-1-(tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)-13-oxa-2,5,8-triazatetradec-14-yl ester,
1,4-dihydro-1-methyl-3-pyridinecarboxylic acid, 3-(1H-indol-3-ylmethyl)-3-methyl-1,4,9,12-tetraoxo-7-phenyl-1-(tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)-13-oxa-2,5,8-triazapentadec-10-en-15-yl ester,
1,4-dihydro-1-methyl-3-pyridinecarboxylic acid, 3-(1H-indol-3-ylmethyl)-3-methyl-1,4,9,12-tetraoxo-7-phenyl-1-(tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)-13-oxa-2,5,8-triazatetradex-10-en-14-yl ester,
butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-, (2,2-dimethyl-1-oxopropoxy)methyl ester, R-(R*,R*)!-,
butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!amino!-4-oxo-, chloromethyl ester, R-(R*,R*)!-,
pentanedioic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-1,4-dioxobutoxy!methyl ester, R-(R*,R*)-, compd. with 1-deoxy-1-(methylamino)-D-glucitol,
butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2,3-dihydro-1H-inden-5-yl ester, R-(R*,R*)!-, and
butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-, 2-(diethylamino)ethyl ester, R-(R*,R*)!-.
The compounds of the present invention include compounds of formula I wherein the indole moiety is a 2- or 3-indolyl.
The compounds include solvates and hydrates and pharmaceutically acceptable salts of the compounds of formula I.
The compounds of the present invention can have multiple chiral centers including those designated in the above formula I by a , , depending on their structures. For example, when R 3 taken with R 12 and R 4 taken with R 13 form double bonds to these carbon atoms they are no longer chiral. In addition, centers of asymmetry may exist on substituents R 1 , R 9 , R 3 , R 4 and/or Ar. In particular the compounds of the present invention may exist as diastereomers, mixtures of diastereomers, or as the mixed or the individual optical enantiomers. The present invention contemplates all such forms of the compounds. The mixtures of diastereomers are typically obtained as a result of the reactions described more fully below. Individual diastereomers may be separated from mixtures of the diastereomers by conventional techniques such as column chromatography or repetitive recrystallizations. Individual enantiomers may be separated by convention method well known in the art such as conversion to a salt with an optically active compound, followed by separation by chromatography or recrystallization and reconversion to the nonsalt form.
Biologically significant amino acids are illustrated in Table I below.
TABLE I______________________________________Biologically Significant Amino Acids*______________________________________Alanine Isoleucineβ-Alanine IsovalineAlloisoleucine LeucineAllthreonine LysineArginine MethionineAsparagine NorleucineAspartic Acid NorvalineCysteine OrnithineGlutamic Acid PhenylalanineGlutamine ProlineGlycine SerineHistidine ThreonineHomocysteine TyrosineHomosexine Tryptophan Valine______________________________________ *The side of alanine is CH.sub.3- and of aspartic acid is HOOC--CH.sub.2 -- and so forth.
Pharmaceutically acceptable counter cations or anions are shown below:
Acetate, benzenesulfonate, benzoate, bicarbonate, bitartrate, bromide, calcium acetate, camsylate, carbonate, chloride, citrate, dihydrochloride, edetate, edisylate, estolate, esylate, fumarate, glucaptate, gluconate, glutamate, glycollylarsanilate, hexylresorcinate, hydrabamine, hydrobromide, hydrochloride, hydrochloride, hydroxynaphthoate, iodide, isethionate, lactate, lactobionate, malate, maleate, mandelate mesylate, methylbromide, methylnitrate, methylsulfate, mucate, napsylate, nitrate, pamoata (embonate), pantothenate, phosphate/diphosphate, polygalacturonate, salicylate, stearate, subacetate, succinate, sulfate, tannata, tartrate, teoclate, triethiodide, benzathine, chloroprocaine, choline, diethanolamine, ethylenediamine, meglumine, procaine, aluminum, calcium, lithium, magnesium, potassium, sodium, and zinc.
The compounds of the present invention can be formed by coupling individual substituted α-amino acids by methods well known in the art. (See, for example, standard synthetic methods discussed in the multi-volume treatise "The Peptides, Analysis, Synthesis, Biology," by Gross and Meienhofer, Academic Press, New York.) The individual substituted alpha amino acid starting materials are generally known or, if not known, may be synthesized and, if desired, resolved by methods within the skill of the art. (Synthesis of racemic DL!-α-methyl tryptophan methyl ester--see Brana, M. F., et al, J. Heterocyclic Chem. 17:829, 1980.)
A key intermediate in the preparation of compounds of formula I is a compound of formula ##STR11## wherein R is selected from R 1 , 9-fluorenylmethyl, Bz and other suitable N-blocking groups. These are useful as intermediates in the preparation of compounds of formula I. The compounds wherein R is 1-adamantyl, 2-adamantyl, 4-protoadamantyl, exo-bornyl, endo-bornyl, exo-norbornyl, endo-norbornyl, 2-methylcyclohexyl, 2-chlorocyclohexyl, or camphoryl are novel and are preferred.
The disclosure of U.S. Pat. No. 4,757,151 is hereby incorporated by reference. It describes the 9-fluorenylmethyl blocking group.
Compounds of formula II are prepared by reacting
ROH III
wherein R is as defined above, with phosgene or a phosgene substitute to produce a corresponding compound of formula
ROCOCl IV
and then reacting a compound of formula IV with α-methyl-tryptophan to produce the desired compound of formula II above.
Alternatively, a compound of formula IV can be reacted with an α-methyltryptophan methyl ester to produce ##STR12## which can be converted to a compound of formula II by known means such as hydrolysis with aqueous lithium hydroxide.
Novel intermediates of the instant invention include compounds of formula ##STR13## wherein n=1-3 and ##STR14##
This includes also α positions in both formulae. Further, the moiety of formula VIII ##STR15## provides novel intermediates.
The compounds in Schemes I and Ia below were prepared by solution synthesis, from the C-terminus, using standard peptide protocols, and illustrated by the synthesis of 2-adamantyloxycarbonyl-D-a-methyltryptophenyl-L-alanyl-β-alanine (6a) (see Scheme I). ##STR16##
Reagents and conditions:
i) WSCDJ(DCCI), HOSt.H 2 O, DIPEA, CH 2 Cl 2 (EtOAc)
ii) TsOH.H 2 O, CH 2 Cl 2 -THF or TFA, CH 2 Cl 2
iii) 0.1N OH - , THF
iv) 10% Pd--C, MeOH, 1,4 cyclohexadiene
Scheme Ia below describes synthetic steps towards compounds of type 10 and 11, a, k, l Examples 5-10 inclusive. S-2-tert-Butyloxycarbonylamino-3-phenylpropionic acid 7 was condensed with, for example, glycine ethyl ester 2k to give the amide 8k. Removal of the tBoc protecting group with trifluoroacetic acid gave the free amine 9k which was condensed with 2-adamantyloxycarbonyl-R-α-methyltryptophan to give 10k (Example 6) which was saponified using lithium hydroxide to the carboxylic acid 11k (Example 9). ##STR17##
Scheme III below illustrates procedures for preparing final products of the instant invention. The following compounds can be prepared using Method A:
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3,17,17-trimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanoate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaeicosanedioate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3,17,17-trimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanedioate,
bis(tricyclo 3.3.1.1 3 ,7 !dec-2-yl) 3,25-bis(1H-indol-3-ylmethyl)-3,25-dimethyl-4,9,12,16,19,24-hexaoxo-7,21-diphenyl-13,15-dioxa-2,5,8,20,23,26-hexaazaheptacosanedioate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaheptadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanoate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,6,11-trioxo-9-phenyl-13,15-dioxa-2,5,7,10-tetraazatetraadecandioate, 14-anhydride with 2-methylpropanoic acid,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaeicosanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7,16-diphenyl-13,15-dioxa-2,5,8-triazahexadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 17-amino-3-(1H-indol-3-ylmethyl)-3,18-dimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanedioate, and
19-methyl 1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 17-amino-3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanedioate.
The following compounds can be prepared using Method B:
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3,17,17-trimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaheptadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaoctadecanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanoate,
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,6,11-trioxo-9-phenyl-13,15-dioxa-2,5,7,10-tetraazatetraadecandioate, 14-anhydride with 2-methylpropanoic acid,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazaeicosanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7,16-diphenyl-13,15-dioxa-2,5,8-triazahexadecanoate,
1-ethyl 16-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 14-(1H-indol-3-ylmethyl)-3,14-dimethyl-5,8,13-trioxa-10-phenyl-2,4-dioxa-9,12,15-triaazahexadecanedioate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 17-amino-3-(1H-indol-3-ylmethyl)-3,18-dimethyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanedioate, and
19-methyl 1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 17-amino-3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12,16-tetraoxo-7-phenyl-13,15-dioxa-2,5,8-triazanonadecanedioate.
The following compounds can be prepared using Method C:
1-tricyclo 3.3.1.1 3 ,7 !dec-2-yl 16-ethyl-3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12-trioxo-7-phenyl-13-oxa-2,5,8,16-tetraazaoctadecanoate,
2,3-dihydro-1H-inden-5-yl 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 14-(2,2-dimethyl-1,3-dioxolan-4-yl)-3-(1H-indol-3-ylmethyl)-3-methyl-4,9,12-trioxo-7-phenyl-13-oxa-2,5,8-triazatetradecanoate, and
1,3-dihydro-3-oxo-1-isobenzofuranyl 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoate.
The following compounds can be prepared using Method D:
N 5 - 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!ethyl!phenyl!-L-glutamine,
N 5 - 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!methyl!-L-glutamine,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 2- (propylamino)acetyl!amino!phenyl!ethyl!amino!ethyl!carbamate, and
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2-oxo-2- 2- 2- (propylamino)acetyl!amino!methyl!phenyl!ethyl!amino!ethyl!carbamate.
The following compounds can be prepared using Method E:
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2- 2- 2- (1-methyl-3-oxo-1-butenyl)amino!phenyl!ethyl!amino!-2-oxoethyl!carbamate,
tricyclo 3.3.1.1 3 ,7 !dec-2-yl 1-(1H-indol-3-ylmethyl)-1-methyl-2- 2- 2- (1-methyl-3-oxo-1-butenyl)amino!methyl!phenyl!ethyl!amino!-2-oxoethyl!carbamate,
ethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!amino!-2-butenoate,
ethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!methyl!amino!-2-butenoate,
1,1-dimethylethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!amino!-2-butenoate, and
1,1-dimethylethyl 3- 2- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!phenyl!methyl!amino!-2-butenoate. ##STR18##
BIOLOGICAL ACTIVITY
The biological activity of compounds of the present invention was evaluated employing an initial screening test which rapidly and accurately measured the binding of the tested compound to known CCK receptor sites. Specific CCK receptors have been shown to exist in the central nervous system. (See Hays et al, Neuropeptides 1:53-62, 1980; and Satuer et al, Science 208:1155-1156, 1980).
In this screening test, the cerebral cortices taken from male CFLP mice weighing between 30-40 g were dissected on ice, weighed, and homogenized in 10 volumes of 50 mM Tris-HCl buffer (pH 7.4 at 0°-4° C.). The resulting suspension was centrifuged, the supernate was discarded, and the pellet was washed by resuspension in Tris-HCl buffer followed by recentrifugation. The final pellet was resuspended in 20 volumes of 10 nM Hepes buffer (pH 7.2 at 23° C.) containing 130 mM NaCl, 4.7 nM KCl, 5 nM MgCl 2 , 1 nM EDTA, 5 mg/mL bovine albumin, and bacitracin (0.25 mg/mL).
In saturation studies, cerebral cortical membranes were incubated at 23° C. for 120 minutes in a final volume of 500 μL of Hepes incubation buffer (pH 7.2) together with 0.2-20 nM tritiated-pentagastrin (Amersham International, England).
In the displacement experiments, membranes were incubated with a single concentration (2 nM) of iigand, together with increasing concentrations (10 -11 to 10 -14 M) of competitive test compound. In each case, the nonspecific binding was defined as that persisting in the presence of the unlabeled octapeptide CCK 26-33 (10 -6 M).
Following incubation, radioactivity bound to membranes was separated from that free in solution by rapid filtration through Whatman GF/B filters and washed three times with 4 mL of ice cold Tris-HCl buffer. Filters from samples incubated with tritiated-pentagastrin were placed in polyethylene vials with 4 mL of scintillation cocktail, and the radioactivity was estimated by liquid scintillation spectrometry (efficiency 47-52%).
The specific binding to CCK receptor sites was defined as the total bound tritiated-pentagastrin minus the amount of tritiated-pentagastrin bound in the presence of 10 -6 octapeptide, CCK 26-33 .
Saturation curves for specific tritiated-pentagastrin binding to mouse cortical membranes were analyzed by the methods of Scatchard (Ann. New York Acad. Sci. 51:660-672, 1949, and Hill (J. Physiol. 40:IV-VIII, 1910, to provide estimates for the maximum number of binding sites (B max ) and the equilibrium dissociation constant (K a ).
In displacement experiments, inhibition curves were analyzed by either logit-log plots or the iterative curve fitting computer program ALLFIT (DeLean, Munson and Redbard, 1978) to provide estimates of the IC 50 and nH (apparent Hill coefficient) values). (IC 50 values were defined as the concentration of test compound required to produce 50% inhibition of specific binding.)
The inhibition constant (K i ) of the test compound was then calculated according to the Cheng-Prusoff equation: ##EQU1## where L! is the concentration of radiolabel and K a is the equilibrium dissociation constant.
The K i values for several representative compounds are presented in Table II below.
TABLE II______________________________________Compound* Receptor AffinityNumber CCI-B/nM n______________________________________ 6a 27.9 ± 4.1 3 6h 1170 2 6i 1520 1 6j 7.41 ± 1.04 3 5f 110 2 5d 173 210a 21.2 ± 5.4 310k 17.9 110l 66.4 211a 9.44 211k 4.4 ± 0.6 311l 10.6 ± 0.12 3______________________________________ *Compound as numbered in Schemes I and IA. n = Number of assays
Compounds of the present invention are useful as appetite suppressants as based on the tests described hereinbelow.
In the Palatable Diet Feeding assay, adult male Hooded Lister rats weighing between 200-400 g are housed individually and trained to eat a palatable diet. This diet consists of Nestles sweetened condensed milk, powdered rat food and rat water which when blended together set to a firm consistency. Each rat is presented with 20-30 g of the palatable diet for 30 minutes per day during the light phase of the light-dark cycle over a training period of five days. The intake of palatable diet is measured by weighing the food container before and after the 30-minute access period (limits of accuracy 0.1 g). Care is taken to collect and correct for any spillage of the diet. Rats have free access to pellet food and water except during the 30-minute test period.
After the training period, dose-response curves are constructed for CCK8 and several representative compounds of the present invention (n=8-10 rats per dose level). MPE 50 values (±95% confidence limits) are obtained for the anorectic effects of these compounds. In therapeutic use as appetite suppression agents, the compounds of the instant invention are administered to the patient at dosage levels of from about 200 to about 2800 mg per day.
Male Hooded Lister rats (175-250 g) are housed individually and fasted overnight (free access to water). They are anesthetized with urethane (1.5 g/kg IP) and the trachea cannulated to aid spontaneous respiration. The stomach is perfused continuously using a modification of the original method of Ghosh & Schild in "Continuous recording of acid secretion in the rat", Brit. J. Pharmac. 13:54-61, 1956 as described by Parsons in "Quantitative studies of drug-induced gastric acid secretion". (Ph.D. Thesis, University of London, 1969). The cavity of the stomach is perfused at a rate of 3 mL/min with 5.4% w/v glucose solution through both the esophageal and body cannula. The fluid is propelled by a roller pump (Gilson, Minipuls 2), through heating coils to bring its temperature to 37°±10° C. The perfusion fluid is collected by the fundic collecting funnel and passed to a pH electrode connected to a Jenway pH meter (PHM6). An output is taken from the pH meter to a Rikadenki chart recorder for the on-line recording of the pH of the gastric perfusate.
Pentagastrin is stored as a frozen aliquot and diluted to the required concentrations with sterile 0.9% w/v NaCl. Novel compounds are dissolved in sterile 0.9% w/v NaCl on the day of the experiment. Drugs are administered IV through a cannulated jugular vein as a bolus in a dose volume of 1 mL/kg washed in with 0.15 mL 0.9% w/v NaCl. Basal pH is allowed to stabilize before administration of compounds is begun. Typically 30 minutes elapses between surgery and the first compound administration.
The compounds of the instant invention are also useful as antiulcer agents as discussed hereinbelow.
Aspirin-induced gastric damage is assessed in groups of 10 rats each.
All animals are fasted for 24 hours before and throughout the experiment. Drug or vehicle is given 10 minutes before an oral dose of 1 mL of a 45-mg/mL suspension of aspirin in 0.5% carboxymethylcellulose (CMC).
The animals are sacrificed 5 hours after aspirin administration and the stomachs removed and opened for examination.
Gastric damage is scored as follows:
______________________________________Score______________________________________1 Small hemorrhage2 Large hemorrhage3 Small ulcer4 Large ulcer5 Perforated ulcer______________________________________
The specific dosages employed, however, may be varied depending upon the patient, the severity of the condition being treated, and the activity of the compound employed. Determination of optimum dosages is within the skill of the art.
The compounds of the instant invention are also useful as anxiolytic agents as described and discussed below.
Anxiolytic activity is assessed in the light/dark exploration test in the mouse (B. J. Jones, et al, Brit. J. Pharmacol. 93:985-993, 1988).
The apparatus is an open-topped box, 45 cm long, 27 cm wide, and 27 cm high, divided into a small (2/5) area and a large (3/5) area by a partition that extended 20 cm above the walls. There is a 7.5×7.5 cm opening in the partition at floor level. The small compartment is painted black and the large compartment white. The floor of each compartment is marked into 9 cm squares. The white compartment is illuminated by a 100-watt tungsten bulb 17 cm above the box and the black compartment by a similarly placed 60-watt red bulb. The laboratory is illuminated with red light.
All tests are performed between 13 hundred hours, 0 minutes and 18 hundred hours, 0 minutes. Each mouse is tested by placing it in the center of the white area and allowing it to explore the novel environment for 5 minutes. Its behavior is recorded on videotape and the behavioral analysis is performed subsequently from the recording. Five parameters are measured: the latency to entry into the dark compartment, the time spent in each area, the number of transitions between compartments, the number of lines crossed in each compartment, and the number of rears in each compartment.
In this test an increase in the time spent in the light area is a sensitive measure of, that is directly related to, the anxiolytic effects of several standard anxiolytic drugs. Drugs are dissolved in water or saline and administered either subcutaneously, intraperitoneally, or by mouth (PO) via a stomach needle.
The compounds of the instant invention are useful as antipsychotic agents. Compounds are tested for their ability to reduce the effects of intra-accumbens amphetamine in the rat as described hereinafter.
Male Sprague Dawley (CD) Bradford strain rats are used. The rats were housed in groups of five at a temperature of 21+±2° C. on a 12 hour light-dark cycle of lights-on between 07 hours 00 minutes and 20 hours 00 minutes. Rats are fed CRM diet (Labsure) and allowed water ad libitum.
Rats are anesthetized with chloral hydrate (400 mg/kg SC) and placed in a Kopf stereotaxic frame. Chronically indwelling guide cannulae (constructed of stainless steel tubing 0.65 mm diameter held bilaterally in Parspex holders) are implanted using standard stereotaxic techniques to terminate 3.5 mm above the center of the nucleus accumbens (Ant. 9.4, Vert. 0.0, Lat. 1.6) or 5.0 mm above the central nucleus of the amygdala (Ant. 5.8, Vert. -1.8, Lat. ±4.5) (atlas of De Groot, 1959). The guides are kept patent during a 14-day recovery period using stainless steel stylets, 0.3 mm diameter, which extended 0.5 mm beyond the guide tips.
Rats are manually restrained and the stylets removed. Intracerebral injection cannulae, 0.3 mm diameter, are inserted and drugs delivered in a volume of 0.5 μL over 5 seconds (a further 55 seconds was allowed for deposition) from Hamilton syringes attached via polythene tubing to the injection units. Animals are used on a single occasion only.
Behavioral experiments are conducted between 07 hours 30 minutes and 21 hours 30 minutes in a quiet room maintained at 22°±2° C. Rats are taken from the holding room and allowed 1 hour to adapt to the new environment. Locomotor activity is assessed in individual screened Perspex cages (25×15×15 cm (high) (banked in groups of 30) each fitted with one photocell unit along the longer axis 3.5 cm from the side; this position has been found to minimize spurious activity counts due to, for example, preening and head movements when the animal is stationary. Interruptions of the light beam are recorded every 5 minutes. At this time animals are also observed for the presence of any nonspecific change in locomotor activity, e.g., sedation, prostration, stereotyped movements, that could interfere with the recording of locomotor activity.
The abilities of compounds to inhibit the hyperactivity caused by the injection of amphetamine into the nucleus accumbens of the rat are measured.
An increase in locomotor activity follows the bilateral injection of amphetamine (20 μg) into the nucleus accumbens; peak hyperactivity (50 to 60 counts 5 minutes -1 ) occurs 20 to 40 minutes after injection.
Intraperitoneal injection of the rats with a compound (20 mg/kg or 30 mg/kg) or (10 mg/kg) reduces the hyperactivity caused by the intra-accumbens injection of amphetamine. This test is known to be predictive of antipsychotic activity (Costall, Domeney & Naylor & Tyers, Brit. J. Pharmac. 92:881-894).
The compounds of the instant invention prevent and treat the withdrawal response produced when chronic treatment by a drug is stopped or when alcohol abuse is stopped. These compounds are therefore useful as therapeutic agents in the treatment of chronic drug or alcohol abuse as discussed and described below.
The effect of the compounds of the instant invention is illustrated, for example, in the mouse "light/dark box" test.
Five animals are given nicotine, 0.1 mg/kg i.p. b.d. for 14 days. After a 24-hour withdrawal period, a compound is given at 1.0 mg/kg i.p. b.d. The increased time spent in the light area is a sensitive measure of the effect of the compound as an agent to treat withdrawal effects from nicotine.
The effect of long-term treatment and withdrawal from nicotine using a compound of the invention. Five mice are given nicotine at 0.1 mg/kg i.p. b.d. for 14 days. After a withdrawal period of 24 hours, the compound is given at 10 mg/kg i.p. b.d. The effect of the compound can be seen in the increase of time spent in the light area.
The effect of long-term treatment and withdrawal from diazepam with intervention with a compound of the invention is demonstrated by the following. Five mice are given diazepam, at 10 mg/kg i.p. b.d. for 7 days. Withdrawal is for a 24-hour period; the compound is given at 1.0 mg/kg i.p. b.d. The increased time spent in the light section shows the effect of the compound.
The effect of a compound of the invention on the long-term treatment and withdrawal from diazepam is demonstrated by the following. Five mice were given diazepam at 10 mg/kg i.p. b.d. for 7 days. After a withdrawal period of 24 hours, the compound is given at 10 mg/kg i.p. b.d. The amount of time spent in the light section after the compound is administered demonstrates the effectiveness of the compound.
The effect of a compound of the invention on the long-term treatment and withdrawal from alcohol is demonstrated by the following. Five mice are given alcohol in drinking water 8% w/v for 14 days. After a withdrawal period of 24 hours, the compound is given at 1.0 mg/kg i.p. b.d. The amount of time spent in the light section after the compound is administered demonstrates the effectiveness of the compound.
The effect of a compound of the invention on long-term treatment and withdrawal from alcohol is demonstrated by the following. Five mice were given alcohol in drinking water, 8% w/v for 14 days. After a withdrawal period of 24 hours, the compound is given at 10 mg/kg i.p. b.d. The increased time spent in the light section shows the effect of the compound on the mice.
The effectiveness in the long-term treatment and withdrawal from cocaine of a compound of the invention. Five mice are given cocaine as 1.0 mg/kg i.p. b.d. for 14 days. The increased time in the light section illustrates the effectiveness of the compound in the treatment.
The effect of long-term treatment and withdrawal from cocaine with the intervention of a compound of the invention is demonstrated by the following. Five mice are given cocaine at 1.0 mg/kg i.p. b.d. for 14 days after a withdrawal period of 24 hours, the compound is given at 1.0 mg/kg i.p. b.d. The effect of intervention with the compound is shown by the increase in time spent in the light section.
The anxiolytic effects of a compound of the invention is shown in the Rat Social Interaction Test on a dose range of 0.001 to 1.0 mg/kg when paired rats are dosed s.c. The anxiolytic effect of the compound are indicated by the increase in time spent in social interaction compared with the control value C. (Costall, B., University of Bradford)
The anxiolytic effects of a compound of the invention is shown in the Rat Elevated X-Maze Test on a dose range of 0.01 to 1.0 mg/kg s.c. The anxiolytic effect is indicated by the time spent in the open arm end section compared with control C.
Compounds of the invention depress the flexor response in a stimulated spinalized decerebrated rat preparation similar to morphine. The effect of giving a compound with morphine greatly potentiates the effect which lasts for 3 hours.
For preparing pharmaceutical compositions from the compounds of this invention, inert, pharmaceutically acceptable carriers can be either solid or liquid. Solid form preparations include powders, tablets, dispersible granules, capsules, cachets, and suppositories.
A solid carrier can be one or more substances which may also act as diluents, flavoring agents, solubilizers, lubricants, suspending agents, binders, or tablet disintegrating agents; it can also be an encapsulating material.
In powders, the carrier is a finely divided solid which is in a mixture with the finely divided active component. In tablets, the active component is mixed with the carrier having the necessary binding properties in suitable proportions and compacted in the shape and size desired.
For preparing suppository preparations, a low-melting wax such as a mixture of fatty acid glycerides and cocoa butter is first melted and the active ingredient is dispersed therein by, for example, stirring. The molten homogeneous mixture is then poured into convenient sized molds and allowed to cool and solidify.
The powders and tablets preferably contain 5 to about 70% of the active component. Suitable carriers are magnesium carbonate, magnesium stearate, talc, lactose, sugar, pectin, dextrin, starch, tragacanth, methyl cellulose, sodium carboxymethyl cellulose, a low-melting wax, cocoa butter, and the like.
A preferred pharmaceutically acceptable salt is the N-methyl glucamine salt.
The term "preparation" is intended to include the formulation of the active component with encapsulating material as a carrier providing a capsule in which the active component (with or without other carriers) is surrounded by a carrier which is thus in association with it. Similarly, cachets are included.
Tablets, powders, cachets, and capsules can be used as solid dosage forms suitable for oral administration.
Liquid form preparations include solutions, suspensions, and emulsions. Sterile water or water-propylene glycol solutions of the active compounds may be mentioned as an example of liquid preparations suitable for parenteral administration. Liquid preparations can also be formulated in solution in aqueous polyethylene glycol solution.
Aqueous solutions for oral administration can be prepared by dissolving the active component in water and adding suitable colorants, flavoring agents, stabilizers, and thickening agents as desired. Aqueous suspensions for oral use can be made by dispersing the finely divided active component in water together with a viscous material such as natural synthetic gums, resins, methyl cellulose, sodium carboxymethyl cellulose, and other suspending agents known to the pharmaceutical formulation art.
Preferably the pharmaceutical preparation is in unit dosage form. In such form, the preparation is divided into unit doses containing appropriate quantities of the active component. The unit dosage form can be a packaged preparation, the package containing discrete quantities of the preparation, for example, packeted tablets, capsules, and powders in vials or ampoules. The unit dosage form can also be a capsule, cachet, or tablet itself, or it can be the appropriate number of any of these packaged forms.
EXAMPLES
Example 1
(2-Adoc-D-MeTrp-L-Phe-B-Alanine (6a)) β-Alanine, N- N- α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !-dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl! ##STR19## Boc-L-phenylalanyl-β-alanine, benzyl ester; (3a)
Boc-L-phenylalanine (1.32 g, 5.00 mmol) was dissolved in dichloromethane (50 mL) and treated with HoBt.H 2 O (1.53 g, 2.00 mmol) followed by WSCDI (water soluble carbodiimide) (1.00 g, 5.24 mmol). After stirring for 40 minutes, β-alanine benzyl ester tosylate (1.85 g, 5.27 mmol) was added, followed by DIPEA (diisopropylethylamine) (1.29 g, 10 mmol). Stirring was continued overnight, then the solvent removed. The residue was dissolved in ethyl acetate (30 mL) and washed with water, 10% sodium bicarbonate solution, then 10% citric acid solution. The organic layer was dried (MgSO 4 ) and evaporated to a white solid--a single component by TLC, 1.74 g, 82% of (32). NMR (CDCl 3 ) δ 1.41 (9H, s), 2.47 (2H, m), 3.01 (2H, m), 3.45 (2H, m), 4.25 (1H, br.q), 5.00 (1H, br.s), 5.07 (2H, s), 6.21 (1H, br.t), 7.15-7.38 (10H, m).
L-Phenytalanyl-β-alanine benzyl ester tosylate (4a)
The solid described above was dissolved in CH 2 Cl 2 :THF (1:1, 50 mL) and treated with p-toluenesulphonic acid (1.62 g) at reflux for 2 hours following removal of the solvents. The residue was triturated with diethyl ether, giving a white powder, 1.87 g, 64%. NMR (D 2 O) δ 2.38 (3H, s), 2.45 (2H, m), 3.03 (2H, m), 3.27 (1H, m), 3.49 (1H, m), 4.01 (1H, t), 5.12 (2H, s), 7.20-7.66 (12H, m), 7.97 (2H, d).
2-Adoc-D-MeTrp-L-Phe-β-Alanine benzyl ester (5a)
2-Adoc-D-MeTrp (1.00 g, 2.52 mmol) was dissolved in ethyl acetate (25 mL) and treated with HOBt.H 2 O (400 mg, 2.61 mmol) and DCC1 (550 mg, 2.66 mmol). After 30 minutes the mixture was filtered and the filtrate treated with (4a), produced above, followed by DIPEA (374 mg, 2.89 mmol). After stirring overnight, the mixture was filtered and the filtrate concentrated. The residue was chromatographed on silica (5% MeOH/CH 2 Cl 3 ), giving 1.206 (68%) of product (5a). NMR (CDCl 2 ) δ 1.25 (3H, s), 1.53 (2H, br.d), 1.71-1.97 (12H, m), 2.54 (2H, m), 3.04 (2H, qd), 3.46 (2H, abq), 3.49 (2H, m), 4.67 (1H, q), 4.76 (1H, br.s), 4.94 (1H, s), 5.09 (2H, s), 6.21 (1H, d), 6.89 (1H, d), 6.99-7.36 (14H, m), 7.54 (1H, d), 8.20 (1H, s).
2-Adoc-D-Metrp-L-Phe-β-Alanine (6a)
500 mg of product (5a) was dissolved in methanol (20 mL) and the solution treated with 2,4-cyclohexadiene (2 mL) and 10% Pd/C (400 mg) and the mixture stirred until TLC revealed all starting material had been consumed. After filtering and concentration of the filtrate, the residue was purified by RP-HPLC (C 18 , MeOH:H 2 O-1:1), giving 267 mg of a white solid (6A), 63%. NMR (DMS-D 6 ) δ 1.05 (3H, s), 1.52 (2H, t), 1.71-2.04 (12H, m), 2.42 (2H, t), 2.74-3.31 (8H, m), 4.54 (1H, br.m), 4.75 (1H, s), 6.84-7.40 (12H, m), 7.84 (2H, m), 10.90 (1H, s); IR (CHBr 3 film) 1659, 1700 cm -1 .
The products (5 b-d, f, and g) were prepared in a similar manner to (5a).
2-Adoc-D-MeTrp-L-Phe-GABA-OMe (5b)
NMR (DMSO-d 6 ) δ 1.02 (3H, s), 1.48 (2H, 5), 1.62-2.07 (16H, m), 2.33 (2H, t), 2.90 (1H, t), 3.08 (3H, m), 3.30 (2H, m), 3.59 (3H, s), 4.52 (1H, m), 4.71 (1H, br.s), 6.87 (2H, m), 6.99 (1H, t), 7.16-7.35 (9H, m), 7.63 (1H, br.t), 7.83 (1H, br.d), 10.86 (1H, s).
2-Adoc-D-MeTrp-L-Phe-DAVA-OMe (5c)
NMR (DMSO-d 6 ) δ 1.03 (3H, s), 1.45-1.60 (6H, m), 1.69-1.98 (12H, m), 2.31 (2H, t), 2.91 (1H, t), 3.07 (3H, complex), 3.32 (3H, m), 3.58 (3H, s), 4.50 (1H, m), 4.71 (1H, br.s), 6.85-7.46 (1H, m), 7.76 (1H, br.d), 7.82 (1H, br.d), 10.85 1H, s).
2-Adoc-D-MeTrp-L-Phe-EACA-OMe (5d)
L-Phenylalaninamide, α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl-N-(6-methoxy-6-oxohexyl) ##STR20##
NMR (CDCl 3 ) δ 1.22 (3H, s), 1.29 (2H, m), 1.45-1.99 (16H, m), 3.0 (1H, dd), 3.21 (3H, m), 3.37 (2H, dd), 3.65 (3H, s), 4.72 (2H, m), 4.88 (1H, s), 6.19 (1H, d), 6.89-7.25 (11H, m), 7.36 (1H, d), 7.54 (1H, d), 8.15 (1H, s).
2-Adoc-D-MeTrp-L-Phe-L-Glu(OMe) 2 (5f) L-Glutamic acid, N- N- α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl -, dimethyl ester ##STR21##
NMR (CDCl 3 ) δ 1.34 (3H, s), 1.73-2.36 (14H, m), 3.09 (2H, qd), 2.37 (2H, abq), 3.65 (3H, s), 3.71 (3H, s), 4.50 (1H, m), 4.68 (2H, m), 4.91 (1H, s), 6.38 (1H, d), 6.90-7.24 (10H, m), 7.34 (1H, d), 7.56 (1H, d), 8.15 (1H, s).
2-Adoc-D-MeTrp-L-Phe-NHCH(CO 2 Et) 2 (5g)
NMR (DMSO-d 6 ) δ 1.12 (3H, s), 1.22 (6H, m), 1.45 (2H, br.t), 1.68-2.00 (14H, m), 2.89-3.09 (3H, m), 4.20 (4H, m), 4.68 (2H, br.m), 5.09 (1H, d), 6.682 (1H, br.s), 6.87 (2H, br.s), 7.00 (1H, t), 7.17-7.38 (8H, m), 7.78 (1H, br.d), 8.78 (1H, br.d), 10.79 (1H, s).
Example 2
2-Adoc-D-MeTrp-L-Phe-L-Asp (6h)
L-Aspartic acid, N- N- α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl! ##STR22##
Similarly prepared was (6H) via the dibenzyl ester (5e).
2-Adoc-D-MeTrp-L-Phe-L-Asp (6h)
NMR (DMSO-D 6 ) δ 1.07 (3H, s), 1.38 (1H, d), 1.49 (2H, t), 1.60-2.09 (14H, m), 2.51-3.30 (6H, complex), 4.56 (2H, br.d), 4.74 (1H, s), 6.73-7.39 (10H, m), 7.83 (1H, d), 8.14 (1H, d), 10.83 (1H, s), 12.60 (1H, br); IR (CHBr 3 film) 1645, 1705 cm -1 .
Example 3
2-Adoc-D-MeTrp-L-Phe-Glu (6i)
L-Glutamic acid, N- N- α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl! ##STR23##
(6i) was prepared by slow saponification of the precursor methyl ester (5f) using 0.1N LiOH (or NaOH) in THF or dioxan.
NMR (DMSO-d 6 ) δ 1.08 (3H, s), 1.49 (2H, t), 1.70-2.05 (18H, m), 2.32 (2H, t), 2.93 (1H, dd), 3.08-3.50 (5H, m), 4.25 (1H, m), 4.68 (2H, br.m), 6.78 (1H, br.s), 6.88-7.42 (11H, m), 7.83 (2H, br.d), 10.80 (1H, s), 12.40 (1H, br. s).
Example 4
2-Adoc-D-MeTrp-L-Phe-Gly (6j)
Glycine, N- 2-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-D-tryptophyl!-L-phenylalanyl- ##STR24##
2-Adoc-D-MeTrpOPfp (1.68 g, 3.00 mmol) was added to a solution of PheGly (0.732 g, 3.30 mmol) and DIPEA (0.851 g, 6.60 mmol) in DMF (20 mL). After stirring overnight, the solvent was removed and the residue chromatographed on silica (10% MeOH/CH 2 Cl 2 +1% AcOH) giving 846 mg of a white solid (6i), 47%. NMR (DMSO-d 6 ) δ 1.15 (3H, s), 1.47 (2H, t), 1.68-2.00 (12, m), 2.93 (1H, dd), 3.20 (2H, dd), 3.17 (1H, m), 3.66 (2H, br.s), 4.60 (1H, m), 4.68 (1H, s), 6.72-7.41 (12H, m), 7.96 (1H, br.s), 10.85 (1H, s); IR (CHBr 3 film) 1665 cm -1 .
The following were prepared as in Scheme IA.
Example 5
β-Alanine, N- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-4-phenylbutyl!-, methyl ester, R-(R*,S*)! (10a) ##STR25##
NMR (CDCl 3 ) δ 1.26 (3H, t), 1.37 (3H, s), 1.52 (2H, m), 1.71-2.01 (15H, m), 2.29 (1H, dd), 2.50 (1H, br.dd), 2.77 (2H, m), 3.30 (2H, s), 3.74 (1H, dd), 4.09-4.21 (3H, m), 4.42 (1H, m), 4.74 (1H, s), 5.16 (1H, s), 6.72 (1H, br.s), 6.91 (1H, s), 7.08-7.32 (10H, m), 7.57 (1H, d), 8.13 (1H, s).
Example 6
Glycine, N- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-4-phenylbutyl!-, ethyl ester, R-(R*,S*)!- (10k) ##STR26##
NMR (CDCl 3 ) δ 1.45 (3H, s), 1.52 (2H, br.d), 1.71-2.03 (16H, m), 2.22 (2H, qd), 2.52 (2H, t), 2.74 (2H, qd), 3.36 (2H, abq), 3.47 (2H, m), 3.69 (3H, s), 4.35 (1H, m), 4.80 (1H, br.s), 5.23 (1H, s), 6.27 (1H, br.t), 6.88 (1H, d), 7.04-7.33 (10H, m), 7.59 (1H, d), 8.25 (1H, s).
Example 7
2-Adoc-D-MeTrp-L-NHCH(CH 2 Ph)CH 2 CO-GABA-OEt (101)
L-Phenylalaninamide, α-methyl-N- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!-L-tryptophyl-N-(4-ethoxy-4-oxobutyl) ##STR27##
NMR (CDCl 3 ) δ 1.24 (3H, 5), 1.45 (3H, s), 1.51 (2H, br.d), 1.71-2.01 (16H, m), 2.21 (2H, qd), 2.33 (2H, t), 2.74 (2H, qd), 3.21 (2H, m), 3.36 (2H, q), 4.11 (2H, q), 4.36 (1H, m), 4.79 (1H, br.s), 5.22 (1H, s), 6.05 (1H, br.t), 6.89 (1H, d), 7.03-7.33 (10H, m), 7.58 (1H, d), 8.38 (1H, s).
Example 8
β-Alanine, N- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-4-phenylbutyl!-, R-(R*,S*)! ##STR28##
NMR (CDCl 3 ) δ 1.37 (3H, s), 1.50 (2H, br.d), 1.68-1.98 (16H, m), 2.27 (2H, m), 2.73 (2H, m), 3.24 (2H, q), 3.76 (1H, dd), 4.04 (1H, dd), 4.38 (1H, m), 4.74 (1H, s), 4.90 (1H, br.s), 6.83 (1H, s), 7.02-7.19 (10H, m), 7.29 (1H, d), 7.52 (1H, d), 8.52 (1H, br.s).
Example 9
Glycine, N- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-4-phenylbutyl-, R-(R*,S*)!- (11k) ##STR29##
NMR (DMSO-d 6 ) δ 1.15 (3H, s), 1.47 (2H, t), 1.59-1.97 (16H, m), 2.20 (2H, m), 2.37 (2H, t), 2.72 (2H, m), 3.22 (4H, m), 4.22 (1H, m), 4.66 (1H, br.s), 6.81 (2H, s), 6.89 (1H, t), 7.01 (1H, t), 7.03-7.30 (6H, m), 7.42 (1H, d), 7.79 (1H, d), 7.96 (1H, br.s), 10.87 (1H, s).
Example 10
2-Adoc-D-MeTrp-L-NHCH(CH 2 Ph)CH 2 CO-GABA (111)
Butanoic acid, 4- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-oxo-4-phenylbutyl!amino!-, R-(R*,S*)! ##STR30##
NMR (CDCl 3 ) δ 1.42 (3H, s), 1.51 (2H, d), 1.70-2.00 (14H, m), 2.21 (2H, m), 2.34 (2H, t), 2.76 (2H, m), 3.21 (2H, m), 3.30 (2H, q), 4.37 (1H, m), 4.79 (1H, s), 5.30 (1H, s), 6.43 (1H, br.s), 6.90 (1H, s), 6.99-7.33 (12H, m), 7.55 (1H, d), 8.52 (1H, s).
Example 11
2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-3-phenylpropyl R-(R*,S*)!-1,4-dihydro-1-methyl-3-pyridinecarboxylate ##STR31##
A solution of the pyridinium salt (150 mg, 0.193 mmol) dissolved in dichloromethane (10 mL) was stirred at 5° C. (internal temperature) with a Na 2 HPO 4 /KH 2 PO 4 buffer solution (pH 7.0, 10 mL) while nitrogen was bubbled through the solution for 30 minutes to deaerate the system. Sodium dithionite (335 mg, 1.93 mmol, 10 equiv.) was added in one portion and the mixture stirred under a nitrogen atmosphere for 3 hours. The layers were separated, the aqueous and the combined organic phases washed with cold deaerated water, dried (MgSO 4 ), filtered, and concentrated to a yellow resin. Chromatographic purification of this crude product (reverse phase, LiChroprep RP18, Merck 13900, MeOH:H 2 O, 4:1) gave the title compound as a yellow powder (44 mg, 35%); m.p. 116°-121° C. (amorphous); δ (CDCl 3 ); 1.49-2.05 (17H, m, adamantyl H and quaternary CH 3 ), 2.57 (1H, dd, J=8.4 Hz, 13.6 Hz), and 2.81 (1H, dd, J=5.3 Hz, 13.6 Hz, phCH 2 ), 2.90 (3H, s, NCH 3 ), 3.04 (2H, br s, pyr C(4)H) 3.33 (1H, d, J=14.8 Hz) and 3.42 (1H, d, J=14.8 Hz, CH 2 indole), 3.93 (1H, dd, J=3.9 Hz, 11.5 Hz) and 4.03 (1H, dd, J=5.4 Hz, 11.5 Hz, CH 2 OCOpyr), 4.28 (1H, m, CHmethine), 4.76 (1H, dt, J=4.2 Hz, 8.0 Hz, pyr C(5)H), 4.80 (1H, br s, adamantyl C(2)H), 5.32 (1H, br s, carbamate, CONH), 5.61 (1H, dd, J=1.6 Hz, CONH), 6.92 (1H, d, J=2.3 Hz, indole C(2)H), 6.95 (1H, d, J=1.4 Hz, pyr C(2)H), 7.06-7.33 (8H, m, PhH and indole C(5)H, C(6)H and C(7)H), 7.61 (1H, d, J=7.7 Hz, indole C(4)H), 8.22 (1H, br s, indole NH; ν max (nujol mull), 3326, 1664, 1593, 1497 cm -1 .
Example 12
2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-3-phenylpropyl R-(R*,S*)!-triqonelline iodide ##STR32##
A solution of the nicotinate ester (186 mg, 0.29 mmol) in nitromethane (2 mL) containing iodomethane (0.5 mL, excess) was stirred in a stoppered flask at room temperature for 24 hours, concentrated in vacuo with addition of ether to precipitate material as a solid and dried at 50° C. in vacuo, leaving the title compound as a yellow powder (220 mg, 98%); m.p. 132°-136° C.; δ (DMSO-d 6 ), 1.10 (3H, s, quaternary (3H, s, CH 2 Ph and one CH 2 indole), 3.31-3.49 (2H, m, one CH 2 indole and NH), 4.23 (2H, dd, J=8.0 Hz, 10.0 Hz, CH 2 OCOpyr), 4.44 (3H, s, N + CH 3 ), 4.49 (2H, m, adamantyl C(2)H and CH methine), 6.83-6.91 (3H, m, indole C(5 or 6)H, C(2)H, amide CONH), 7.00 (1H, apparent t, J=7.5 Hz, indole C(5 or 6)H), 7.20-7.31 (6H, m) and 7.22 (1H, d, J=2.3 Hz, PhH and indole C(4)H, C(7)H), 7.81 (1H, d, J=8.8 Hz, indole NH), 8.28 (1H, dd, J=7 Hz, pyr C(5)H), 9.01 (1H, d, J=2 Hz, pyr C(4)H), 9.18 (1H, d, J=6.2 Hz, pyr C(6)H), 9.51 (1H, s, pyr (C(2)H), ν max (mull) 3628, 1738, 1702, 1658, 1496 cm -1 ; α D =+60.2° C. (MeOH, C, 0.01); m/e (found) 649.3386 C 39 H 45 N 4 O 5 (excluding I - ) requires m/e 649.3386 C 39 H 45 N 4 O 5 I.2H 2 O requires C, 57.63; H, 6.07; N, 6.89. Found; C, 57.88; H, 6.35; N, 6.90.
Example 13
2- 3- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!-propyl!amino!-3-phenylpropyl R-(R*,S*)!-3-pyridine-carboxylate ##STR33##
To a solution of the alcohol (377 mg, 0.71 mmol), DMAP (8) mg, 0.07 mmol, 0.1 equiv.) and nicotinic acid (88 mg, 0.71 mmol, 1 equiv.) in dry dichloromethane (8 mL) was added N,N'-dicyclohexylcarbodiimide (154 mg, 0.74 mmol, 1.05 equiv.), and the mixture stirred at room temperature for 16 hours. The opaque mixture was then diluted with ether, filtered, concentrated to a white resin and chromatographically purified (reverse phase, MeOH:H 2 O, solid); (307 mg, 68%); m.p. 86°-88° C.; δ (CDCl 3 ) 1.45-1.90 (17H, m, adamantyl H and quaternary CH 3 ), 2.73 (1H, dd, 13.7 Hz, 7.8 Hz), and 2.88 (1H, dd, J=6.2 Hz, 13.7 Hz, CH 2 Ph), 3.24 (1H, d, J=14.7 Hz) and 3.48 (1H, d, J=14.7 Hz, CH 2 indole), 4.23 (2H, d, J=4.8 Hz, CH 2 OCO pyr), 4.53 (1H, m, CH methine), 4.71 (1H, m, adamantyl C(2)H), 5.20 (1H, s, carbamate OCONH), 6.79 (1H, d, J=8.1 Hz, amide CONH), 6.93 (1H, d, J=2.2 Hz, indole C(2)H, C(7)H), 7.35 (1H, dd, J=7.9 Hz, 4.7 Hz, pyr C(5)H), 7.56 (1H, d, J=7.8 Hz, indole C(4)H), 8.22 (1H, dt, J=1.8 Hz, 8.0 Hz, pyr C(4)H), 8.46 (1H, m, indole NH), 8.76 (1H, dd, J=3.2 Hz, 4.8 Hz, pyr C(6)H), 9.16 (1H, d, J=1.7 Hz, pyr C(2)H), ν max (mull) 3320, 1719, 1660 cm -1 ; α D =+31.2° C. (CHCl 3 , CiO 0.006); C 38 H 42 N 4 O 5 requires C, 71.90; H, 6.67; N, 8.82%. Found: C, 71.45; H, 6.66; N, 8.73%.
Example 14
Butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-, (2,2-dimethyl-1-oxopropoxy)methyl ester, R-(R*,R*)! ##STR34##
To a solution of the above acid (500 mg) in DMF (5 mL) was added NEt 3 (117 mg) followed by CCCH 2 O 2 CCMe 3 (247 mg). The reaction mixture was stirred for 5 days at room temperature and then poured into H 2 O. The product was extracted with EtOAc and the organic layer dried (MgSO 4 ) and concentrated to yield a gum (750 mg).
The crude product was purified by column chromatography (50% to 75% EtOAc/hexane) to yield the desired dilute ester (2) as an amorphous white solid (120 mg), mp 110°-116° C.; IR (film) 3317, 3061, 1757, 1700, 1666 cm -1 ; 1 HNMR (d 6 -DMSO) δ 1.12 (12H, brs), 1.49 (2H, brs) 1.60-2.05 (12H, m), 2.50 (4H, m, observed by DMSO), 3.20-3.40 (4H, m, observed by H 2 O), 4.69 (1H, brs), 4.96 (1H, m), 5.65 (2H, s), 6.72 (1H, brs), 6.93 (2H, brs), 7.01 (1H, t, J 8 Hz), 7.30 (6H, m), 7.43 (1H, d, J 8 Hz), 7.74 (1H, t, J 4 Hz), 8.16 (1H, brs), 10.86 (1H, s).
Example 15
Butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!amino!-4-oxo-, chloromethyl ester, R-(R*,R*)!- ##STR35##
To a suspension of R-(R*,R*)!-4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxobutanoic acid (CI-988) (500 mg, 0.81 mmol), sodium hydrogen carbonate (240 mg, 2.86 mmol), and tetrabutyl ammonium hydrogen sulphate (28 mg, 0.08 mmol) in CH 2 Cl 2 (5 mL) and water (5 mL) was added dropwise a solution of chloromethyl sulphonyl chloride (163 mg, 0.99 mmol) in CH 2 Cl 2 (3 mL). The mixture was stirred at room temperature for 5 hours and then 10% citric acid solution and CH 2 Cl 2 were added. The organic phase was separated, dried (MgSO 4 ), filtered, and evaporated. Purification by column chromatography on silica gel eluting with ethyl acetate/hexane mixtures gave butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!ethyl!amino!-4-oxo-, chloromethyl ester, R-(R*,R*)!- as an amorphous white solid (343 mg, 52%), mp 155°-122° C. 300 MHz NMR (CDCl 3 δ 1.42 (s, 3H), 1.50-1.60 (m, 2H), 1.70-2.00 (m, 12H), 2.55-2.80 (m, 4H), 3.25-3.40 (m, 3H), 3.47 (d, J 14.6 Hz, 1H), 4.00-4.15 (m, 1H), 4.89 (s, 1H), 5.20-5.30 (m, 2H), 5.60-5.70 (m, 2H), 6.30-6.40 (m, 1H), 6.95 (d, J 2.3 Hz, 1H), 7.05-7.40 (m, 10H), 7.56 (d, J 7.8 Hz, 1H), 8.46 (s, 1H).
Analysis for C 36 H 43 ClNO 6 .0.5H 2 O. Calcd: C, 64.32; H, 6.59; N, 8.33. Found: C, 64.14; H, 6.45, N, 8.23.
Example 16
Pentanedioic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-1,4-dioxobutoxy!methyl ester, R-(R*,R*)!-, compd. with 1-deoxy-1-(methylamino)-D-glucitol ##STR36##
A. To a solution of glutaric acid monobenzyl ester (170 mg, 0.77 mmol) in CH 2 Cl 2 (5 mL) and water (5 mL) was added tetrabutyl ammonium hydrogen sulphate (26 mg, 0.077 mmol) and sodium hydrogen carbonate (225 mg, 2.68 mmol), followed by chloromethyl sulphonyl chloride (153 mg, 0.93 mmol) in CH 2 Cl 2 (3 mL). The reaction mixture was stirred at room temperature for 3 hours and then citric acid solution added and the organic phase separated, washed, dried, and evaporated to give a colorless oil (220 mg, 106%). 300 MHz NMR (CDCl 3 ) δ 1.9-2.05 (m, 2H), 2.4-2.5 (m, 4H), 5.12 (s, 2H, CH 2 ), 5.68 (s, 2H, CH 2 ), 7.3-7.4 (m, 5H).
B. To a solution of CI-988 (222 mg, 0.36 mmol) in DMF (5 mL) was added triethylamine (55 mg, 0.54 mmol), followed by chloromethyl benzyl glutarate (146 mg, 0.54 mmol). After 9 days ethyl acetate and water were added and the organic phase separated, washed, dried, and evaporated to give a yellow gum. Purification by column chromatography on silica gel, eluting with ethyl acetate hexane mixtures, gave the product as an amorphous solid (110 mg, 36%). 300 MHz NMR (CDCl 3 ) δ 1.45 (s, 3H), 1.50-2.00 (m, 16H), 2.30-2.70 (m, 8H), 3.30-3.40 (m, 2H), 3.48 (d, J 14.7, 1H), 3.90-4.05 (m, 1H), 4.86 (s, 1H), 5.05-5.15 (m, 5H), 5.70-5.75 (m, 2H), 6.30-6.40 (m, 1H), 6.99 (d, J 2.1 Hz, 1H), 7.10-7.40 (m, 16H), 7.58 (d, J 7.7, 1H), 8.32 (s, 1H).
C. The benzyl ester from B (110 mg, 0.13 mmol) was dissolved in ethanol (50 mL) and hydrogenated over Pearlman's catalyst (10 mg) at 45 psi for 4 hours. The solution was filtered to remove catalyst and evaporated to dryness to give an amorphous solid (105 mg, 100%). 300 MHz NMR DMSO δ 1.19 (s, 3H), 1.40-2.00 (m, 14H), 2.23 (6, J 7.3 Hz, 2H), 2.36 (t, J 7.4 Hz, 2H), 2.40-2.60 (m, obscured by DMSO), 3.10-3.40 (m, obscured by water), 4.68 (s, 1H), 4.95-5.00 (m, 1H), 5.65 (s, 2H), 6.77 (bs, 1H), 6.85-6.95 (m, 2H), 7.01 (t, J 7.7 Hz, 1H), 7.20-7.35 (m, 7H), 7.43 (d, J 7.8 Hz, 1H), 7.84 (bs, 1H), 8.23 (bs, 1H).
Analysis calculated for C 48 H 67 N 5 O 10 .H 2 O. Calcd: C, 59.30; H, 7.15; H, 7.20. Found: C, 58.85; H, 7.11; N, 7.08.
Example 17
Butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2,3-dihydro-1H-inden-5-yl ester, R-(R*,R*)! ##STR37##
To a solution of CI-988 (200 mg, 0.33 mmol) in DMF (5 mL) was added 5-indanol (44 mg, 0.33 mmol), BOP reagent (158 mg, 0.36 mmol), and diisopropylethylamine (92 mg, 0.71 mmol). After stirring for several weeks at room temperature the reaction mixture was poured onto 10% citric acid solution and extracted with ethyl acetate to give a brown gum (175 mg). Purification by column chromatography on silica, eluting with hexane/ethyl acetate 4:6 gave butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-2,3-dihydro-1H-inden-5-yl ester, R-(R*,R*)!- as an amorphous solid (38 mg, 16%), mp 93°-98° C. 300 MHz NMR (CDCl 3 ) δ 1.43 (s, 3H), 1.45-2.10 (m, 16H), 2.55-2.70 (m, 2H), 2.80-3.00 (m, 6H), 3.25-3.35 (m, 2H), 3.46 (d, J 14.6 Hzβ, 1H), 3.95-4.05 (m, 1H), 4.85 (s, 1H), 5.04 (s, 1H), 5.10-5.20 (m, 1H), 6.30-6.40 (m, 1H), 6.77 (d, J 8.1 Hz, 1H), 6.87 (s, 1H), 6.97 (d, J 2.3 Hz, 1H), 7.05-7.25 (m, 8H), 7.32 (d, J 7.9 Hz, 1H), 7.56 (d, J 8.0 Hz, 1H), 8.24 (s, 1H).
Analysis calculated for C 44 H 50 N 4 O 6 .H 2 O. Calcd: C, 70.56; H, 7.00; N, 7.48. Found: C, 70.80; H, 6.81; N, 7.54.
Example 18
Butanoic acid, 4- 2- 3-(1H-indol-3-yl)-2-methyl-1-oxo-2- (tricyclo 3.3.1.1 3 ,7 !dec-2-yloxy)carbonyl!amino!propyl!amino!-1-phenylethyl!amino!-4-oxo-, 2-(diethylamino)ethyl ester, R-(R*,R*)! ##STR38##
To a cooled solution of CI-988 in DMF (40 mL) was added dimethyl amino pyridine (32 mg, 0.26 mmol), diethylethanolamine (0.60 g, 5.12 mmol), and then dicyclohexylcarbodiimide (0.528 g, 2.56 mmol). After allowing the reaction to warm up slowly to room temperature overnight, the reaction was stirred at room temperature for 3 days. The reaction was poured onto ethyl acetate and water. The organic phase was separated, washed with water, dried (MgSO 4 ), filtered, and solvents evaporated to give an oil. Purification by column chromatography on silica gel, eluting with ethyl acetate/hexane 3:2 gave the product as a pale pink sold, mp 115°-120° C. 300 MHz NMR (CDCl 3 ) δ 0.85-2.00 (m, 29H), 2.55-2.80 (m, 4H), 3.20-3.30 (m, 1H), 3.30-3.45 (m, 2H), 3.50-3.60 (m, 1H), 3.80-3.95 (m, 1H), 4.05-4.20 (m, 1H), 4.83 (s, 1H), 4.90-5.00 (m, 1H), 5.25 (s, 1H), 6.30-6.40 (m, 1H), 7.00-7.25 (m, 8H), 7.40 (d, J 8.0 Hz, 1H), 7.50-7.60 (m, 2H), 9.05 (s, 1H).
Microanalysis calculated for C 41 H 55 N 5 O 6 . Calcd: C, 68.91; H, 7.76; N, 9.81. Found: C, 69.29; H, 8.06; N, 9.90.
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Novel pro-drugs to new and unnatural dipeptoids of α-substituted Trp-Phe derivatives useful as agents in the treatment of obesity, hypersecretion of gastric acid in the gut, gastrin-dependent tumors, or as antipsychotics are disclosed. Further, the dipeptoids are antianxiety agents and antiulcer agents. They are agents useful for preventing the response to the withdrawal from chronic treatment or with use of nicotine, diazepam, alcohol, cocaine, caffeine, or opioids. The pro-drugs are also useful in treating and/or preventing panic attacks. Also disclosed are pharmaceutical compositions and methods of treatment using the pro-drugs as well as processes for preparing them and novel intermediates useful in their preparation. An additional feature of the invention is the use of the subject pro-drug compounds in diagnostic compositions.
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BACKGROUND OF THE INVENTION
The present invention relates to a mixer and more particularly to a continuous mixer type that generally has a pair of rotors located adjacent to each other in parallel cylinders that form the mixer barrel.
In the manufacture of thermoplastic materials, the mixer receives the plastic material in its hopper and delivers such materials to a rotor means located in the mixer barrel wherein the rotor means advances, mixes and works the plastic materials to produce a homogeneous mix for general further processing. The art of converting solid thermoplastic materials into a satisfactory mixed and flowing homogeneous melt without overheating or chemical degradation depends in part on the type of thermoplastic material being worked on as well as the type of design of extruder or mixer used. During such mixing operation, it is essential to remove gases to obtain a high quality mix. Cost consideration requires efficient removal of gases otherwise the entrapped gases show up as porosity in the final product such as wire coating and transparent film. Entrapped gases lower the effective output capacity of the mixer by as much as twenty percent. Heretofore, degassing, if available, consisted essentially of mere venting of the mixer housing as by vent holes which became plugged with the material being mixed and advanced in the barrel. The remedy for this situation consisted of drilling the vent holes on a timed basis which could result in damage to the mixing screw or housing. The present invention contemplates the use of a vent hole or a series of holes which house a rotating vent screw. There is sufficient clearance between the vent screw and the vent hole to permit the escape of gases. In addition, the gases are permitted to escape through the screw flight openings.
SUMMARY OF THE INVENTION
The present invention contemplates a mixing apparatus having a pair of mixing screws or rotors or both housed in the main cylindrical barrel which has two adjacent bores that extend in a longitudinal direction and that communicates with a discharge opening. Such cylindrical barrel has a vent hole communicating the interior passageways with the atmosphere A vent screw is journaled in such vent hole and powered to rotate continuously to feed the mixed material back into the central passageways while allowing the venting of gasses through the clearance space provided between the vent screw and its vent hole.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic side elevational view of a continuous mixer apparatus with a portion of the cylindrical mixer housing or barrel broken away to disclose a portion of the mixing rotor and the vent screw with its motive rotating means;
FIG. 2 is an enlarged fragmentary cross sectional view taken on line 2--2 of FIG. 1 of the mixer vent screw located within the mixer barrel and with the motive power means for the vent screw;
FIG. 3 is a further enlarged fragmentary cross sectional view of the vent screw and the vent screw housing illustrating the clearance space to de-gas or vent the gas formed in the mixing process;
FIG. 4 is an enlarged side elevational view of the vent screw; and
FIG. 5 is a diagrammatic side elevational view of a modification of the invention as applied to an extruder apparatus and
FIG. 6 is a diagrammatic side elevational view of a further modification of the invention as illustrated in FIG. 5 but showing a plurality of vents and vent screws.
DETAILED DESCRIPTION
Referring to the drawings, wherein like reference characters designate like or corresponding parts throughout the several views, there is shown in FIG. 1 a continuous type of mixer 10 supported by a pair of spaced brackets 11. Mixer 10 has a hopper 12, a discharge opening in die means 13, transmission means 14, drive motor 15 and joined cylindrical housings 16, 17 and 18 in which a pair of rotors 20 and 21 (FIG. 2) are journaled for rotation. The joined cylindrical housings extend in a longitudinal direction and have a pair of adjacent bores 22 and 23 (FIG. 2) that extend from the hopper 12 to the opening in discharge die means 13. In lieu of the joined cylindrical housings 16, 17 and 18, one may have a single longitudinally extending housing. Such bores 22 and 23 communicate with each other along their entire length and may be considered parallel chambers. The rotors 20 and 21 which are journaled in such parallel bore 22 and 23 are driven in rotation from the motor 15 via transmission means 14. Such transmission means 14 rotate the rotors 20 and 21 in opposite directions. Such rotors are provided with lobes 25. The rotors are identical in construction and accordingly only one rotor will be described.
At the hopper end of the mixer 10, rotor 20 has a screw-like section 24 which conveys or feeds material to be mixed from the hopper 12 to the mixing section that contains the lobes 25 which may be considered helices 26. The material is mixed by helices 26 and axially advanced toward the reverse helices 27. Although only one set of helices 26 and 27 are shown, there may be any given number of such sets of helices of varying configurations to provide the desired successive melting and mixing of the material feed from the hopper through the bores 22 and 23. Such mixing by the helices 26 and 27 of the respective rotors 20 and 21 which rotate in opposite directions generates gases and moisture within the material which it is desirable to remove.
As seen in FIG. 2 the intermediate cylindrical housing 17 have their parallel chambers or bores 22 and 23 form an apex 30 along their upper juncture A bore 31 in the upper portion of housing 17 intersects the apex 30 and communicates the chambers or bores 22 and 23 with atmosphere. The axis of bore 31 extends at an acute angle (as seen in FIG. 1) relative to the linear apex 30 when viewed along such apex as extending in a direction toward the hopper 12. A sleeve 3 with a central bore 33 is press fitted into such bore 31 and defines a vent opening to atmosphere from such chambers. The axis of bore 33 makes an acute angle with the upstream longitudinal linear line of the apex 30 and an obtuse angle with the downstream linear line of the apex 30. The linear apex 30 is parallel to the longitudinal center line of bores 22 and 23 and when upstream or downstream direction of the apex 30 is used, the basis is made to the upstream or downstream flow of material through bores 22 and 23. Such reference is made since bore 33 does not intersect the axis of bores 22 and 23 but intersects the horizontal plane that passes through the axis of such bores.
As seen in FIGS. 1 and 2, a bracket 35 is suitably secured to the upper portion of cylindrical housing 17. Bracket 35 has a pair of threaded bores 36 receiving bolts 37. A bracket 38 having a pair of slots 39 aligned with spaced bores 36 and receiving bolts 37 allows the longitudinal alignment and adjustment of such bracket 38 relative to bracket 35.
A pair of spaced frame members or brackets 40 are welded to bracket 38 such that frame members or brackets 40 are parallel to the longitudinal axis of bores 31 and 33. Each frame member 40 is generally U-shaped in configuration having a pair of spaced bores 42. A slide member 43, H-shaped in plan view, has four slots 44. Such slide member 43 is slidably mounted on frame members 40 such, that bolts 45 extending through such slots 44 and through bores 42 permits longitudinal adjustment thereof. The slide member 43 has a cross brace 46 (part of the H-shaped slide member) which has a variable speed motor 47 suitably mounted thereon. The output shaft 48 of motor 47 is suitably connected via a coupling 49 to an output shaft 50 which in turn is connected to a feed or vent screw 51 which is journaled for rotation in sleeve 32. Feed or vent screw 51 is a double flighted helical screw which as shown in FIG. 3 has a slight clearance with the internal diameter of sleeve 32. Although there has been described but one vent bore or opening to atmosphere, there may be provided a plurality of such vent openings 32 with corresponding vent screws 51 to perform the function of venting gases to atmosphere while returning the extrudate mix back into the central chambers or bores 22 and 23 for further mixing.
In the operation of the above described extruder, the PVC material being processed by the mixer moves through the central chambers or bores 22 and 23 of the mixer barrel and is fed by the twin rotors 20 and 21 towards the discharge outlet in the die means 13. As the material is so moved, it is worked and heated whereby the solid PVC is dispersed, melted and mixed for dumping through the discharge opening. During such working action of the PVC material by the twin rotors 20 and 21, there is significant heating up of the PVC materials due to the shearing forces produced by the rotating twin rotors 20 and 21 which melts the particulate PVC or plastic materials which thereby releases volatile gases and moisture within the chambers or bores 22 and 23. Such gases escape through the pre-set clearance between the rotating vent screw 51 and the bore 33 that communicates the central chambers with atmosphere. The mixed melt is kept within the central twin chambers by the rotation of the screw 51 powered by the motor 47 which feeds the mixed material or melt that tries to exit via bore 33 back into the central chamber or bores 22 and 23 for movement via the flights of the rotors towards the discharge openings. With the gases thus removed during the mixing/compounding operation, the quality of the finished product is materially improved in an efficient and cost effective manner. It must be remembered that the entrapped gases lower output as they reduce effective internal volume capacity which lower apparent viscosity of the product thus lowering pumping capacity. Such lowering of capacity can be up to twenty percent of output capacity.
Although the invention has been described with respect to a continuous type mixer, such principle may be applied to a conventional extruder as depicted by FIG. 5. There is shown in FIG. 5, an extruder 60 having as in the first described embodiment a plurality of axially joined housings 61, 62 and 63, although a one-Piece cylindrical housing may be used. Extruder 60 has a hopper 64 at one end and a discharge die 65 at the other end. The respective axially joined housings 61, 62 and 63 have a central bore 67 that extends for the full length of such extruder, joining the hopper 64 with the die means 65. Journaled for rotation in the central bore 67 of extruder 60 is a feed screw 70 with a single flight 71 for the entire length thereof however terminating adjacent to the die means 65.
Other types of extruder screws may be used, however, the single flighted screw is shown as one example only. The extruder screw 70 is shown as driven by the transmission means 72 with its tip situated downstream of an outlet 75 which outlet 75 is connected to the die means 65. The core of the screw 70 may have flights of varying pitch and varying depth.
In the described embodiment of FIG. 5 the intermediate cylindrical housing 62 has a bore 31' similar to the first described embodiment which communicates the central bore 67 of extruder 60 with atmosphere. The axis of bore 31' makes an obtuse angle with the downstream longitudinal axis of central bore 67 and an acute angle with the upstream longitudinal axis of central bore 67.
As in the first embodiment such bore 31' receives a sleeve that is press fitted therein. Also as in the first described embodiment a power driven screw 51' is journaled for rotation in such bore 3l' and operates in the same manner as the first described embodiment. The support structure, motor drive means and brackets for the second embodiment of FIG. 5 is identical to the first embodiment and will not be described in detail since its structure is identical and it operates in the same manner.
In the operation of the embodiment of FIG. 5, the material being processed by the extruder moves through the central bore 67 of the extruder barrel and is fed by the helical flights 71 of extruder screw 70 towards the outlet 75 of the extruder. As the material is so moved, it is worked and heated whereby the material is dispersed and melted into a homogeneous mix by the time it reaches the die means 65. During such working action of the material in the extruder barrel, there is significant heating up of the materials due to the shearing forces produced by the rotating screw which melts the particulate or thermoplastic materials which thereby releases volatile gases within the barrel. Such gases escape through the preset clearance between the rotating vent screw 51' and its bores as in the first described embodiment thereby communicating the central extruder bore with atmosphere. The mixed extrudate is kept within the central bore 67 by the rotation of the screw 51' which feeds the extrudate that tries to exit via bore 31' from the central bore 67 such that the processed material is fed evenly via flights 71 for discharge through the die means 65. With the gases thus removed during the compounding operation, the quality of the finished product is materially improved in a very efficient manner. It must be remembered that the entrapped gases lower output as they reduce effective internal volume capacity which lower apparent viscosity of the product thus lowering pumping capacity. Such lowering of capacity can be up to twenty percent of output capacity. FIG. 6 illustrates a further embodiment consistent with the specification above, wherein there may be provided a plurality of vent openings with corresponding vent screws to perform the function of venting gaases to atmosphere. FIG. 6 illustrates this feature in a conventional extruder substantially identical to the described in FIG. 6 wherein like reference numerals refer to like parts except that FIG. 6 discloses but two axially joined housing 62 and 63 and further that the one housing 62 has two bores 31' rather than one bore 31' which communicate the central bore 67 with atmosphere and with each bore 31' having jounaled therein for rotation a power driven screw 51'.
The operation of the embodiment of FIG. 6 is identical as that described with respect to FIG. 5.
Various modifications are contemplated and may obviously be resorted to by those skilled in the art without departing from the described embodiments, as hereinafter defined by the appended claims, as only preferred embodiments thereof have been disclosed.
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A mixing apparatus for mixing thermoplastic compounds wherein the mixing body has a pair of parallel chambers with a pair of rotors rotatably journaled therein. Such mixer has at least one bore communicating the parallel chambers with atmosphere to vent gases from the central bore. A rotatable screw is mounted in the bore which upon rotation continuously feeds the mixed thermoplastic material back into the chambers but allows the gases generated to be vented out of such bore.
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CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 60/922,602 filed on Apr. 10, 2007, the contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates principally to components of devices for cleaning fluid-containing vessels and more particularly, although not necessarily exclusively, to valve assemblies for water interruption-type automatic cleaners for swimming pools.
BACKGROUND OF THE INVENTION
[0003] Commonly-owned U.S. Pat. No. 4,642,833 to Stoltz, et al. (the “Stoltz Patent”), whose contents are incorporated herein in their entirety by this reference, discloses various valve assemblies useful for automatic swimming pool cleaners. These assemblies typically include flexible, generally tubular diaphragms surrounded by chambers, with the diaphragms interposed in the main fluid-flow paths through the cleaners. In response to variation in pressure internally and externally, the diaphragms contract and expand transversely along at least part of their lengths, thereby controlling fluid flow therethrough.
[0004] Mentioned in the Stoltz Patent is that versions of the diaphragms may have “substantially oval-shaped or diamond-shaped cross section . . . when a total fluid flow interruption is to be achieved.” See Stoltz Patent, col. 3, ll. 36-38. Also detailed in the Stoltz Patent is use of longitudinal ribs “along that part [of a diaphragm] which contracts to the greatest extent.” See id., col. 5, ll. 32-33. According to the Stoltz Patent, such ribs enable a diaphragm to contract to an X-shaped pattern depicted in FIG. 7 of the patent. See id. ll. 33-35.
[0005] Commonly-owned U.S. Pat. No. 4,742,593 to Kallenbach (the “Kallenbach Patent”), the contents of which also are incorporated herein in their entirety by this reference, discloses additional valve assemblies for use with automatic swimming pool cleaners. These assemblies too are generally tubular in shape and made of flexible material. As noted in the Kallenbach Patent:
The body [of the tubular valve] has an intermediate section between the ends that assumes a substantially collapsed condition over a segment thereof in absence of a pressure differential between the interior and exterior. The section preferably is collapsed transversely over a segment. Along the collapsed segment, the body has diverging interior walls in the direction of water flow therethrough. The walls diverge from a substantially constant diameter that extends for a portion of the section adjacent the first end to a substantially constant, but larger, diameter that extends for a portion of the section adjacent the second end. Further, the divergence is a substantially linear function of the distance along the segment.
See Kallenbach Patent, col. 1, ll. 28-42.
[0008] U.S. Pat. No. 6,098,228 to Chang (the “Chang Patent”), entitled “Pool Cleaner Diaphragm Valve,” likewise addresses diaphragm-style valves and ancillary assemblies for automatic swimming pool cleaners. Apparently, however, these valves are of the type specified in the Kallenbach Patent. Indeed, according to the Chang Patent, this type of valve “is ideal” for the purposes described therein. See Chang Patent, col. 6, ll. 60-65.
[0009] Commonly-owned U.S. Patent Publication No. 2006/0054229 of van der Meijden, et al. (the “van der Meij den Publication”), whose contents are incorporated herein in their entirety by this reference, addresses further generally-tubular valve assemblies. Preferred embodiments of the assemblies include mouths divided into three parts. As stated in the van der Meij den Publication, this division “admits a larger through hole within the valves, in turn enabling larger debris to pass.” See van der Meijden Publication, p. 1, ¶ 0008.
SUMMARY OF THE INVENTION
[0010] The present invention provides alternatives to the valves of the Stoltz and Kallenbach Patents and the van der Meijden Publication. Included in the present valves is a closure region substantially larger than those in existing flexible valves. This region advantageously is shaped substantially in the form of a parabola or “V,” thus causing it to resemble the beak of a duck. At least in part because of its generally parabolic shape, the closure region does not present linear transverse cross-section to water flowing toward it.
[0011] Additionally, at least a portion of the closure region is closer to the inlet of the valve than in conventional valves. This portion, including the “tip” part (vertex) of the “beak” (parabola), may extend significantly below the lateral center line of the flexible valve. By contrast, for example, section 98 of valve 14 of commonly-owned U.S. Patent Publication No. 2006/0032539 of van der Meijden, et al. appears at or near the lateral center line of valve 14 of that publication.
[0012] By reshaping the closure region, flexible diaphragm-type valves of the present invention change their hinging action as well. In particular, substantial surface area is now included as the hinge, reducing the flexure load on the outlet from that experienced in existing valves. Valves of the present invention thus are expected to have more durable hinges than conventional flexible valves and thereby reduce wear at their outlets.
[0013] Present valves also may include teeth at or near the hinges of the closure region. Such teeth, together with corresponding recesses, function to reduce the likelihood of lateral movement of one portion of the valve relative to another. This decreased lateral movement further reduces wear in the vicinity of the hinging area. Reinforcing material, moreover, may be provided either internal or external to the valve walls.
[0014] It thus is an optional, non-exclusive object of the present invention to provide novel valves for devices such as automatic swimming pool cleaners.
[0015] It is an additional optional, non-exclusive object of the present invention to provide flexible valves having closure regions of substantially parabolic or “V” shape.
[0016] It is also an optional, non-exclusive object of the present invention to provide flexible valves, in the form of diaphragms, having closure regions extending closer to the fluid inlets of the valves.
[0017] It is another optional, non-exclusive object of the present invention to provide valves with hinging areas for enhanced durability.
[0018] It is a further optional, non-exclusive object of the present invention to provide valves including teeth and corresponding recesses for limiting lateral movement of one portion of the valves relative to another.
[0019] It is, moreover, an optional, non-exclusive object of the present invention to provide valves which do not present linear transverse cross-section to water flowing toward them.
[0020] It is yet another object of the present invention to provide reinforcing material for the valve walls.
[0021] Other objects, features, and advantages of the present invention will be apparent to those skilled in the appropriate field with reference to the remaining text and the drawings of this application.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is an elevational view of one side of a valve of the present invention.
[0023] FIG. 2 is an elevational view of FIG. 1 with the valve having been rotated approximately ninety degrees.
[0024] FIG. 3 is a longitudinal cross-sectional view of the valve of FIG. 1 .
[0025] FIG. 4 is a longitudinal cross-sectional view of the valve as rotated in FIG. 2 .
[0026] FIG. 5 is a lateral cross-sectional view of the valve of FIG. 1 .
DETAILED DESCRIPTION
[0027] Illustrated in FIGS. 1-5 is exemplary valve 10 of the present invention. Valve 10 comprises body 14 together with inlet 18 and outlet 22 . Body 14 has exterior surface 26 and interior surface 30 and preferably, although not necessarily, is generally tubular in shape. Body 14 typically is formed of a flexible, rubbery material and molded as a single part; those skilled in the appropriate art will, however, recognize that other types of body 14 may be suitable instead.
[0028] Depicted as well in FIGS. 1-5 are collars 34 and 38 , recess 42 , and one or more flexible sealing rings 46 of body 14 useful for, among other things, connecting valve 10 to other components of an automatic swimming pool cleaner. Collar 34 and recess 42 , forming part of exterior surface 26 at or adjacent outlet 22 , typically interlock directly or indirectly (or are co-molded with) extension pipes of the cleaner so as to fix the position of outlet 22 relative to the pipes (which in turn typically connect directly or indirectly to a flexible hose). Conventional valves are subject to wear in the region where the interlock occurs.
[0029] Collars 38 and rings 46 likewise form part of exterior surface 26 . Near inlet 18 , collar 38 and rings 46 connect body 14 of valve 10 to components within a head of the cleaner adjacent the mouth thereof. None of collars 34 or 38 , recess 42 , or rings 46 need necessarily be present on body 14 , however, as other connecting mechanisms may be used instead.
[0030] Preferably, valve 10 is positioned in the main fluid flow path within the cleaner. If so positioned, fluid in the form of water entering the mouth of the cleaner must pass through body 14 of valve 10 before exiting via the extension pipes. Entrained in the water stream typically will be debris (e.g., sticks, leaves, etc.), some or all of which also must pass through valve 10 and may tend to clog the passage defined by interior surface 30 of body 14 .
[0031] Intermediate inlet 18 and outlet 22 of valve 10 is section 66 . As illustrated in each of FIGS. 1-5 , section 66 beneficially is collapsed transversely so as to form mouth 70 of body 14 . FIG. 3 , especially, details a preferred mouth 70 having somewhat of a parabolic, or “V,” shape (shown in dashed lines) extending generally from a (nominally) upper portion 74 of valve 10 toward inlet 18 . Vertex 78 of mouth 70 , further, is positioned well below lateral center line LCL of body 14 , substantially closer to inlet 18 than are mouths of conventional valves.
[0032] Hence, rather than presenting an essentially linear transverse cross-section to fluid flowing through body 14 , mouth 70 presents a curved, non-linear cross-section effectively tailing away toward outlet 22 . This shape and the positioning of mouth 70 are advantageous in many situations, as they permit achievement of different closing forces and timing than in existing valves. Depending on the characteristics of pumps which will influence operation of valve 10 and the aquatic environments in which cleaners containing valve 10 will be used, beneficial operations of the cleaners may result.
[0033] Termination of mouth 70 remote from vertex 78 occurs in upper portion 74 of valve 10 . Termination regions 82 and 86 are formed (at least in some respects) as hinges for mouth 70 , flexing as mouth 70 cyclically opens and closes in use. Also present as part of body 14 are semi-circumferential hinging areas 88 A-B. Illustrated in FIGS. 2 and 4 as scalloped regions, hinging areas 88 A-B bend as mouth 70 open and closes. Because hinging areas 88 A-B are large relative to corresponding sections of other valves, they distribute the bending force over a larger area than is conventional, lowering flexure stress to which upper portion 74 is subjected. Displacing flexure load to these hinging areas 88 A-B likewise decreases flexure of valve 10 at or adjacent outlet 22 , resulting in less wear of body 14 at the outlet 22 (i.e. where connection to extension pipes occurs).
[0034] Shown especially in FIGS. 3-5 are teeth 90 and recesses 94 . Teeth 90 preferably are formed on interior surface 30 within first longitudinal portion 98 of body 14 , while recesses 94 are created within interior surface 30 in second longitudinal portion 102 of body 14 . Placement of teeth 90 and recesses 94 correspond so that teeth 90 fit within recesses 94 when mouth 70 closes. This fitting helps reduce any tendency of first longitudinal portion 98 to move laterally relative to second longitudinal portion 102 as the hinges flex, assisting preventing frictional wear that would result should such lateral movement occur. Although six teeth 90 and six recesses 94 (three of each in each of termination regions 82 and 86 ) are depicted in the figures, more or fewer (or none) of such teeth 90 and recesses 94 may be employed instead.
[0035] Formed (preferably) on exterior surface 26 of body 14 is reinforcing material 106 for the valve wall. Material 106 may be harder than the material from which body 14 is made, thus providing greater structural rigidity to portions of the body 14 . Although typically molded onto body 14 , reinforcing material 106 , if present, may be attached or connected to or within body 14 in any suitable way.
[0036] In some embodiments of valve 10 , material 106 has a complex outer shape comprising a generally parabolic section 110 and a generally circumferential section 114 . Vertex 118 of section 110 is placed near vertex 78 of mouth 70 ; by contrast, circumferential section 114 is positioned near the hinges formed at termination regions 82 and 86 . As illustrated in FIGS. 2 and 4 , material 106 preferably is incorporated onto each of first and second longitudinal portions 98 and 102 . To assist molding, exterior surface 26 may include flanges 122 with which material 106 interacts.
[0037] Similar to ribs of the valve of the Kallenbach patent, reinforcing material 106 functions to, among other things, stiffen valve 10 in the axial or longitudinal direction. The stiffness facilitates valve 10 resisting forces acting on it during closure of mouth 70 , reducing likelihood of section 66 collapsing (undesirably) in the vicinity of outlet 22 . Although, as noted above, reinforcing material 106 may be harder than body 14 , it need not necessarily always be so.
[0038] In use, valve 10 typically is deployed within an automatic pool cleaner in fluid communication with the inlet side of a pump. When the pump operates, its generally tends to evacuate the interior region of valve 10 , causing debris-laden water of a swimming pool to pass therethrough. More specifically, operation of the pump produces cyclical opening and closing of mouth 70 , creating water-hammer effect as mouth 70 closes to supply motive force to the cleaner. Those skilled in the art will understand that mouth 70 need not necessarily close completely as it cycles; instead, substantial closure may produce satisfactory results.
[0039] The foregoing is provided for purposes of illustrating, explaining, and describing embodiments of the present invention. Modifications and adaptations to these embodiments will be apparent to those skilled in the art and may be made without departing from the scope or spirit of the invention.
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Flexible valves principally (although not necessarily exclusively) for automatic swimming pool cleaners are addressed. The valves have generally parabolic closure regions and do not present linear transverse cross-sections to water flowing through them. The closure regions may extend substantially below the transverse center lines of the valves, which additionally may include teeth at or near hinges of the closure regions. Including the hinges reduces likelihood of undesired wear at or near the outlets of the valves.
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FIELD OF THE INVENTION
The following invention relates to electronic storage of data. More particularly, the present invention relates to systems and methods for memory allocation and writing in devices recording vehicle events.
BACKGROUND OF THE INVENTION
Video recording systems are commonly used to monitor places where it may be desirable to monitor security levels. For example, in a security zone, breaches of security may be recorded if video monitors area arranged around the space to be monitored. When an incident occurs, a video record of the related activity is available from the recording system.
During periods when no breaches of security occur, a considerable amount of data is still generated by the video recording system, which has little or no value. Thus, such data can be readily discarded without loss. The act of ‘discarding’ data amounts to merely rewriting new data over old recorded data. Indeed, most video security systems are arranged with a recording medium that is reused continuously.
When a video camera generates an amount of image data sufficient to fully consume the available memory, newly collected data is recorded at the beginning of the memory. Therefore, the act of writing newly acquired data causes old data to be discarded; that is, the old data is lost to the ‘write’ operation of the newly collected data.
In old videotape systems, this is sometimes called a ‘round robin’ arrangement. A memory medium fashioned as a tape in a continuous loop provides data storage for those video security systems. In such systems the tape has no end and no-beginning, but instead the tape continuously passes by a recording head where new images are written to the tape and at the same time old images are discarded.
When an incident of interest occurs, the tape may be stopped to prevent loss of data which relates to the relevant incident. The related images may be recovered from the tape and transferred to a permanent medium, while the tape is returned to the video system for further recording. Such re-use of memory is well known in the prior art.
In a round-robin scheme, the data that is overwritten, or discarded, is the data which came into the system earliest, or was ‘first in’ the system. This arrangement is sometimes referred to as “first-in, first overwritten,” which is analogous to the “first-in, first-out” arrangement in electronic buffer systems. In both cases, we will refer to this method as FIFO.
A FIFO base system is generally a very good system for buffer management, because the oldest data in a buffer is typically the least valuable. Therefore, the oldest data, or the least valuable data, may be discarded without regard for its loss. However, in buffer systems the earliest received data, or the ‘first-in’ data, may not always be the least valuable data. In some instances it may be advisable not to overwrite the oldest data, but rather to provide an overwrite scheme which preserves certain portions of interest of the oldest data.
With specific reference to the monitoring of vehicle activities, vehicle event recorders are video recorder systems mounted within the vehicle to provide a video record related to the environment surrounding a vehicle during its operation. These systems are known in the art and are employed, for example, in conjunction with police activity. Many police departments in the United States are equipped with vehicle event recorders, which capture activity, sometimes criminal, occurring in the proximity of a police vehicle.
The application of vehicle event recorders is not limited to police vehicles. More and more commercial vehicles are now equipped with systems that record activity associated with the use of the vehicle and within the environments in which the vehicle is used. These systems are particularly advantageous with fleet vehicles that are subject to heavy professional use and frequent incidents, including traffic accidents, theft, and vandalism, among others. With a video record, vehicle fleet managers are better equipped to manage and control costs associated with operations of large vehicle fleets. Safety is improved, driver performance is improved, a better understanding of accidents is achieved, and other benefits are derived from the use of vehicle recorder systems.
Vehicle recorder systems are described, for example, in U.S. Pat. Nos. 6,389,340, 6,405,112, 6,449,540, and 6,718,239, all to Rayner. In general, these inventions relate to a small device mounted on the vehicle rearview mirror to capture video images of traffic incidents ahead of the vehicle.
In particular, the '112 patent discloses a system that includes a vehicle operator performance monitor, which records a video of the vehicle operator, and which may be used to determine how the operator's actions affect use of the vehicle.
The '540 patent instead is an event recorder mounted in a vehicle, which includes one or more wave pattern detectors for detection and recognition of a predetermined wave produced outside the vehicle, and for producing a trigger signal denoting the presence of the predetermined wave. In particular, a detective wave is a wave of the type produced by a police or fire department emergency vehicle. Detection of this wave triggers a capture function which stores video images a long-term storage memory.
The '329 patent includes a video recorder system having a one-way hash function to perform a validation function. This way, the integrity of the recorded video data can be protected.
Finally, the '340 patent teaches a recording system having a certain relationship between two different types of memory. A first memory is arranged to store video for the short-term and to transfer some of that stored video in response to a trigger event. Data from this short term memory is transferred to a more durable and long term memory, and the short term memory is continuously overwritten in a scheme described by Rayner as “first-in, first-overwritten”. This way, Rayner teaches the coupling of a high-speed, high-performance volatile semiconductor memory with a flashlight memory good for long-term storage of large amounts of data even when power is removed. As will be described in detail later, Rayner's first in first overwritten scheme necessarily creates a loss of important and valuable data.
While systems and inventions in the prior art are designed to achieve particular goals and objectives, these inventions also include limitations which prevent their use in more extended applications, and cannot be used to realize the advantages and objectives of the inventions taught hereinafter.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide high-performance memory allocation systems for vehicle event recorders.
It also is an object of the present invention to provide for set memory allowances and for extended recording periods.
It is a further object to provide memory overwrite schemes that provide a time dilation on either end of a recording period.
These and other objects of the present invention are accomplished by apparatus and methods for allocating memory in vehicle event recording systems that provide improved memory allocation and writing schemes to preserve data over extended time periods, thereby improving prior art devices and methods that cannot record events over a large time range when equipped with a memory of a predetermined size.
One difference between memory allocation of the present invention and the prior art can be seen in relation to time dilation, which may be applied on the extremities of discrete capture periods. In one embodiment, a memory of limited size is subject to an advanced managed loop memory allocation scheme and the rate of storage frame is adjusted throughout a predetermined capture time period. At the extremities of a time period, a frame capture process is subject to a reduced frame rate. In the proximity to an event of interest, or an ‘event moment’, the frame rate—is increased to improve detail around that particular time, enabling a greater temporal range at the expense of temporal resolution. Losses in temporal resolution are however pushed away from the event moment and allocated to the extremities of the capture time period.
An overwrite scheme selects which frames are expired and subject to being discarded. At any random moment, video is continuously captured at a maximum frame rate. However, these frames are not stored into memory in a conventional first-in, first overwritten manner, but rather, these frames are added to the memory locations which are determined to be available in accordance with the overwrite scheme. Therefore, the oldest frames are not necessarily those that are overwritten. Quite to the contrary, an overwrite action may be applied to a frame which is newer than at least one other frame stored in the memory.
As a result, newly acquired frames are placed into memory in processes which necessarily cause older frames to be discarded. However, the newly captured frames are written to memory positions in an ‘interleaved’ fashion, whereby some of older frames are preserved. When a capture event occurs, data in the memory may be transferred to a more permanent storage. When data is transferred, a timeline is reconstructed. The recorded timeline is unique in that it contains various frame rates over the capture period. At both the beginning and at the end of the capture period, the frame rate is modest. At the point of greatest interest in the capture period, the frame rate is the highest. This throttling of frame rate provides for a memory of given size to accommodate a timeline of greater temporal extent.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects and advantages of the present inventions will become better understood upon consideration of the following description, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a timeline illustration in conjunction with a graphic that illustrates a plurality of memory bin units;
FIG. 2 is a timeline illustration and memory graphic illustrating an overwrite operation; FIG. 3 illustrates the overwrite operation in conjunction with a trigger event;
FIG. 4 illustrates particular memory bins with various levels of importance associated therewith;
FIG. 5 illustrates an advanced overwrite scheme to protect certain ‘high-value’ video frames;
FIG. 6 further illustrates this overwrite scheme near the end of memory space;
FIG. 7 illustrates memory allocation with pointers to memory bins to be saved and pointers to those bins to be erased;
FIG. 8 illustrates four alternative timeline illustration in different embodiments of the invention;
FIG. 9 is a block diagram of one embodiment of the invention;
FIG. 10 is a block diagram representing an embodiment of a methods for memory management; and
FIG. 11 is a more detailed block diagram of the method of FIG. 10 .
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to apparatus and methods are provided for overwriting memory in vehicle event recorder systems. Embodiments are described hereinafter, that are constructed in accordance with the principles of the present invention, In order to facilitate the understanding of the described embodiments, definitions are provided for terms that may not be readily available in popular dictionaries.
Vehicle Event Recorders: Video image recording systems which are responsive to triggers indicative of some event of interest.
Time Dilation: An expansion of a video sequence timeline by way of frame rate manipulation.
Trigger: Electronic means for setting some instant in time associated with a particular event of interest and further for causing initiation of some associative processes.
Expanded Timeline Definition: A prescribed set of rules which sets forth and defines a timeline associated with a video frames sequence having more than one frame rate associated with any particular portion of the timeline.
Overwrite Manager: A computer module determining, in accordance with an expanded timeline definition, which data recorded in memory and associated with a particular video frame is to be discarded and may be overwritten with data from a newly collected video frame.
Video event recorder systems are typically built around and deployed with memories of limited sizes, in order to contain cost. While mass storage and mass storage management may be included in such devices, for example, a computer-type hard drive, these types of components remains quite expensive, causing overall systems to double in cost if such memories were included. Instead, a ‘lightweight’ memory solution is envisioned in the present invention, in which an abbreviated memory or memory buffer is used to temporarily store information collected during a predetermined time of service, for example a day, of a vehicle equipped with this type of video event recorder. Upon return to base, a vehicle may transfer the information collected to a different memory for management and analysis. Accordingly, the present invention makes it possible to equip vehicles with video event recorders having very inexpensive cameras and memory.
Memories of such video event recording systems are preferably handled in the following manner. A memory system is divided into two portions: a fast, managed loop memory buffer, and a temporary mass storage memory.
Video continuously received from a video camera may be put into the fast memory buffer. However, the amount of data generated by a video system is quite extensive and most of the time totally uninteresting, but certain portions of the video may become of great interest. For example, when a vehicle is involved in a traffic accident, the captured video may yield important clues as to fault, cause, identity, and response, among others. In this event, it is important to preserve video data associated with these select video capture periods.
To this end, a trigger is arranged, whereby the occurrence of some incident of interest, such as an automobile accident, causes data stored in the memory buffer to be transferred to a more permanent memory facility. Old data in the memory buffer is continuously overwritten by new data received from the video camera in real-time. In common and simplistic versions, this step is performed in a “first-in, first-overwritten” manner.
Because the memory buffer is limited in its capacity to store video frames, “first in first overwritten” schemes provide a timeline of limited extent. For example, at a frame rate of four frames per second, a given memory buffer may be suitable for storing 30 seconds of video frame data, or a 30 second video timeline. In ‘first-in, first overwritten’ schemes, this timeline may be arranged as 15 seconds of continuous video before a trigger event and 15 seconds of continuous video after a trigger event.
However, a continuous frame rate throughout the entire event capture period need not be maintained. It is possible to have a modest frame rate at times associated with the capture period extremities, and a high frame rate during periods around an event trigger. Therefore, the storage frame rate may be adjusted throughout a prescribed capture time period, allowing for an extended temporal range. Instead of a 30 second timeline, is entirely possible to have a 48 second timeline for the same memory. Such a timeline may be embodied as 12 seconds of video at a frame rate of one frame per second for the periods of time furthest apart from the event trigger, both before and after. In addition, the video sequence may include video for 24 continuous seconds, 12 seconds before and 12 seconds after an event trigger, at a video frame rate of four frames per second. This way, the temporal range is extended but the temporal resolution is compromised in the time periods furthest from the trigger event.
To create such a managed loop memory buffer management system, an overwrite scheme is provided to select which frames are ‘expired’ and no longer part of the particular extended timeline scheme. It should be remembered that video is continuously captured at all times, and that video is captured at the maximum frame rate, because it is not known in advance when an event trigger will occur. Accordingly, the system always captures video at the maximum frame rate as the capture frame rate cannot be adjusted in view of any event trigger which may come in the future.
Video captured at the maximum frame rate is put into the memory and as it is put in the memory it displaces previously recorded video frames. These frames are added to the memory locations determined to be available in accordance with a prescribed overwrite scheme such as the one mentioned above. However, this step is provided differently from a first in first overwritten scheme. In the presently described embodiment, most frames being overwritten are actually newer than at least one other frame stored elsewhere in the memory buffer. Newly captured frames are written to memory positions in a pseudo-‘interleaved’ fashion while some of older frames are preserved.
When a trigger event occurs, data in memory is transferred from the memory buffer to a memory of more permanent nature. When such data is transferred, an expanded timeline is reconstructed as a timeline having at least two frame rates. At the extremities of the capture period timeline, the frame rate is reduced. At and about the point of greatest interest (trigger event) the frame rate is maximized during the capture period. This ‘throttling’ of frame rate provides for a memory of preset size to accommodate a timeline of greater temporal extent, although in some places resolution may be reduced.
Referring now to FIG. 1 , a first timeline is shown that is associated with a memory system divided into a plurality of memory bins. For exemplary purposes, some arbitrary numbers for memory size, number of bins, video frame rates, etcetera, have been selected. It is to be understood that these are not necessarily preferred values, but values selected to promote an understanding of the example provided.
The memory related to FIG. 1 is a high-speed, high-performance memory of limited extent, and is arranged as a buffer. This memory communicates with incoming video data recorded by a video camera, and its output is directed to another means for data storage means, such as a memory system having a greater capacity but lower speed, for example a semiconductor DRAM type memory. Alternatively, the memory of FIG. 1 may be a non-volatile, high-performance memory based on ferromagnetic principles, which can respond in real-time to video collected by a video camera, but is of limited size and not suitable for saving the mass amounts of data generated by video image systems.
In general, the memory of FIG. 1 may be limited to a few megabytes and may temporarily hold a limited number of video frames, which may or may not be transferred to a more permanent memory in a transfer operation. In particular, the memory may be divided into 120 bins, with each bin be sufficient for storing the data associated with a single video frame.
A timeline 1 is associated timeline 1 with this memory, and is comprised of a 30 second time interval. The timeline is marked in the Figure from 0 to 30. A one second interval 2 is illustrated at the beginning of the timeline. Further, that one second interval is divided into quadrants, representing a quarter of a second interval 3 . For the video systems of immediate interest, his quarter of a second interval nicely accommodates a single video frame (implicitly setting a frame rate of four frames per second). While most modern video systems have far higher performance than recording four frames per second, four frames per second is a useful rate for vehicle recorder systems, which tend to have limited memories in the interest of maintaining a low cost. Further, the kinds of events being recorded in vehicle recorder systems are appropriately captured with frame rates of a few frames per second.
When video images are captured by a camera, frame-by-frame, each frame images can be recorded into a memory bin 4 . A first frame is recorded and put into a first memory bin. Thereafter, a quarter of second later, a second frame is recorded and put into an another memory bin, for example, an adjacent bin. This frame-by-frame recording scheme may continue for up to 30 seconds before all memory bins becomes full and the supply of empty bins is exhausted. In FIG. 1 , the first 116 memory bins are shaded to indicate that one frame each of video data has been written to those bins. This is equivalent to recording of a video signal 5 of four frames per second for 29 seconds. FIG. 1 also illustrates four empty memory bins 6 , which would be filled in the next second of video recording. Because the recording of video images in this manner is known in the art, Figure a is labeled as prior art.
FIG. 2 illustrates a similar timeline 21 in conjunction with a graphical illustration of a memory having 120 memory bins. As in FIG. 1 , a time interval equivalent to one second 22 as well as a time interval of one quarter second 23 is illustrated for reference. The graphical depiction of the memory includes lightly shaded areas 24 and 25 . The memory bins presented as 24 represent those bins having data written thereto from a video which was collected from a time t=14 up to a time t=30. The demarcation indicated as dotted line 26 indicates time t=14. At time t=30, the memory is completely full. Video data collected for 30 seconds at four frames per second fills 120 memory bins. The video data collected at time t=31 cannot be saved to memory unless a portion of the memory already allocated and consumed in a previous data write step is overwritten. Thus, in the graphic of FIG. 2 , memory bins indicated by 25 on a second line represent—that video frame data that is recorded in these memory bins at the expense of data captured 30 seconds prior. Accordingly, for the time period indicated, i.e. video data collected from t=0 to t=14, that video data is lost to an overwrite step. In FIG. 2 , those bins shaded dark are indicated as 27 , representing the overwritten bins. This illustrates the so-called ‘round-robin’ or ‘first-in, first-overwritten’ FIFO memory management schemes. Since these schemes are also known in the art, FIG. 2 is also labeled as prior art.
The FIFO memory management scheme is very useful. When a new video frame is collected by the video camera, it is placed into memory at the same location as the oldest frame in the memory which is discarded in the overwrite step. Therefore, the FIFO memory management scheme implies that the oldest video information in the memory is the least valuable.
The memory described is a buffer memory, that is, this memory temporarily holds the data of a video series for some specified time, but also continuously discards previously recorded information. When the buffer contains a data set associated with an important event, that data is transferred from the buffer memory to a more permanent memory before becoming subject to being lost by overwrite actions. A video series becomes ‘important’ when a detectable event occurs which implicitly indicates video is valuable; for example, if a vehicle is involved in a traffic accident, accelerometers can detect the accident and trigger a transfer of data from the buffer memory to a permanent memory.
In those vehicle event recorder systems, a trigger is sometimes arranged to indicate that such an event has occurred, that is, an event for which the video images associated therewith may be of extreme importance. In this case, the short term buffer memory of 120 video frames should be transferred to a more permanent long-term memory for example, a durable flash type memory.
FIG. 3 is directed at illustrating a timeline which includes an event moment. FIG. 3 includes a timeline 31 , and the dashed line 32 to indicate the 29th second along with a marker ‘X’ 33 to indicate a trigger event has occurred at the 29th second. When a trigger event occurs, it is important to preserve the video data which occurred after the accident as well as the video data which occurred before the accident. Video images collected during a time period starting 15 seconds before the accident are in the bins indicated by 34 ; i.e. those video image frames collected between t=14 and t=29. Memory bins at the end of the time line indicated by 35 include four video frames collected during the first second after the accident. Video image frames collected between t=30 and t 44 are placed in the memory bins indicated by 36 . Thus, the memory buffer contains video images for the 15 seconds prior to the accident and the 15 seconds after the accident. Because the memory is of limited size, it can only hold video image data which represents 30 seconds of video recording.
At this point in time, no new frames are recorded to memory; overwrite is prevented, and the memory buffer is “locked”. Rather, the system pauses to transfer data in the buffer memory to a permanent flash memory. After data is successfully transferred to the flash memory, the buffer is “unlocked” and may be used again in the fashion described. As video data which was placed into buffer memory bins between time t=30 and time t=44, it caused older data to be displaced, overwritten and forever destroyed. Data which was recorded between t=0 and t=14 is completely lost and no access is possible any more to this information, which at one time resided in those memory bins, because that information was destroyed in the overwrite step. However, some of this information may be very valuable and, accordingly, it is quite undesirable to lose it entirely; in fact, some of this data may be more important than data which saved in its place.
Since the moments leading to a vehicle accident can explain a great deal about the what actually happened, it is highly desirable to have at least some limited information that relates to the accident scene at t=1, for example. If one can just see one frame at t=1, that may be extremely valuable in explaining what happened in the accident. Therefore, the FIFO scheme may actually destroy critically useful data.
This is also apparent from FIG. 4 , which explicitly shows certain bins A-F associated with various points of the timeline 41 and with reference to trigger event 42 time at time t=29. The following discussion further illustrates the importance of bins A-F.
In a FIFO system, all memory bins, indicated by reference numerals 44 and 45 , are preserved in the memory buffer. Amongst the oldest recorded video frames remaining are those which reside in memory bins A and B, and which represent two adjacent frames, or frames captured within a quarter of a second from each other. Since these frames represent images very close in time, these frames are expected to be quite similar to each other. While it is sometimes desirable in video systems to have high temporal resolution, i.e. as many frames per second as possible, one will appreciate that at higher frame rates, a frame will contain very similar information as the frame closest thereto. Accordingly, where memory is limited, these adjacent frames lose their importance as most of the information contained in each frame is similarly contained in the adjacent frame. Thus, if we keep frame A and discard frame B, most of the information of frame B can be known by examining frame A.
On the other hand, frames D, E and F, which are discarded in a FIFO system, may actually contain extremely important information. Frame D is separated in time from frame E by one second. In a video scene, there may be considerable differences between one frame captured an entire second later than another frame. Further, frame D occurs a full 29 seconds before the trigger event. In a traffic accident, it can be quite useful to know about what was happening at time periods before and after a trigger moment. Thus, it may be possible in a memory having a finite number of memory bins to trade some of the bins associated with less important time slots for bins associated with time slots having a greater importance. If we discard frame B, and preserve frame D, we may gain a greater overall understanding of the incident being recorded. In effect, we can trade some time resolution (frame rate) at t=15, for improved overall temporal range to realize an extended timeline.
One skilled in the art will notice that if video data associated with a frame rate of one frame per second was preserved, in seconds 1-12, then 36 memory bins into would remain available, which would accommodate newly captured video data. Thus, rather than completely overriding the oldest video data in memory, one can perform an overwrite action on 3 of every 4 memory bins in the overwrite portion of the timeline, thereby maintaining ¼ th of the oldest video data in those memory bins. That is to say, for the oldest video data in memory, it may be useful to save one frame per second. To this end, when the overwrite operation is executed, new data is written to three memory bins, before one bin is skipped, and the process is repeated.
Timeline 51 includes a trigger event 52 at time t=29. In one overwrite scheme of interest, it is required that a timeline be comprised of 12 seconds of low temporal resolution, 24 seconds full temporal resolution and a further 12 seconds of low temporal resolution. This is further defined in detail as: a 12 second period of one frame per second video, a 24 second period of four frames per second video, and finally a 12 second period of one frame per second; for a total video sequence of 48 seconds. Since it cannot be known at what time in the future an event trigger will occur, a data overwrite scheme must preserve data associated with various frames, of which a prescribed timeline is comprised. In the present example, continuous video data at a frame rate of four frames per second is preserved for a period of 12 seconds 54 before the trigger event; that data is in memory bins indicated by 53 . While in the FIFO system one can preserve data at four frames per second for up to 15 seconds before and after the trigger event, in the system of the present embodiment only 12 seconds of four frames per second data be kept. However, it will be shown that the present embodiment enables the expansion of the total timeline of the video sequence to 48 seconds in contrast to the 30-second timeline of the FIFO system.
In the 31st second, the first overwrite operation begins. Whether or not a trigger has occurred, newly captured video data is written to every three out of four memory bins, leaving the fourth memory bin undisturbed. Therefore, old data is preserved, albeit at one quarter of the frame rate from which it was originally recorded. Video data after the trigger event is recorded in the memory bins 55 at a frame rate of four frames per second. Just because some bins are skipped, the frame rate of video data collected after the trigger event is not necessarily reduced. This is readily understood in consideration of the time point indicated by 57 which indicates the time t=41 seconds, while, without skipping bins, this point in memory would have been time t=45. Careful observation will prove that the bins indicated by 55 will accommodate data at four frames per second for the entire 12 seconds after the event trigger.
After the time point indicated by 57 , several memory bins remain available for further overwrite operation before reaching the memory bins which contain data to be. preserved in agreement with the timeline definition 12/24/12. At least some of those memory bins up to the position indicated by 54 are available for overwrite. After the full 12 seconds of four frames per second video is recorded, it is desirable to continue recording video data at one frame per second for an additional 12 seconds. Data captured in this period can be stored in memory bins, which are scattered in various locations about the memory buffer. FIG. 6 illustrates on example of such locations.
More particularly, FIG. 6 illustrates memory bin locations which are available for overwrite as the memory approaches its full capacity for the particular schemes presented herein. Once a trigger event occurs, i.e. is set in time, it is possible to compute which video frames must be saved in accordance with the particular timeline definition, and which frames may be discarded. For example, 48 frames at four frames per second may be preserved immediately before the trigger event. In addition, 12 frames at a video rate of one frame per second may be preserved for the time t=5 up to t=17. These frames must be protected from any further overwrite operation, and are marked “must be saved” in FIG. 6 . These frames are saved as they are included in the timeline definition.
All frames which precede t=5 are in condition for being discarded. that is, such frame lie outside the time range which is to be preserved. Accordingly, frames indicated for example as 69 have aged sufficiently and are may be erased. These are the frames which originally were preserved in the overwrite operation as skipped frames.
Video frames captured after the trigger event are also saved in the memory. For 12 seconds after the trigger event, t=29 to t=41, video is captured at a rate of four frames per second. Such a video data 65 is put into memory in accordance with the need to save particular frames of the oldest video data. When all video frames from the period t=29 to t=41 are properly recorded, the system continues to record data at the frame rate of one frame per second. This is different from the earlier operation, in which the overwrite action resulted in the preservation of one frame per second.
For the time period 12 seconds after the event trigger up to 24 seconds after the event trigger, data is put into memory at the reduced frame rate of one frame per second. Other frames may be captured by the camera, but are discarded before entering the memory or instantly thereupon. Thus, the frames represented by 67 are put into memory bins which are available in accordance with the “OK to erase” label in the drawing. A person skilled in the art will note that after three of these frames are placed in the memory, the fourth frame 68 cannot be placed into the memory in the same repeating geometric position. That is to say, those memory bins are not available for overwrite. Therefore, video captured after that time must be carefully managed and fit into the available memory bins.
FIG. 7 illustrates the steps taken in the final filling of the remaining memory bins. In timeline 71 , event trigger 72 is situated at time t=29. In agreement with this exemplary timeline definition, video captured at a frame rate of four frames per second from t=17 to t=29 is stored in memory, as indicated by 73 . Similarly, video captured for a 12 second period at a frame rate of four frames per second from t=29 to t=41 is stored in memory, as shown by reference numeral 74 . Finally, video frames captured during a 12 second period from t=42 to t=54 at a frame rate of one frame per second include those particular frames represented as 75 , which must be inserted into the memory bins remaining available for overwrite.
Arrows 76 indicate that these frames may be placed in locations near the beginning of the memory, where data had once been stored but is now expired because the trigger event occurs at t=29. Once a trigger event is established, the bins which may be overwritten can be determined according to the particular rules defining the timeline.
The example of FIG. 7 clearly illustrates that careful management of an overwrite scheme enables a memory buffer to dilate a timeline by manipulating which video frames are preserved and which are overwritten. Consequently, temporal resolution is sacrificed to extend temporal range, that is, the frame rate of “saved data” is altered in order to make more space available for video frames captured further in time from the event trigger. Accordingly, the greatest amount of information can be preserved in a memory buffer of the limited size.
While the example of FIG. 7 illustrates where the data may be written in memory, those skilled in the art will note that the physical positions of memory bins may be altered. Therefore, after a timeline definition is set, an algorithm may be developed defining the bins containing data that has expired and thus implicitly defining a bin available for overwrite at any moment time.
While the example presented of FIGS. 5-7 illustrates one possible solution, it should be understood that other arrangements may provide for a time dilation in accordance with the spirit of the present invention, and that specific values may be used that are different from those presented in the above exemplary timeline definition. In another exemplary timeline definition, one might arrange a system whereby two periods of eight seconds are used to capture video of a high frame rate, and two periods of 28 seconds are used to capture data at a low frame rate, thus achieving a total expanded timeline of 72 seconds.
The advantages offered by the above examples do not depend upon the particular values chosen in these examples. One should also recognize that because capturing/saving video at two different frame rates enables a user one to expand the timeline, capturing/saving video at three different frame rates also enables a user to expand the timeline with greater flexibility. Accordingly, the memory may be manages to preserve frames for some time periods at a rate of four frames per second, and in other time periods at a rate of two frames per second, and in still other time periods at a rate of one frame per second. This arrangement provides for very high temporal resolutions for the periods immediately surrounding an accident (trigger event), for medium level resolutions for periods further away from the trigger event, and finally for low temporal resolutions at the extremities of the time range.
In addition, asymmetric timeline definitions are possible, that is, the time periods on either side of the event trigger may not be equal in extent or in number. A timeline definition may be devised that has a long, high resolution period before the event trigger, and a short high resolution period after the event trigger. FIG. 8 illustrates various timeline definitions of interest, and is related to several examples each working equally well within the common concept of timeline dilation. FIG. 8 graphically illustrates a first memory buffer 81 , which was discussed in detail in a previous example, and in which there are two frame rates, namely, a high video frame rate of four frames per second and a low video frame rate of one frame per second.
A trigger event 82 occurring at some instant in time implicitly sets the time periods for any particular example, and time period 83 starts immediately after the trigger event and extends for 12 seconds. A second time period 84 extends from the trigger event to 12 seconds prior to the trigger event. In both of these time periods, video is captured and put into the memory buffer at a rate of four frames per second.
The number of shaded memory bins reflects a frame rate of 4 frames per second. Time periods at the extremities of the timeline, periods 85 and 86 , are each also configured to be 12 seconds in length. However, since only one frame per second is collected in those time periods, the number of memory bins consumed is considerably smaller, i.e. ¼ of those consumed in the other time periods. This arrangement provides for a total timeline of 48 seconds, and in memory buffers that do not overwrite/store data at variable rates, the same memory size could only accommodate a timeline of 30 seconds. FIFO memories of the same size are restricted to 30 seconds.
A second example presented as 87 in FIG. 8 suggests two high temporal resolution periods of 10 seconds each. In addition, there are two low temporal resolution periods of 20 seconds each. While there is a reduced overall period of high-resolution video data, the total timeline is extended to 60 seconds.
A third example is presented through the memory buffer of graphic 88 , and illustrates that an asymmetric timeline definition may also be configured. The two periods with a high rate of video recording need not be the same in extent. In fact, video may be recorded at a high frame rate for a longer period after a trigger event than that in the period immediately preceding the trigger event. In the present example, video is recorded in the memory buffer for 16 seconds after the trigger event, but only for four seconds prior to the trigger event. Accordingly, the total high-resolution time period is the same as in the previous example, 20 seconds, but greatly favors preserving information after the trigger event, at the expense of information preceding the trigger event.
In a fourth example, there are six distinct time periods comprised in the timeline. Two 9 second periods occur symmetrically about an event trigger. In these time periods video may be captured a rate of four frames per second. Two additional periods each of 8 seconds may be used to record/overwrite data at a frame rate of two frames per second. Two additional 8 second periods are provided to store data at a frame rate of one frame per second. One skilled in the art will appreciate that in the timeline of this example, two of the 8 second periods are of different sizes with respect to memory capacity, i.e. greater number of bins, than the other two 8 second periods. This is consistent with the higher frame rate used in two of the 8 second periods.
One skilled in the art will also appreciate the great latitude available for managing a memory buffer of limited capacity to expand a timeline. One skilled in the art will further appreciates that where memory buffers deploy FIFO or ‘round-robin’ strategies for overwrite operations, very important data may be lost. FIFO and ‘round-robin’ strategies discriminate against the oldest data in a memory buffer, and in situations where the oldest data is not the least valuable, FIFO and round-robin systems are inferior to the system of the present invention.
Referring now to FIG. 9 , the fundamental elements of apparatus according to the present invention is described. Video camera 91 is operable for collecting optical energy and for converting the image of a scene into electrical signals, suitable for processing by common electronic means such as digital semiconductor memories and processors. In addition, these systems include a trigger mechanism 92 .
In one embodiment, a trigger mechanism is the device arranged to provide an electrical signal that indo indicates that a particular video series should be transferred to permanent memory for long-term storage. A trigger may be an accelerometer operable for detecting abrupt changes in speed, for example, speed changes related to a traffic accident. Triggers may be activated by other events such as heavy braking or swerving maneuvers, and may be activated by means other than accelerometers. For example, a user panic button can be used to activate a trigger event.
When the user believes that a video series should be saved, he can hit a panic button to activate one type of trigger. It is not relevant what precisely causes a trigger to be activated, but rather how memory performs once a trigger event has occurred. Overwrite manager 93 is a control module that interfaces with the trigger and a video camera, and also with a buffer memory 94 . An overwrite manager includes means where a timeline definition may be set and further means for executing overwrite operations in agreement with the stored timeline definitions. Further, an overwrite manager may additionally integrate with flush-module 95 .
When a trigger event occurs, overwrite manager 93 continues to overwrite data to buffer memory 94 in accordance with the timeline definition, by way of an overwrite pointer which is associated with a cell subject to an impending overwrite action. Overwrite manager 93 sends a signal. 96 to flush module 95 that cause flush module 95 to copy buffer memory 94 and to transfer the video data set with the prescribed expanded timeline to high-capacity long-term storage 97 . Overwrite manager 93 controls the algorithms and the necessary processing components for writing to buffer memory 94 and save selected data while purging redundant data in accordance with a particular expanded timeline definition.
FIGS. 10 and 11 which illustrate the primary steps of methods in accordance with the present invention. In particular, FIG. 10 describe such methods in the most general sense to include step 101 , whereby frame data is received from a video camera, and step 102 , whereby the newly received data is written over old data stored in the memory buffer according to an expanded timeline definition.
FIG. 11 illustrates these methods in greater detail. Frame data 111 is received from a video camera in a first step. Buffer memory data write step 113 includes sub-step 114 , in which the frame is written to a bin marked open. It is important that data be written in the buffer memory in an organized fashion, without disturbing particular data frames, necessary to fill the prescribed expanded timeline definition. Therefore, a bin is marked ‘open’ when it no longer contains frame data necessary for the expanded timeline definition.
In second sub-step 115 , a determination is made as to which memory bin contains frame data that is no longer needed in agreement with the timeline definition. This determination made during each cycle. For every new frame entering the buffer memory, another frame becomes no longer necessary at the same instant.
Finally, in third sub-step 116 , the bin which contained data that is no longer required is marked ‘open’. In following cycle 112 , the next incoming frame is written to the appropriate bin. It is helpful to set a buffer memory pointer to direct the incoming frame to a bin marked ‘open’.
One skilled in the art will appreciate that advanced memory management schemes may be deployed to expand a recorded timeline in memory buffers having limited capacity.
While embodiments of the invention have been described above, it will be apparent to one skilled in the art that various changes and modifications may be made. The appended claims are intended to cover all such changes and modifications that fall within the true spirit and scope of the invention.
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A vehicle event recorder is provided that includes a camera for capturing a video as discrete image frames, and that further includes a managed loop memory and a management system for generating a virtual ‘timeline dilation’ effect. To overcome size limits in the buffer memory of the video event recorder, the maximum time extension of a video series is increased by enabling a reduction in temporal resolution in exchange for an increase in the temporal extension. Memory cells are overwritten in an ‘interleaved’ fashion to produce a reduced frame rate for the recording of certain time periods connected to an event moment. In time periods furthest from the event moment, the resulting frame rate is minimized while in time periods closest to the event moment, the resulting frame rate is maximized.
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CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation-in-part of U.S. patent application Ser. No. 471,597, filed Mar. 3, 1983 now U.S. Pat. No. 4,486,560.
BACKGROUND OF THE INVENTION
This invention relates to carbonate polymer compositions containing additives which act as flame retardants.
Carbonate polymers derived from reactions of dihydroxyorganic compounds, particularly the dihydric phenols, and carbonic acid derivatives such as phosgene, have found extensive commercial application because of their excellent physical properties. These thermoplastic polymers are suitable for the manufacture of molded parts wherein impact strength, rigidity, toughness, heat resistance and excellent electrical properties are required.
Unfortunately, however, these polymers exhibit a brief but definite burning time when contacted with an open flame. More importantly, as is often the case, the carbonate polymers contain stabilizers and other additives which are often more combustible than the unmodified carbonate polymer. As a result, the modified carbonate polymers frequently exhibit substantially poorer resistance to combustion than does the unmodified carbonate polymer.
In attempts to increase the combustion resistance of carbonate polymers including the modified forms thereof, it has been a common practice to employ monomeric phosphites, phosphoric acid esters, thiophosphoric acid esters containing halogenated alkyl radicals and halogenated organic compounds into the carbonate polymer. However, in order to obtain any noticeable improvement in combustion resistance, these additives have been employed in such large quantities that they often adversely affect many of the desirable physical and mechanical properties of the carbonate polymer.
In view of the deficiencies of conventional fire retardant carbonate polymer compositions, it would be highly desirable to provide a carbonate polymer composition having improved resistance to burning when exposed to an ignition source.
SUMMARY OF THE INVENTION
The present invention is a carbonate polymer composition comprising a carbonate polymer having dispersed therein, in an amount sufficient to provide improved flame retardancy to said carbonate polymer composition, a fire retardant additive comprising (1) a metal salt of an aromatic sulfonamide and/or a metal salt of an inorganic acid, (2) a halogenated organic compound, and (3) a melamine compound. In another aspect, the present invention is a carbonate polymer composition comprising a carbonate polymer having blended therewith, in an amount sufficient to provide improved flame retardancy to said carbonate polymer, a fire retardant additive comprising (1) a metal salt of an aromatic sulfonamide and/or a metal salt of an inorganic acid, (2) a halogenated organic compound and (3) a melamine compound. Hereinafter, such compositions will be referred to as fire retardant carbonate polymer compositions. The fire retardant carbonate polymer compositions of the present invention exhibit surprisingly high resistance to combustion. In addition, said compositions exhibit physical properties comparable to a carbonate polymer containing no fire retardant additive.
The fire retardant carbonate polymer compositions of the present invention are suitably employed in most applications in which polycarbonates have been previously utilized. Applications of particular interest for the utilization of the said carbonate polymer compositions of this invention are as follows: automobile parts, e.g., air filters, fan housings, exterior components, housings for electrical motors, appliances, business and office equipment, and photographic equipment, lighting and aircraft applications.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The carbonate polymers employed in the present invention are advantageously aromatic carbonate polymers such as the trityl diol carbonates described in U.S. Pat. Nos. 3,036,036; 3,036,037; 3,036,038 and 3,036,039; polycarbonates of bis(ar-hydroxyphenyl)-alkylidenes (often called bisphenol-A type diols) including their aromatically and aliphatically substituted derivatives such as disclosed in U.S. Pat. Nos. 2,999,835; 3,038,365 and 3,334,154; and carbonate polymers derived from other aromatic diols such as described in U.S. Pat. No. 3,169,121.
It is understood, of course, that the polycarbonate may be derived from (1) two or more different dihydric phenols or (2) a dihydric phenol and a glycol or a hydroxy- or acid-terminated polyester or a dibasic acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired. Also suitable for the practice of this invention are blends of any one of the above carbonate polymers. Also included in the term "carbonate polymer" are the ester/carbonate copolymers of the types described in U.S. Pat. Nos. 3,169,121; 4,287,787; 4,156,069; 4,260,731 and 4,105,633. Of the aforementioned carbonate polymers, the polycarbonates of bisphenol-A and derivatives, including copolycarbonates of bisphenol-A, are preferred. Methods for preparing carbonate polymers for use in the practice of this invention are well known, for example, several suitable methods are disclosed in the aforementioned patents which are hereby incorporated by reference in their entirety.
The salt form of aromatic sulfonamides which are employed herein advantageously have at least one radical represented by the formula: ##STR1## wherein Ar is an aromatic group, M is a suitable cation such as a metal cation and n is a number corresponding to the valence of M. M is preferably an alkali metal. Alternatively, M is a divalent cation, preferably alkali earth or multivalent cation obtained from copper, aluminum, antimony, and the like. Representative preferred sulfonamide salts include the alkali metal salts of saccharin, N-(p-tolylsulfonyl)-p-toluenesulfonamide, N-(N'-benzylaminocarbonyl)-sulfanilamide, N-(phenylcarboxyl)-sulfanilamide, N-(2-pyrimidinyl)sulfanilamide, N-(2-thiazolyl)-sulfanilamide and other salts of the sulfonamides disclosed in U.S. Pat. No. 4,254,015, which is incorporated herein by reference. Combinations of the above-identified salts can also be employed.
Metal salts of inorganic acids which can include the metal salts of perhalometalate complexes are most preferably alkali metal salts which include, for example, trisodium hexafluoroaluminate, disodium hexafluorotitanate, disodium hexafluorozirconate, sodium pyrophosphate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium bisulfate, and sodium phosphate. Also preferred are the potassium form of the salts listed above. Calcium sulfate and aluminum sulfate can be employed. Combinations of the above-identified salts can also be employed. See U.S. Pat. Nos. 4,336,276 and 4,208,489.
The halogenated organic compound can be virtually any halogenated organic compound commonly used as a fire retardant additive. The preferred compounds are the halo-substituted aromatic compounds (halo is fluoro, chloro, or bromo). Suitable compounds include, for example, decabromo diphenyloxide, tris-(tribromophenoxy)triazine, decabromo diphenyl carbonate, a tetrafluoroethylene polymer, an oligomer or polymer of tetrabromobisphenol A, and a copolymer of bisphenol A/tetrabromobisphenol A. Combinations of the above-identified compounds can be employed. Examples of other suitable monomeric and polymeric halogenated compounds are disclosed in U.S. Pat. No. 4,263,201, which is incorporated herein by reference.
The melamine compounds of the present invention can be virtually any N-substituted melamine which is non-polymeric in nature, and is sufficiently pure in form and compatible with the carbonate polymer. Typical examples of melamine compounds have molecular weights of less than about 800. Examples of highly preferred melamines include monomeric melamine compounds such as cyanurotriamide and N-alkyl substituted melamines, hexa(methoxymethyl)melamine, hexa(ethoxymethyl)melamine, hexa(n-propoxymethyl)melamine, hexa(n-butoxymethyl)melamine, hexa(t-butoxymethyl)melamine, hexa(isobutoxymethyl)melamine, and the like. See, for example, those non-polymeric melamine compounds disclosed in U.S. Pat. No. 4,201,832 which is incorporated herein by reference.
The fire retardant additives of this invention can comprise any amount of the aforementioned components in an effective combination which will provide improved fire retardancy to the carbonate polymer. Most preferred additive combinations comprise from about 10 to about 35, preferably about 15 to about 25, weight percent of a salt of an aromatic sulfonamide or salt of an inorganic acid, from about 10 to 35, preferably about 15 to about 25, weight percent melamine, and from about 30 to about 80, preferably about 50 to about 70, weight percent halogenated organic compound, based on the total weight of the additive. Also preferred are those combinations comprising from about 15 to about 50, preferably about 20 to about 30, weight percent of a salt of an aromatic sulfonamide or salt of an inorganic acid, and from about 50 to about 85, preferably about 70 to about 80, weight percent halogenated organic compound, based on the total weight of the additive. It is also understood that the individual fire retardant additive components must be sufficiently heat stable and pure to survive processing temperatures common to carbonate polymers without causing severe molecular weight degradation of the carbonate polymer with which the component is blended.
The fire retardant carbonate polymer compositions of the present invention are suitably prepared by combining the carbonate polymer with an effective amount of fire retardant additive using any of a variety of blending procedures conventionally employed for incorporating additives into carbonate polymer resins. For example, dry particulates of the carbonate polymer and the fire retardant additive can be dry blended and the resulting dry blend extruded into the desired shape. By "effective amount" is meant that combination of the desired fire retardant additive components is sufficient to provide improved fire retardant character to the carbonate polymer with which it is blended.
While any amount of the fire retardant additive that imparts to the carbonate polymer an improved fire retardant is suitable, preferred amounts of the fire retardancy additive are in the range from about 0.001 to about 10, especially from about 0.005 to about 2, weight percent based on the weight of the carbonate polymer.
Fire retardant carbonate polymer compositions are considerably more difficult to ignite than unmodified carbonate polymer resins or carbonate polymer compositions containing only the individual fire retardant additive components. The fire retardant carbonate polymer compositions of this invention rapidly form a char at the surface of the sample once ignition is achieved. In addition, the compositions of this invention burn for a much shorter time than unmodified carbonate polymer resins or carbonate polymer compositions containing only the individual fire retardant additive components.
In addition to the aforementioned fire retardant additives, other additives can be included in the carbonate polymer composition of the present invention such as fillers (i.e., a tetrafluoroethylene polymer or glass fibers), pigments, dyes, antioxidants, stabilizers, ultraviolet light absorbers, mold release agents and other additives commonly employed in carbonate polymer compositions.
The following examples are given to further illustrate the invention and should not be construed as limiting its scope. In the following examples, all parts and percentages are by weight unless otherwise indicated.
EXAMPLE 1
Samples are prepared using a 3000-g portion of a bisphenol-A polycarbonate sold under the brand name Merlon M50F-1000 by Mobay Chemical Corporation, and a fire retardant additive comprising varying amounts of sodium N-(p-tolylsulfonyl)-p-toluenesulfonamide, decabromo diphenyloxide and hexamethoxy methyl melamine. The constituents are mixed using a Hobart brand mixer until thoroughly and evenly dispersed. The mixture is dried at 250° F. for 4 hours, and extruded on a single screw, 11/4 inch, 20:1 L/D extruder operated at a barrel temperature of 525° F. and a screw speed of 80 rpm. The extruded sample is redried at 250° F. for 4 hours. The pellets are molded into test specimens using a Newbury brand Model H1-30RS injection molding machine under the following conditions: barrel temperature=575° F., mold temperature=175° F., injection polymer pressure sufficient to fill the cavity. The molded bars are tested for combustibility (oxygen index and fire resistance). Data is presented in Table I.
TABLE I__________________________________________________________________________ Fire Retardance.sup.5 Amount Amount Amount Total Avg. After OxygenSample NPTSM.sup.1 DBDPO.sup.2 HMMM.sup.3 Amount.sup.4 Burn Time Rating Index.sup.6__________________________________________________________________________C-1* -- -- -- -- 29.3 HB, HB 25.2C-2* 0.1 -- -- 0.1 2.1 V-O, V-O 39.9C-3* 1.0 -- -- 1.0 6.0 V-1, V-1 29.2C-4* -- 0.1 -- 0.1 14.3 HB, HB 26.6C-5* -- 1.0 -- 1.0 12.7 V-2, V-2 28.6C-6* -- -- 0.1 0.1 -- V-2, V-2 29.6C-7* -- -- 1.0 1.0 -- V-2, V-2 30.6S.sub.1 0.02 0.08 -- 0.1 2.6 V-O, V-O 39.0S.sub.2 0.2 0.8 -- 1.0 1.2 V-O, V-O 44.9S.sub.3 0.02 0.06 0.02 0.1 2.7 V-O, V-O 40.3S.sub.4 0.05 0.15 0.05 0.25 0.9 V-O, V-O 41.0S.sub.5 0.10 0.30 0.10 0.5 0.8 V-O, V-O 43.6S.sub.6 0.20 0.60 0.20 1.0 0.5 V-O, V-O 46.0S.sub.7 0.40 1.20 0.40 2.0 0.5 V-O, V-O 48.0__________________________________________________________________________ *Not an example of the invention. .sup.1 NPTSM is the sodium salt of N--(ptolylsulfonyl)-p-toluenesulfonamide. .sup.2 DBDPO is decabromo diphenyl oxide. .sup.3 HMMM is hexamethoxy methyl melamine. .sup.4 Amount is weight percent based on carbonate polymer. .sup.5 Subject to the test procedure set forth in Underwriters' Laboratories, Inc. Bulletin UL94, Burning Test for classifying materials. Samples are 1/8 inch and two, five bar sets of samples are tested. .sup.6 Method is ASTM D2863-70.
EXAMPLE 2
Samples are prepared and tested as in Example 1. The molded bars are tested for combustibility. Data is presented in Table II.
TABLE II__________________________________________________________________________ Fire Retardance.sup.4 Amount Amount Amount Amount Amount Total Avg. After OxygenSample NPTSM TTBPT.sup.1 K.sub.2 TiF.sub.6.sup.2 DBDPO DBDPC.sup.3 Amount Burn Time Rating Index.sup.5__________________________________________________________________________C-1* -- -- -- -- -- -- 29.3 HB, HB 25.2S.sub.8 0.02 0.08 -- -- -- 0.1 2.8 V-O, V-O 39.6S.sub.9 0.20 0.80 -- -- -- 1.0 1.6 V-O, V-O 45.4S.sub.10 0.02 -- -- -- 0.08 0.1 2.1 V-O, V-O 38.9S.sub.11 0.2 -- -- -- 0.8 1.0 0.9 V-O, V-O 43.9S.sub.12 -- -- 0.02 0.08 -- 0.1 3.0 V-O, V-O 38.1S.sub.13 -- -- 0.2 0.8 -- 1.0 1.1 V-O, V-O 41.7__________________________________________________________________________ *Not an example of the invention. .sup.1 TTBPT is tri(2,4,6-tribromophenoxy)triazine. .sup.2 K.sub.2 TiF.sub.6 is dipotassium hexafluorotitanate. .sup.3 DBDPC is decabromodiphenyl carbonate. .sup.4 See Table I. .sup.5 See Table I.
As evidenced by the data shown in Tables I and II, the fire retardant additives, when blended with the polycarbonate in amounts within the scope of this invention, provide substantial improvement in that the compositions exhibit a reduced tendency to burn.
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A carbonate polymer such as a bisphenol-A homopolycarbonate containing a small amount of (1) a metal salt of an aromatic sulfonamide or a metal salt of an inorganic acid, such as a metal salt of a perhalometalate complex, (2) a halogenated organic compound and, (3) a melamine, exhibits improved flame retardant properties.
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BACKGROUND OF THE INVENTION
The present invention relates generally to equipment for use in subterranean wells and, in a preferred embodiment thereof, more particularly provides a sand control screen having increased erosion and collapse resistance.
Sand control screens are utilized for various purposes in subterranean wells. The name derives from their early use in preventing the production of sand along with fluids from formations. A sand control screen is typically suspended from production tubing extending to the earth's surface and positioned in a wellbore opposite a productive formation. In this way, the sand control screen may exclude the produced sand while permitting the valuable fluids to enter the tubing for transport to the earth's surface.
Other operations in which sand control screens are utilized include fracturing, gravel packing, and water flooding. In fracturing and gravel packing operations, material known as "proppant" or "gravel" is usually suspended in a slurry and pumped down the tubing and into the annular space between the sand control screen and metal casing lining the wellbore. The material typically accumulates in the annular space and eventually fills it, completely covering the exterior surface of the screen. The sand control screen prevents this material from being pumped back to the earth's surface.
In water flooding and other injection operations, fluids are pumped into the formation, for example, to generate steam in a geothermal well, to drive hydrocarbons to an upper portion of a formation, etc. The sand control screen in these cases prevents contaminants and debris from being pumped into the wellbore and formation.
When utilized to prevent production of sand from the formation, the screen is usually eroded by the flow of fluids therethrough. As the velocity of the fluid flow is increased, the rate of erosion also increases. Where the fluid flow rate from one portion of the formation is greater than the fluid flow rate from another portion of the formation, the screen will erode more quickly opposite the higher flow rate portion than it will opposite the lower flow rate portion.
Consequently, sand control screens must be designed to withstand fluid flow from the higher flow rate portion of the formation, which results in uneconomical overcompensation for the fluid flow from the lower flow rate portion of the formation. This problem is exacerbated in gas wells where it is common for a small number of perforations in the casing to have a much higher flow rate than the other perforations.
A similar, but more predictable, problem occurs in fracturing and gravel packing operations. As the material accumulates in the annular area between the screen and the casing, an increasingly large lower portion of the screen is covered with the material, restricting flow of the fluid portion of the slurry therethrough, and the flow rate of the fluid portion through the remaining upper portion of the screen not covered by the material is thereby increased. Therefore, the upper portion of a sand control screen is typically eroded much more than the lower portion during gravel packing and fracturing operations.
If the screen is designed to have very small openings, to compensate for the erosion of the upper portion during fracturing or gravel packing operations, then later, after the fracturing or gravel packing operation is completed and it is desired to produce fluids from the formation, the lower uneroded portion of the screen will have openings too small for a desired production fluid flow rate. If the screen is designed to have relatively large openings, to permit the desired production fluid flow rate after the gravel packing or fracturing operations, the upper eroded portion of the screen will have openings too large to restrict the flow of the material or sand therethrough.
Somewhat similar problems are experienced during injection operations when some portions of the formation receive the injected fluids at a greater flow rate than other portions. Also, when debris accumulates in a lower internal portion of the screen, the flow rate of the injected fluids through the upper portion of the screen is thereby increased, causing greater erosion of the screen in the upper portion.
Because of the increasingly high flow rates experienced during fracturing and gravel packing operations in recent years, screens must be designed to withstand increasingly high collapse pressures. Where a screen has very small openings, overcompensating for expected erosion of a portion of the screen, the collapse pressure for a given flow rate therethrough increases. In the past, an increased number and thickness of support rods have been used in a wire wrapped screen and increased thickness has been used in a sintered metal screen to resist increased collapse pressures. Unfortunately, each of these solutions exacerbates the problem, since each increases the resistance to flow through the screen. Each of these solutions also undesirably increases the cost and outer diameter of the screen.
From the foregoing, it can be seen that it would be quite desirable to provide a sand control screen which does not require an increased number or thickness of support rods or increased thickness of screen material for increased collapse resistance thereof, which is able to compensate for erosion during production, fracturing, gravel packing, and injection operations without overly restricting fluid flow therethrough during production, and which accomplishes these objectives economically and without increasing the outer diameter of the screen. It is accordingly an object of the present invention to provide such a sand control screen.
SUMMARY OF THE INVENTION
In carrying out the principles of the present invention, in accordance with an embodiment thereof, a screen is provided which has improved erosion resistance and collapse resistance, utilization of which permits the screen to withstand greater rates of fluid flow therethrough without requiring the screen to have an increased outer diameter.
According to a preferred embodiment of the present invention, in which a variety of unique features thereof are cooperatively combined, a screen is provided which includes a tubular base pipe and a filtering portion. The filtering portion is externally disposed relative to the base pipe and outwardly overlaps an opening formed radially through the base pipe. The filtering portion, thus, filters fluid flowing radially through the opening.
The screen also includes a support material positioned between the base pipe and the filtering portion. The support material contacts the base pipe and filtering portion and, thus, helps prevent the filtering portion from being radially inwardly collapsed by radially inwardly flowing fluid. The support material may be granular and may be held together by a resin which may be dissolvable to permit the support material, when the resin is dissolved, to flow radially inwardly through the opening, if desired.
The screen also includes a coating exteriorly applied to the filtering portion. The coating may perform one or several of many functions, including retaining the support material, preventing erosion of the filtering portion, and varying the rate of fluid flow through the filtering portion. The filtering portion may have all, or only a part, of its exterior surface covered by the coating.
In addition to the coating, or as an alternative thereto, the filtering portion may be hardened to increase its erosion resistance. Only a portion of the filtering portion may be hardened. For example, only an axial portion or an outer side surface of the filtering portion may be hardened.
The screen may also include an outer jacket and further support material between the filtering portion and the outer jacket. In that instance, the further support material may help prevent radially inward collapse of the outer jacket and radially outward expansion of the filtering portion.
The features listed above are among those provided by the disclosed preferred embodiment of the present invention. Other features will become apparent upon consideration of the detailed description set forth hereinbelow. It will be readily appreciated by one of ordinary skill in the art that these features may be utilized individually or in any combination in a screen embodying principles of the present invention.
The use of the disclosed screen enables higher rates of fluid flow in production, gravel packing, fracturing, injection, and other operations.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 (Prior Art) is a highly schematicized cross-sectional view of a prior art sand control screen operatively positioned within a subterranean wellbore opposite a formation;
FIG. 2 is a side elevational view of a sand control screen embodying principles of the present invention;
FIGS. 3A and 3B are enlarged cross-sectional views, taken along line 3--3 of FIG. 2, showing alternate constructions of the sand control screen of FIG. 2; and
FIG. 4 is an enlarged quarter-sectional view of the sand control screen, taken along line 4--4 of FIG. 3A.
DETAILED DESCRIPTION
Illustrated in FIG. 1 is a prior art sand control screen 10 operatively positioned in a subterranean wellbore 12 opposite a formation 14 which has been lined with protective casing 16. The casing 16 has been perforated to permit fluid flow between the formation 14 and the wellbore 12. Screen 10 is suspended from production tubing 18 which extends to the earth's surface.
During production of fluids, represented by arrows 20, from the formation 14, the fluids enter the screen 10 and are transported to the earth's surface through the production tubing 18. Any sand in the fluid 20 should be filtered out by the screen 10 and not permitted to flow into the tubing 18. The screen 10 is gradually eroded over time as the fluid 20 flows through the screen. Higher rates of flow of the fluid 20 through the screen 10 cause faster erosion of the screen.
If the rate of flow of the fluid 20 through a particular perforation 22 is greater than the rate of flow of the fluid through the other perforations, as is frequently the case in gas wells, a portion 24 of the screen 10 opposite the high flow rate perforation 22 will erode faster than other portions of the screen 10. When the portion 24 of the screen 10 has eroded enough to permit sand and other debris to enter the tubing 18, the entire screen 10 must be replaced at great cost to the well operator, even though most of the screen is not yet eroded.
In gravel packing and/or fracturing operations, a slurry, represented by arrows 26, is pumped into the annular space 28 between the screen 10 and the casing 16, and into the formation 14. Fluid 20 is permitted to enter the screen 10, but proppant or gravel in the slurry 26 accumulates in the wellbore 12, gradually filling the annular space 28. As the annular space 28 is filled, the screen 10 is gradually covered, such that an increasingly smaller portion 30 of the screen is available for relatively unrestricted flow of fluids 20 therethrough. Thus, screen portion 30 experiences a higher flow rate than other portions of the screen 10 and erodes faster than other portions of the screen.
In injection operations, the above-described erosion of the screen 10 due to fracturing and/or gravel packing operations is also present, except with a reverse flow of the fluids 20 from that shown in FIG. 1. As the inside of the screen 10 fills with debris, the increasingly smaller portion 30 is available for relatively unrestricted flow therethrough of fluids 20 from inside the screen to the annular space 28. Therefore, the screen portion 30 erodes faster than other portions of the screen 10 in injection operations, also.
Representatively illustrated in FIG. 2 is a sand control screen 40 embodying principles of the present invention. In the following detailed description of the embodiments of the present invention representatively illustrated in the accompanying figures, directional terms such as "upper", "lower", "upward", "downward", etc. are used in relation to the illustrated screen 40 as it is depicted in the accompanying figures. It is to be understood that the screen 40 may be utilized in vertical, horizontal, inverted, or inclined orientations without deviating from the principles of the present invention.
Screen 40 is representatively illustrated as being of the type known to those skilled in the art as a "wire wrapped" screen, due to a filtering portion 42 of the screen being made of spirally wrapped and generally triangular cross-sectioned wire 44. It is to be understood, however, that features of the present invention hereinbelow described may also be utilized in a sand control screen having a tubular filtering portion 42 made of differently shaped wire, sintered metal, or other materials, without departing from the principles of the present invention.
Screen 40 may be interconnected to tubing or other well equipment, such as tubing 18 shown in FIG. 1, by tubular end connections 46. A tubular base pipe 48 extends axially between the end connections 46 and provides an axial flow passage 50 (see FIG. 3A) for fluid flow therethrough. Preferably, the base pipe 48 has multiple axially and radially extending slots 52 (see FIG. 4) formed thereon. Base pipe 48 may also have differently configured openings, such as circular perforations, without departing from the principles of the present invention.
Screen end caps 54 are welded to opposite ends of the filtering portion 42 and to the base pipe 48. Radially inwardly directed flow through the screen 40 must, therefore, pass first through the screen portion 42, and then through the slots 52 on the base pipe 48, before entering the axial flow passage 50.
Referring additionally now to FIG. 3A, an enlarged cross-sectional view of the screen 40 is shown, taken along line 3--3 of FIG. 2. In this view the manner in which the wire 44 is radially outwardly spaced apart from the base pipe 48 may be clearly seen. Several (seven in the representatively illustrated embodiment) axially extending and circumferentially spaced apart rods 56 are disposed radially between the wire 44 and the base pipe 48. In a conventional manufacturing process, the wire 44 is spirally wrapped externally onto the rods 56 and welded thereto. For purposes of clarity of illustration, the wire 44 is shown as being circularly wrapped about the rods 56, but it is to be understood that the wire may have a polygonal shape due to being stretched between the rods as it is wound thereabout.
As will be readily appreciated by one skilled in the art, when fluid flows radially inward between the spirally wrapped wire 44, a radially inwardly directed force (represented by arrows 60) results, which is applied to the wire. As the flow rate is increased, the resulting force 60 is also increased. If the wire 44 is unsupported circumferentially between the rods 56, and the resulting force 60 is increased, the wire may collapse radially inwardly, resulting in the failure of the screen 40 to effectively filter the fluid flowing therethrough.
If the screen 40 is of the sintered metal type, the force 60 results from the restriction to flow therethrough of the filtering portion 42. In that case, where the filtering portion 42 is unsupported and the resulting force 60 is increased, the filtering portion 42 may break apart or crack, also resulting in the failure of the screen 40 to effectively filter the fluid flowing therethrough.
Radially between the wire 44 and the base pipe 48, and circumferentially between the rods 56, is a permeable support material 58. Preferably, the support material 58 is relatively large grain sand, but may also be ceramic proppant, spherical plastic beads, such as divinyl benzene, sintered metallic material (a generally granular-like permeable material), or other suitable material. If the support material 58 is granular, it is also preferably coated with a resin 62 to consolidate the grains. The resin 62, if used, may also be dissolvable, so that the support material 58 is permitted to flow inwardly through the slots 52 when the resin is dissolved. Use of the dissolvable resin 62 permits the support material 58 to radially outwardly support the wire 44 during high flow rate operations, such as fracturing operations, and then be removed for later, relatively low flow rate, operations wherein added flow restriction due to the support material 58 is undesirable.
It may now be fully appreciated that the support material 58, which radially outwardly supports the wire 44, permits the screen 40 to be utilized in operations wherein relatively high fluid flow rates are experienced, without collapse of the wire. Alternatively, for a given fluid flow rate, the screen 40 may have fewer supporting rods 56 and/or smaller cross-section wire 44, or thinner sintered metal filtering portion 42, than heretofore possible.
Turning now to FIG. 3B, an alternative construction of screen 40 is shown, an enlarged cross-sectional view, taken along line 3--3 of FIG. 2, being representatively illustrated. Additional axially extending and circumferentially spaced apart rods 64 are disposed radially between an outer jacket 66 and the wire 44. The outer jacket 66 may be wire, such as wire 44, it may be a slotted or perforated pipe, such as base pipe 48, or it may be made of sintered metal or other suitable material. If outer jacket 66 is made of sintered metal, or perforated or slotted pipe, rods 64 may not be utilized.
Additional permeable support material 68 is disposed radially between the outer jacket 66 and the wire 44, and circumferentially between the rods 64. Support material 68 may be made of the same material as support material 58 or may be made of different material. Support material 68 may also be coated with resin 70, which may be the same as resin 62, and which may also be dissolvable.
Outer jacket 66 is radially outwardly supported by support material 68 in a similar manner as previously described for wire 44 radially outwardly supported by support material 58. Additionally, support material 68 radially inwardly supports wire 44. Thus, where screen 40 is utilized in injection operations, such as water injection, support material 68 radially inwardly supports wire 44, helping to prevent radially outward expansion of wire 44. Note that, as previously described for wire 44, when outer jacket 66 is made of wire and is spirally wrapped about rods 64, it may have a polygonal shape instead of the representatively illustrated circular shape.
Illustrated in FIG. 4 is an enlarged quarter-sectional view of the first described embodiment of the screen 40, taken along line 4--4 of FIG. 3A. Wire 44 is shown wrapped about a rod 56, which is disposed radially between the wire 44 and the base pipe 48. The support material 58 is representatively illustrated axially between successive wraps of the wire 44, and radially between the wire 44 and the rod 56. Note that, as shown in FIG. 3A, the support material 58 is also disposed radially between the wire 44 and the base pipe 48.
The filtering portion 42, as representatively illustrated in FIG. 4, is partially exteriorly covered with a coating 72. Preferably, coating 72 is a hard and abrasion resistant material, such as flame sprayed metal, chromium, metal plasma, carbide, or other suitable material. It is to be understood that coating 72 may completely exteriorly cover filtering portion 42 without departing from the principles of the present invention. Coating 72 may be applied to the wire 44 before or after the wire is wrapped about the rods 56. For purposes of economy, applicants prefer that coating 72 be applied after the screen 40 is otherwise completely assembled.
Preferably, coating 72 axially outwardly extends from each wrap of wire 44 to which it is applied and, thus, partially closes an axial gap 74 between each wrap of wire 44. In this manner, coating 72 helps to retain the support material 58, helps prevent axial erosion of the wire 44, and provides a means of varying the axial gap 74. Where it is desired to have a relatively large flow restriction initially, and subsequently have a relatively small flow restriction through the screen 40, coating 72 may be made of a material with a desired erosion rate, such that axial gap 74 increases at a known rate as fluid flows therethrough.
As hereinabove described, it is common for one area of the filtering portion 42 to erode before other areas, such as screen portion 30 or 24 shown in FIG. 1. For purposes of economy, coating 72 may be applied only to areas of filtering portion 42 where high rates of erosion are expected. In situations where such erosion protection is desired, wire 44 may also be treated, such as by nitriding, case carburizing, induction hardening, flame hardening, or other suitable treatment.
It is contemplated that, where the filtering portion 42 is hardened, the coating 72 may or may not also be applied. Furthermore, the filtering portion 42 may or may not be completely hardened. For example, it may be desired for only outer side portions of the wire 44 to be hardened. In that case, the filtering portion 42 could be hardened by, for example, flame hardening after the screen 40 is otherwise completely assembled. Additionally, it may be desired for only certain axial portions, such as portion 30 or 24, to be hardened. Preferably, portions of the filtering portion 42 which are hardened as described above will have a hardness of at least about Rockwell b 30C.
The foregoing detailed description is to be clearly understood as being given by way of illustration and example only, the spirit and scope of the present invention being limited solely by the appended claims.
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A screen provides increased erosion resistance and collapse resistance without uneconomical overcompensation and without requiring an increase in the screen's outer diameter. In a preferred embodiment, a sand control screen has a support material radially between a tubular base pipe and a filtering portion. The support material radially outwardly supports the filtering portion to help prevent radially inward collapse of the filtering portion. In another preferred embodiment, a screen has a coating applied to a filtering portion's exterior surface. The coating may alternatively or combinatively provide erosion resistance, radially inwardly retain a support material, and selectively vary flow through the filtering portion.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application Ser. No. 60/294,426 filed May 29, 2001.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for forming from a mold optical articles, in particular ophthalmic articles such as ophthalmic lenses, having several optical coatings thereon.
2. Previous Art
It is a common practice in the art to coat at least one face of an ophthalmic lens with several coatings for imparting to the finished lens additional or improved optical or mechanical properties. Thus, it is usual practice to coat at least one face of an ophthalmic lens substrate typically made of an organic glass material with successively, starting from the face of the substrate, an impact-resistant coating (impact-resistant primer), a scratch-resistant coating (hard coat), an anti-reflecting coating and, optionally, a hydrophobic top coat.
Typically, optical articles made of organic glass materials are formed in a mold comprising two separate parts having optical surfaces which, when the two-parts are assembled, define a molding cavity. A liquid curable composition is then introduced in the molding cavity and cured to form the optical article. The optical article is thereafter recovered upon disassembling of the mold parts.
Examples of typical two-part molds and molding methods are disclosed in U.S. Pat. Nos. 5,547,618 and 5,662,839.
It is known in the art to also apply a scratch-resistant coating composition on the optical surfaces of the parts of a two-part mold, and if necessary precure it, assemble the mold parts, fill the molding cavity with an optical liquid curable material, cure the optical material and disassemble the mold parts to recover the molded optical article having a scratch-resistant coating deposited and adhered thereon.
Such a method is, for example, disclosed in document EP-102847.
U.S. Pat. No. 5,096,626 discloses a method for making an optical article having a scratch-resistant coating and/or an anti-reflecting coating thereon, which comprises:
forming an anti-reflecting coating and/or a scratch-resistant coating onto the optical surfaces of a two-part mold; assembling the two-part mold; pouring an optical liquid curable composition in the molding cavity; curing the optical composition, and disassembling the two-part mold for recovering the molded optical article having a scratch-resistant coating or a scratch-resistant coating and an anti-reflecting coating thereon;
wherein, either at least one release agent is incorporated into the scratch-resistant coating or a film of at least one release agent is formed on the optical surfaces of the mold parts, prior to the formation of the anti-reflecting coating and/or the scratch-resistant coating.
The preferred release agents useful in the method of U.S. Pat. No. 5,096,626 are fluorosilicones, fluoroalkylkoxysilanes and mixtures thereof.
U.S. Pat. No. 5,160,668 discloses a method for transferring an anti-reflecting coating onto a surface of an optical element which comprises:
forming on the optical surface of a part of a two-part mold a release layer of a water soluble inorganic salt;
forming on said release layer an anti-reflecting layer,
assembling the mold parts;
pouring a liquid optical curable composition in the molding cavity,
curing the optical composition,
disassembling the mold parts and dissolving the release layer in water to recover the coated optical element.
U.S. Pat. No. 5,733,483 discloses a method for forming on-site tinted and coated optical elements from a mold which comprises:
forming successively on an optical surface of at least one part of a two-part mold, a polymer release layer, an anti-reflecting coating layer, a coupling agent layer and a hard coat layer;
assembling the two-part mold;
pouring an optical liquid curable material in the molding cavity;
curing the optical material and the anti-reflecting, coupling agent and hard coat layers; and
disassembling the mold parts to recover the coated optical element.
The polymer release layer can be made of a water soluble polymer such as polyvinylic acid (PAA), polyethylene-oxide (PEO), poly(N-vinylpyrolidone) (PNVP), polyvinylalcohol (PVA) or polyacrylamid (PAM); a non-water soluble and UV curable polymer such as polybutadiene-diacrylate (PBD-SA), polyethyleneglycol-diacrylate (PEG-DA) or a highly crosslinked acrylate, and commercial mold release agents such as Dow-Corning 20 Release.
The coupling agent layer generally comprises a (meth)acryloxyalkyltrialkoxysilane. This coupling agent layer is used in order to better extract the anti-reflecting coating from the mold.
What is needed is a method which will provide on-site formation of optical articles having thereon an impact-resistant coating, a scratch-resistant coating, an anti-reflecting coating and, optionally, a hydrophobic top coat by replication of a mold, thereby sufficiently reducing required handling time and costs.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a method for forming from a mold optical articles having an impact-resistant primer coating, a scratch-resistant coating, an anti-reflecting coating and, optionally, a hydrophobic top coat.
It is an additional object of this invention to provide a method for forming coated optical articles in which at least an anti-reflecting coating, a scratch-resistant coating and an impact-resistant primer coating are transferred in a single step from at least one mold optical surface onto a surface of an optical substrate.
It is a further object of this invention to provide a method which does not necessitate the use of a coupling agent layer between the anti-reflecting layer and the scratch-resistant layer.
In accordance with the above objects and those that will be mentioned and will become apparent below, the method for forming a coated optical article comprises:
providing a two-part mold having opposed optical surfaces defining therebetween a molding cavity;
forming successively, on at least one of the optical surfaces of the mold, an anti-reflecting coating, a scratch-resistant coating and an impact-resistant primer coating;
filling the molding cavity with an optical substrate liquid curable composition;
curing the liquid curable composition, and
disassembling the two-part mold for recovering a coated optical article comprising an optical substrate having deposited and adhered on at least one of its faces, an impact-resistant primer coating, a scratch-resistant coating and an anti-reflecting coating.
In a preferred embodiment, the mold is made of a plastic material.
To further improve release of the coated optical article from the mold, a release agent can be incorporated in the plastic material of the mold, or the optical surfaces of the mold parts can be coated with a release agent layer.
In an additional preferred embodiment, to improve adhesion between the scratch-resistant coating and the impact-resistant primer coating or between the primer coating and the substrate, one or more coupling agents can be incorporated into the composition of the scratch-resistant coating and/or of the primer coating.
The preferred coupling agent is a pre-condensed solution of at least one epoxyalkoxysilane and at least one unsaturated alkoxysilane.
Preferably, the anti-reflective coating is a stack of alternated high and low refractive index inorganic material layers. To improve adhesion of such an anti-reflecting coating to the scratch-resistant coating a thin layer of SiO 2 may be interposed between the anti-reflecting coating and the scratch-resistant coating.
BRIEF DESCRIPTION OF THE DRAWING
For the further understanding of the objects and advantages of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawings, in which like parts are given like reference numerals and wherein:
FIG. 1A to FIG. 1C schematically illustrate the main steps of an embodiment of the method of the invention; and
FIG. 2A to FIG. 2C schematically illustrate the main steps of another embodiment of the method of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Although in the following description, only one face of the optical article is being coated with the optical functional coatings according to the invention, it should be understood that both faces of the optical articles can be coated simultaneously using the method of the invention.
With respect to FIG. 1A , there is shown schematically a front part 10 of a two-part mold, on the optical surface 10 a of which has been successively formed an anti-reflecting coating 20 , a scratch-resistant coating 30 and an impact-resistant primer coating 31 .
The two-part mold used in the method of the invention comprises a front part 10 having an optical surface 10 a and a rear part 11 ( FIG. 1B ) having an optical surface 11 a.
Typically the two-parts 10 , 11 of the mold are assembled through a gasket or an adhesive tape (not shown) so that the optical surfaces 10 a , 11 a of the mold parts define therebetween a molding cavity.
Typically the mold parts 10 , 11 are made of mineral glass or a plastic material. In the method of the invention, the mold part are preferably made of a plastic material, in particular a plastic material that promotes easy release of the molded optical article.
Among the plastic materials that can be used for the two-part mold there can be cited: polycarbonates (PC), polyamides (PA), polyimides (PI), polysulfones (PS), copolymers of polyethyleneterephtalate and polycarbonate (PET-CP), crystal polyethyleneterephtalate (crystal PET), glass fiber reinforced polyethyleneterephtalate, and polyolefins such as polynorbornenes. The preferred plastic materials are polycarbonates and polynorbornenes.
A very good plastic material that can be used for the two part mold is a copolymer having the following units
Such copolymer is available from Bayer under the commercial trade name APEC.
This copolymer has a high rigidity which can be an advantage for the use as a mold material.
Preferably, the thickness center for each mold part is at least 4 mm.
To enhance the release effect of the molds, in particular with regard to the anti-reflecting coating, one or more release agents can be incorporated in the polymer material of the mold. Examples of such release agents are trimethylchlorosilane, chloromethyltrimethylsilane, chloropropyltrimethylsilane, chloromethyldodecyl dimethylsilane, chlorine terminated polydimethyl siloxane, (3,3-dimethylbutyl) dimethylchlorosilane, hexamethyldisilazane, octamethyltetrasilazane, aminopropyldimethyl terminated polydimethylsiloxane, 3-trimethoxysilyl propyloctadecyldimethylammonium chloride, tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, trimethylethoxysilane and octadecyltrimethoxysilane.
If necessary the optical surfaces 10 a , 11 a of the parts of the plastic mold may be previously coated with a protective and/or release coating which either protects the optical surfaces from defects such as scratches that may be created during handling, and/or enhance the release effect. This protective and/or release coating may also even the optical surface
Examples of such coatings are:
A UV-curable acrylic layer optionally containing at least one of the above cited release agent or an amine containing polysiloxane layer optionally containing at least one of the above release agent;
A fluorocarbon polymer layer, such as polytetrafluoroethylene (PTFE) polymers, for example Teflon® AF, Teflon® PTFE FEP and Teflon® PTFE PFA;
A buffer layer which may delaminate from the mold part optical surface and from which the anti-reflecting coating or the top coat can release, such as a vacuum-deposited magnesium fluoride (MgF 2 ) layer or a siloxane base coating normally used to input scratch resistance to lenses. Both of these layers release readily from the optical surface of the mold, in particular of a polycarbonate mold. After demolding of the optical article, these layers are eliminated.
The protective and/or release coatings can be deposited by dip coating or spin coating, and depending upon their technical natures they may be UV and/or thermally cured or simply dried. Those protective and/or release coatings have typically a thickness of 2 nm to 10 microns.
The mold parts, usually made of plastic material, are UV transparent and allow UV and/or thermal curing of the different layers and in particular of the optical substrate composition. Preferably, the polymer material of the mold parts are free of UV absorber.
As shown in FIG. 1A , there is first deposited on the optical surface 10 a of the first part 10 of, for example, a polycarbonate mold, an anti-reflecting coating 20 .
Anti-reflecting coatings and their methods of making are well known in the art. The anti-reflecting can be any layer or stack of layers which improves the anti-reflective properties of the finished optical article.
The anti-reflecting coating may preferably consist of a mono- or multilayer film of dielectric materials such as SiO, SiO 2 Si 3 N 4 , TiO 2 , ZrO 2 , Al 2 O 3 , MgF 2 or Ta 2 O 5 , or mixtures thereof.
The anti-reflecting coating can be applied in particular by vacuum deposition according to one of the following techniques:
1)—by evaporation, optionally ion beam-assisted; 2)—by spraying using an ion beam, 3)—by cathode sputtering; or 4)—by plasma-assisted vapor-phase chemical deposition.
In case where the film includes a single layer, its optical thickness must be equal to λ/4 where λ is wavelength of 450 to 650 nm.
Preferably, the anti-reflecting coating is a multilayer film comprising three or more dielectric material layers of alternatively high and low refractive indexes.
Of course, the dielectric layers of the multilayer anti-reflecting coating are deposited on the optical surface of the mold part or the hydrophobic top coat in the reverse order they should be present on the finished optical article.
In the embodiment shown in FIG. 1A , the anti-reflecting coating 20 comprises a stack of four layers formed by vacuum deposition, for example a first SiO 2 layer 21 having an optical thickness of about 100 to 160 nm, a second ZrO 2 layer 22 having an optical thickness of about 120 to 190 nm, a third SiO 2 layer 23 having an optical thickness of about 20 to 40 nm and a fourth ZrO 2 layer 24 having an optical thickness of about 35 to 75 nm.
Preferably, after deposition of the four-layer anti-reflecting stack, a thin layer of SiO 2 25 of 1 to 50 nm thick (physical thickness) is deposited. This layer 25 promotes the adhesion between the anti-reflecting stack and the scratch-resistant coating 30 to be subsequently deposited, and is not optically active.
The next layer to be deposited is the scratch-resistant coating 30 . Any known optical scratch-resistant coating composition can be used to form the scratch-resistant coating 30 . Thus, the scratch-resistant coating composition can be a UV and/or a thermal curable composition.
By definition, a scratch-resistant coating is a coating which improves the abrasion resistance of the finished optical article as compared to a same optical article but without the scratch-resistant coating.
Preferred scratch-resistant coatings are those made by curing a precursor composition including epoxyalkoxysilanes or a hydrolyzate thereof, silica and a curing catalyst. Examples of such compositions are disclosed in U.S. Pat. No. 4,211,823, WO 94/10230, U.S. Pat. No. 5,015,523.
The most preferred scratch-resistant coating compositions are those comprising as the main constituents an epoxyalkoxysilane such as, for example, γ-glycidoxypropyltrimethoxysilane (GLYMO) and a dialkyldialkoxysilane such as, for example dimethyldiethoxysilane (DMDES), colloidal silica and a catalytic amount of a curing catalyst such as aluminum acetylacetonate or a hydrolyzate thereof, the remaining of the composition being essentially comprised of solvents typically used for formulating these compositions.
In order to improve the adhesion of the scratch-resistant coating 30 to the impact-resistant primer coating 31 to be subsequently deposited, an effective amount of at least one coupling agent can be added to the scratch-resistant coating composition.
The preferred coupling agent is a pre-condensed solution of an epoxyalkoxysilane and an unsatured alkoxysilane, preferably comprising a terminal ethylenic double bond.
Examples of epoxyalkoxysilanes are γ-glycidoxypropyl-termethoxysilane, γ-glycidoxypropylpentamethyldisiloxane, γ-glycidoxy-propylmethyldiisopropenoxysilane, (γ-glycidoxypropyl)methyldiethoxy-silane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyl-diisopropylethoxysilane and (γ-glycidoxypropyl)bis(trimethylsiloxy)methylsilane.
The preferred epoxyalkoxysilane is γ-glycidoxypropyl-trimethoxysilane.
The unsatured alkoxysilane can be a vinylsilane, an allylsilane, an acrylic silane or a methacrylic silane.
Examples of vinylsilanes are vinyltris(2-methoxyethoxy)silane, vinyltrisisobutoxysilane, vinyltri-t-butoxysilane, vinyltriphenoxysilane, vinyltrimethoxysilane, vinyltriisopropoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinylmethyldiethoxysilane, vinylmethyldiacetoxy-silane, vinylbis(trimethylsiloxy)silane and vinyldimethoxyethoxysilane.
Examples of allylsilanes are allyltrimethoxysilane, alkyltriethoxysilane and allyltris(trimethylsiloxy)silane.
Examples of acrylic silanes are 3-acryloxypropyltris(trimethylsiloxy)silane, 3-acryloxypropyltrimethoxysilane, acryloxypropylmethyl-dimethoxysilane, 3-acryloxypropylmethylbis(trimethylsiloxy)silane, 3-acryloxypropyldimethylmethoxysilane, n-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.
Examples of methacrylic silanes are 3-methacryloxypropyltris (vinyldimethoxylsiloxy)silane, 3-methacryloxypropyltris(trimethylsiloxy) silane, 3-methacryloxypropyltris(methoxyethoxy)silane, 3-methacrylo-xypropyltrimethoxysilane, 3-methacryloxypropylpentamethyl disiloxane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyl-diethoxysilane, 3-methacryloxypropyldimethyl methoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropenyltrime-thoxysilane and 3-methacryloxypropylbis(trimethylsiloxy)methylsilane.
The preferred silane is acryloxypropyltrimethoxysilane.
Preferably, the amounts of epoxyalkoxysilane(s) and unsaturated alkoxysilane(s) used for the coupling agent preparation are such that the weight ratio
R = weight of epoxyalkoxysilane weight of unsaturated alkoxysilane
verifies the condition 0.8≦R≦1.2.
The coupling agent preferably comprises at least 50% by weight of solid material from the epoxyalkoxysilane(s) and unsaturated alkoxysilane(s) and more preferably at least 60% by weight.
The coupling agent preferably comprises less than 40% by weight of liquid water and/or organic solvent, more preferably less than 35% by weight.
The expression “weight of solid material from epoxyalkoxy silanes and unsatured alkoxysilanes” means the theoritical dry extract from those silanes which is the calculated weight of unit Q k Si O (4-k)/2 where Q is the organic group that bears the epoxy or unsaturated group and Q k Si O (4-k)/2 comes from Q k Si R′O (4-k) where Si R′ reacts to form Si OH on hydrolysis.
k is an integer from 1 to 3 and is preferably equal to 1.
R′ is preferably an alkoxy group such as OCH 3 .
The water and organic solvents referred to above come from those which have been initially added in the coupling agent composition and the water and alcohol resulting from the hydrolysis and condensation of the alkoxysilanes present in the coupling agent composition.
Preferred preparation methods for the coupling agent comprises:
1) mixing the alkoxysilanes
2) hydrolysing the alkoxysilanes, preferably by addition of an acid, such a hydrochloric acid
3) stirring the mixture
4) optionally adding an organic solvent
5) adding one or several catalyst(s) such as aluminum acetylocetonate
6) stirring (typical duration: overnight).
Typically the amount of coupling agent introduced in the scratch-resistant coating composition represents 0.1 to 15% by weight of the total composition weight, preferably 1 to 10% by weight.
The scratch-resistant coating composition can be applied on the anti-reflecting using any classical method such as spin, dip or flow coating.
The scratch-resistant coating composition can be simply dried or optionally precured before application of the subsequent impact-resistant primer coating 31 . Depending upon the nature of the scratch-resistant coating composition thermal curing, UV-curing or a combination of both can be used.
Thickness of the scratch-resistant coating 30 , after curing, usually ranges from 1 to 15 μm, preferably from 2 to 6 μm.
Before applying the impact resistant primer on the scratch resistant coating, it is possible to subject the surface of the scratch resistant coating to a corona treatment or a vacuum plasma treatment, in order to increase adhesion.
The impact-resistant primer coating 31 can be any coating typically used for improving impact resistance of a finished optical article. Also, this coating generally enhances adhesion of the scratch-resistant coating 30 on the substrate of the finished optical article.
By definition, an impact-resistant primer coating is a coating which improves the impact resistance of the finished optical article as compared with the same optical article but without the impact-resistant primer coating.
Typical impact-resistance primer coatings are (meth)acrylic based coatings and polyurethane based coatings.
(Meth)acrylic based impact-resistant coatings are, among others, disclosed in U.S. Pat. No. 5,015,523 whereas thermoplastic and cross linked based polyurethane resin coatings are disclosed inter alia, in Japanese Patents 63-141001 and 63-87223, EP-0404111 and U.S. Pat. No. 5,316,791.
In particular, the impact-resistant primer coating according to the invention can be made from a latex composition such as a poly(meth)acrylic latex, a polyurethane latex or a polyester latex.
Among the preferred (meth)acrylic based impact-resistant primer coating compositions there can be cited polyethyleneglycol(meth)acrylate based compositions such as, for example, tetraethyleneglycoldiacrylate, polyethyleneglycol (200) diacrylate, polyethyleneglycol (400) diacrylate, polyethyleneglycol (600) di(meth)acrylate, as well as urethane (meth)acrylates and mixtures thereof.
Preferably the impact-resistant primer coating has a glass transition temperature (Tg) of less than 30° C.
Among the preferred impact-resistant primer coating compositions, there may be cited the acrylic latex commercialized under the name Acrylic latex A-639 commercialized by Zeneca and polyurethane latex commercialized under the names W-240 and W-234 by Baxenden.
In a preferred embodiment, the impact-resistant primer coating may also includes an effective amount of a coupling agent in order to promote adhesion of the primer coating to the optical substrate and/or to the scratch-resistant coating.
The same coupling agents, in the same amounts, as for the scratch-resistant coating compositions can be used with the impact-resistant coating compositions.
The impact-resistant primer coating composition can be applied on the scratch-resistant coating 30 using any classical method such as spin, dip, or flow coating.
The impact-resistant primer coating composition can be simply dried or optionally precured before molding of the optical substrate. Depending upon the nature of the impact-resistant primer coating composition, thermal curing, UV-curing or a combination of both can be used.
Thickness of the impact-resistant primer coating 31 , after curing, typically ranges from 0.05 to 20 μm, preferably 0.5 to 10 μm and more particularly from 0.6 to 6 μm.
The next step of the method is, as shown in FIG. 1B , assembling the front part 10 coated with the anti-reflecting, scratch-resistant and impact-resistant primer coatings 20 , 30 , 31 with the rear part 11 of the two-part mold as described, for example, in U.S. Pat. Nos. 5,547,618 and 5,562,839.
The molding cavity is then filled with a liquid curable optical composition which is cured to form the optical substrate 40 .
The optical substrate can be made from any typical liquid, curable composition used in the optical field.
Examples of such optical substrates are substrates resulting from the polymerization of:
diethylene glycol bis (allylcarbonate) based compositions, (meth)acrylic monomer based compositions, such as compositions comprising (meth)acrylic monomers derived from bisphenol-A; thio(meth)acrylic monomer based compositions; polythiourethane precursor monomer based compositions; and epoxy and/or episulfide monomer based compositions.
Depending upon the nature of the curable optical material, the optical material can be thermally cured, UV-cured or cured with a combination of both, or cured at ambient temperature.
As shown in FIG. 1C , once the optical substrate 40 has been cured, and optionally concurrently the scratch-resistant coating 30 and the impact-resistant primer coating 31 if not previously cured, the mold part 10 , 11 are disassembled to recover the optical substrate 40 having transferred on one face, the impact-resistant primer coating 31 , the scratch-resistant coating 30 and the anti-reflecting coating 20 .
There is shown in FIGS. 2A to 2 C another embodiment of the method of the invention.
The essential difference between the method described in connection with FIGS. 1A to 1 C and the method illustrated by FIGS. 2A to 2 C is that an additional hydrophobic top coat 50 is deposited onto the optical surface 10 a of the front part 10 of the mold prior to the deposition of the anti-reflecting coating 20 .
The hydrophobic top coat 50 , which in the finished optical article constitutes the outermost coating on the optical substrate, is intended for improving dirty mark resistance of the finished optical article and in particular of the anti-reflecting coating.
As known in the art, a hydrophobic top coat is a layer wherein the stationary contact angle to deionized water is at least 60°, preferably at least 75° and more preferably at least 90°.
The stationary contact angle is determined according to the liquid drop method in which a water drop having a diameter smaller than 2 mm is formed on the optical article and the contact angle is measured.
The hydrophobic top coats preferably used in this invention are those which have a surface energy of less than 14 m Joules/m 2 .
The invention has a particular interest when using hydrophobic top coats having a surface energy of less than 13 m Joules/m 2 and even better less than 12 m Joules/m 2 .
The surface energy values referred just above are calculated according to Owens Wendt method described in the following document: “Estimation of the surface force energy of polymers” Owens D. K.—Wendt R. G. (1969) J. Appl. Polym. Sci., 1741-1747.
Such hydrophobic top coats are well known in the art and are usually made of fluorosilicones or fluorosilazanes i.e. silicones or silazanes bearing fluor-containing groups. Example of a preferred hydrophobic top coat material is the product commercialized by Shin Etsu under the name KP 801M.
The top coat 50 may be deposited onto the optical surface 10 a of mold part 10 using any typical deposition process, but preferably using thermal evaporation technique.
Although the deposition of the top coat is preferably made by transfer from the mold, the top coat can be also applied by any classical means (for example dip coating) on an antireflective lens previously obtained by the transfer method (without any top coat applied on the mold).
Thickness of the hydrophobic top coat usually ranges from 1 to 30 nm, preferably 1 to 15 nm.
The remaining steps of this second embodiment of the method of the invention are identical to those described in relation with FIGS. 1A to 1 C.
The following examples illustrate the present invention. In the examples, unless otherwise stated, all parts and percentages are by weight.
1. Two-Part Mold
In all the examples the mold used was made of polycarbonate (General Electric Company).
2. Scratch-resistant coating compositions (hard coating composition) The following thermal and/or UV curable hard coating compositions were prepared by mixing the components as indicated hereinunder.
Component Parts by weight Hard coating composition n° 1: thermally curable Glymo 21.42 0.1N HCI 4.89 Colloidal Silica 1034A 30.50 (35% by weight of solid) Methanol 29.90 Diacetone alcohol 3.24 Aluminum acetylacetonate 0.45 Coupling agent 9.00 Surfactant (1/10 dilution) 0.60 Hard coating composition n° 2: thermally curable Glymo 18.6 0.1N HCI 6.62 Dimethyldiethoxysilane (DMDES) 9.73 Colloidal Silica/MeOH (1) 60.1 Aluminum acetylacetonate 1.2 Methyl Ethyl Ketone (MEK) 3.65 Coupling agent 5.00 Surfactant FC 430 (2) 0.05 Hard coating composition n° 3: thermally curable Glymo 18.6 0.1N HCI 6.62 Dimethyldiethoxysilane 9.73 Colloidal Silica/MeOH (1) 60.1 Aluminum acetylacetonate 1.2 Methyl Ethyl Ketone (MEK) 3.65 Surfactant FC430 (2) 0.05 Hard coating composition n° 4: (UV curable) Glymo 23.75 n-propanol 14.25 Colloidal Silica MeOH (1) 47.51 Tyzor DC (1% dilution) (3) 14.25 UVI-6974 (4) 0.2735 Coupling agent: precondensed solution of: Glymo 10.0 Acryloxypropyltrimethoxysilane 10.0 0.1N HCI 0.5 Aluminum acetylacetonate 0.2 Diacetone alcohol 1.0 (1) Sun Colloid MA-ST from NISSAN Company (30% by weight of solid SiO 2 ) (2) FC430: surfactant commercialized by 3M Company (3) Tyzor: (4) UVI-6974: Mixture of: and
3. Impact-Resistant Primer Coating Compositions (Primer Coating Compositions)
Several primer coating compositions were made by mixing the various components as indicated below:
Component Parts by weight Impact Primer Coating Composition n° 1a (UV curable Acrylic) Tetraethylene glycol diacrylate (SR-268) 12.42 Aliphatic urethane triacrylate (EB-265) 16.87 n-propanol 20.27 Dowanol PM (5) 20.27 Dowanol PnP (6) 20.27 Coupling agent 9.00 ITX (7) 0.063 Irgacure 500 (8) 0.60 Surfactant FC-430 (50% dilution) 0.21 Impact Primer Coating Composition n° 1b (UV curable Acrylic) Polyethylene (400) glycol diacrylate 12.42 (SR-344) Aliphatic urethane triacrylate (EB-265) 16.87 n-propanol 20.27 Dowanol PM 20.27 Dowanol PnP 20.27 Coupling agent 9.00 ITX 0.063 Irgacure 500 0.60 Surfactant FC-430 (50% dilution) 0.21 Impact Primer Coating Composition n° 2 (thermal curable polyurethane latex W-234) Polyurethane Latex W-234 (9) 35.0 Deionized Water 50.0 2-Butoxy Ethanol 15.0 Coupling agent 5.0 or Polyurethane Latex W 234 40.0 Deionized Water 40.0 Dowanol PnP 20.0 Coupling agent 5.0 Surfactant L77 (10) 0.5 Impact Primer Coating Composition n° 3 (Thermal curable, Acrylic latex A-639) Acrylic latex A-639 (11) 40.0 Deionized water 40.0 2-Butoxy Ethanol 20.0 Impact Primer Coating Composition n° 4 (UV curable Hybrid) UVR6110 (12) 13.00 HDODA (13) 10.89 Pentaerithritol pentaacrylate 30.36 GE 21 (14) 30.29 Diethylene glycol diacrylate 7.01 Isobornyl acrylate 2.29 Surfactant 0.09 Mixed triarylsulfonium 0.30 hexafluoroantimonate salts Impact Primer Coating Composition n° 5 (UV curable Hybrid) UVR6110 13.00 HDODA 10.89 Polyethylene glycol (400) diacrylate 30.36 GE 21 30.29 Diethylene glycol diacrylate 7.01 Isobornyl acrylate 2.29 Surfactant 0.09 Mixed triarylsulfonium 0.30 hexafluoroantimonate salts (5) Dowanol PM: 1-methoxy-2-propanol and 2-methoxy-1-propanol solvent commercialized by DOW CHEMICAL. (6) Dowanol PnP: solvent commercialized by DOW CHEMICAL which is a mixture of: 1-propoxy-2-propanol, 2-propoxy-1-propanol, Propyleneglycol, Diethyleneglycol, Dipropylglycolmonopropylether (7) ITX: Isopropylthioxanthone (8) Irgacure 500: 1/1 mixture of benzophenone + 1-hydroxycyclohexylphenyl (9) Polyurethane latex commercialized by Baxenden (10) L77 surfactant commercialized by OSI Specialities (11) Acrylic Latex-A-639 commercialized by Zeneca (12) UVR6110 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbonate + monoepoxide of 3-cyclohexenylmethyl-3-cyclocarboxylate (13) HDODA 1,6-hexanediol diacrylate (14) GE21 1,4-butanediol diglycidylether
4. Optical Substrate Compositions
Component Parts by weight Optical substrate composition n° 1 (UV/Thermally curable) The following mixture was prepared at 40° C. in the dark. Tetraethoxy bisphenol A dimethacrylate 980 Methyl butene-1 ol 20 Irgacure 1850 (15) 1.75 Optical substrate composition n° 2 (UV/Thermally curable) Polypropyleneglycol (400) 51 dimethacrylate Urethane methacrylate (Plex ® 66610) 34 Isobornyle methacrylate 15 Irgacure 1850 0.1 Optical substrate composition n° 3 (UV/Thermally curable) Thiomethacrylate (16) 70 Dicyclopentadiene dimethacrylate 10 FA321M (17) 20 Methylbutene-1-ol 0.3 UV 5411 (18) 0.1 Irgacure 819 (19) 0.1 (15) Irgacure 1850: mixture (50/50 by weight) of: (16) Thiomethacrylate: Plex (6856) sold by RÖHM. (17) FA 321M (18) UV 5411: 2-(2-hydroxy-5-t-ocylphenyl)benzotriazole. (19) Irgacure 819: photoinitiator of formula:
5. Preparation of the Mold
Unless otherwise stated, the polycarbonate molds used in the examples were prepared as follows:
a) The injection-molded polycarbonate mold is de-gated and then edged. The edging process may create scratches on the surface of the mold, so tape covering of at least the central portion of the mold surface is used during edging. b) After edging, the mold is wipped, cleaned in ultrasonic system, and then heated in a clean oven for half an hour at 100° C.
6. Deposition of Hydrophobic Top Coat and Anti-Reflecting Coating
Unless otherwise stated, hydrophobic top coat and anti-reflecting coating were deposited on the optical surface of the front part of the mold as follows:
The hydrophobic top coat and anti-reflecting treatments are accomplished in a standard box coater using well known vacuum evaporation practices.
a—The mold is loaded into the standard box coater such as a Balzers BAK760 and the chamber is pumped to a high vacuum level. b—Hydrophobic top coat, a fluorosilazane (Shin Etsu KP801M), is deposited onto the optical surface of the first part of the mold using a thermal evaporation technique, to a thickness in the range of 2-15 nm. c—The dielectric multilayer anti-reflecting (AR) coating, consisting of a stack of high- and low-index materials is then deposited, in reverse of the normal order. Details of this deposition are as such:
The first layer is a layer of of SiO 2 having a physical thickness of 80-110 nm (optical thickness about 100-160 nm). The second layer is a layer of ZrO 2 having an optical thickness of about 160 nm, the third layer is a SiO 2 layer having an optical thickness of about 30 nm and the fourth layer is a ZrO 2 layer having an optical thickness of about 55 nm (optical thickness are given at a warelength of 550 nm).
d—At the completion of the deposition of the four-layer anti-reflecting stack, a thin layer of SiO 2 , having a physical thickness of 1-50 nm, is deposited. This layer is to promote adhesion between the oxide antireflecting stack and the subsequent hard-coating which will be deposited on the coated mold at a later time.
EXAMPLE 1
The front part of a polycarbonate two-part mold already coated with a hydrophobic top coat and an AR coating was coated with Hard Coating Composition n o 1. Hard coating application speed was set at 400 rpm for 8 seconds and spin off speed at 800 rpm for 10 seconds. Hard Coating Composition is cured by IR for 30 seconds with 725F setting, using Lesco IR curing unit. The coated mold was allowed to cool to room temperature and Impact Primer Coating Composition n o 1a is applied at the same speed and timing as mentioned above. Impact Primer Coating composition is cured by UV light, using Fusion system H bulb with belt speed of (5 feet per minute) 1.526 m/minute.
Final coating cure was achieved using Lesco IR curing unit set at 725F for 30 seconds.
The coated plastic mold was assembled, filled with optical substrate composition n o 1 and polymerized within 20 minutes. Upon disassembly of the plastic mold, all of the coatings were transferred to the finished lens.
EXAMPLE 2
The first part of a polycarbonate two-part mold already coated with a hydrophobic top coat and an AR coating was coated with Hard Coating Composition n o 1. Hard coating application speed was set at 400 rpm for 8 seconds and spin off speed at 800 rpm for 10 seconds. Hard Coating Composition cured by IR for 30 seconds with 725F setting, using Lesco IR curing unit. The coated mold was allowed to cool to room temperature and Impact Primer Coating Composition n o 1b was applied at the same speed and timing as mentioned above. Impact Primer Coating Composition was cured by UV light, using Fusion system H bulb with belt speed of (5 feet per minute) 1.524 m/minute.
Final coating cure was achieved using Lesco IR curing set at 725F for 30 seconds.
The coated plastic mold was assembled, filled with optical substrate Composition n o 1 and polymerized within 20 minutes. Upon disassembly of the plastic mold, all of the coatings were transferred to the finished lens.
EXAMPLE 3
The front part of a polycarbonate two-part mold already coated with a hydrophobic top coat and an AR coating was coated with Hard Coating Composition n o 2. Hard coating application speed was 500 rpm for 8 seconds and spin off at 1200 rpm for 10 seconds. Hard Coating Composition precured in a thermal heated oven for 10 minutes at 80° C. The coated mold was allowed to cool to room temperature. Impact Primer Coating Composition n o 2 was applied at the application speed 400 rpm for 8 seconds and spin off 1000 rpm for 10 seconds. Impact Primer Coating was precured at the same temperature and timing as the Hard Coating.
Final coating curing was done in a thermal heated oven for 1 hour at 90° C.
The coated plastic mold was assembled, filled with optical substrate composition n o 1 and polymerized within 20 minutes. Upon disassembly of the molds, all of the coatings transferred to the finished lens.
EXAMPLE 4
The front part of a polycarbonate two-part mold already coated with a hydrophobic top coat and an AR coating was coated with Hard Composition n o 3, this hard coating did not contain a coupling agent. Hard coating application speed was 500 rpm. for 8 seconds and spin off. at 1200 rpm. for 10 seconds. Hard Coating was precured in a thermal heated oven for 10 minutes at 80° C. The coated mold was allowed to cool to room temperature. Impact Primer Coating Composition n o 2 was applied at the application speed 400 rpm for 8 seconds and spin off 1000 rpm for 10 seconds. Impact Primer Coating was precured at the same temperature and timing as the Hard Coating.
Final coating curing was done in a thermal heated oven for 1 hour at 90° C.
The coated plastic mold was assembled, filled with optical substrate composition n o 1 and polymerized within 20 minutes. Upon disassembly of the mold, all of the coatings transferred to the finished lens.
EXAMPLE 5
The front part of a polycarbonate two-part mold already coated with a hydrophobic coat and an AR coating was coated with Hard Coating Composition n o 2. Hard coating application speed was 500 rpm for 8 seconds and spin off at 1200 rpm. for 10 seconds. Hard Coating was precured in a thermal heated oven for 10 min at 80° C. Coated mold was cooled down to room temperature. Impact Primer Coating Composition 3 was applied at the application speed 600 rpm for 8 seconds and spin off 1500 rpm for 10 seconds. Impact Primer Coating was precured at the same temperature and timing as Hard Coating Composition n o 2.
Final coating curing was achieved in a thermal heated oven for 2 hours at 90° C.
The coated molds were assembled, filled with optical substrate composition n o 1 and polymerized within 20 minutes. Upon disassembly of the plastic mold, all of the coatings transferred to the finished lens.
EXAMPLE 6
The front part of a polycarbonate two-part mold already coated with a hydrophobic top coat and an AR coating was coated with Hard Coating Composition n o 4. Hard coating application speed was set at 600 rpm for 8 seconds and spin off speed at 1200 rpm for 10 seconds. Hard Coating was UV cured by Fusion system H bull at (5 feet per minute) 1.524 m/minute and followed by 30 seconds IR cure at 725F for 30 seconds, using Lesco IR curing unit. Coated mold was allowed to cool to room temperature and impact Primer Coating Composition n o 4 was applied at the same speed and timing as mentioned above. Impact Primer Coating was cured by UV light, using Fusion system H bulb with belt speed of (5 feet per minute) 1.524 m/minute.
Final coating curing was achieved using Lesco IR curing unit set at 725F for 30 seconds.
The coated plastic mold was assembled, filled with optical composition n o 1 and polymerized within 20 minutes. Upon disassembly of the mold, all of the coatings transferred to the finished lens.
EXAMPLE 7
The front part of a polycarbonate two-part mold already coated with a hydrophobic top coat and an AR coating was coated with Hard Coating Composition n o 4. Hard coating application speed was set at 600 rpm for 8 seconds and spin off speed at 1200 rpm for 10 seconds. Hard Coating UV is cured by Fusion system H bulb at (5 feet per minute) 1.524 m/minute and followed by 30 seconds IR cure at 725F for 30 seconds, using Lesco IR curing unit. Coated mold was allowed to cool to room temperature and Impact Primer Coating n o 5 was applied at the same speed and timing as mentioned above. Impact Primer Coating was cured by UV light, using Fusion SYSTEM H bulb with belt speed of (5 feet per minute) 1.524 m/minute.
Final coating curing was achieved using Lesco IR curing unit set at 725F for 30 seconds.
The coated plastic mold was assembled, filed with optical substrate Composition n o 1 and polymerized within 20 minutes. Upon disassembly of the mold, all of the coatings transferred to the finished lens.
The performances of the finished lenses of examples 1 to 7 are given in Table below:
Steel
Dry
Bayer
wool
Transmission
Example No.
adhesion test
abrasion test
test
(%)
Impact energy (mJ)
1
Well
4.47
1
98.8
692.40
Tc = 1.68 mm
2
Well
4.73
1
98.8
1126.60
Tc = 2.56 mm
3
Well
5.35
0
98.9
711.00
Tc = 1.38 mm
4
Well
4.37
0
98.9
844.00
Tc = 1.46 mm
5
Well
4.81
0
97.9
339.80
Tc = 1.48 mm
6
Well
4.22
0
98.8
62.40
Tc = 1.37 mm
7
Well
2.66
5
98.6
849.00
Tc = 1.34 mm
Tc = Thickness at center
EXAMPLE 8
This example illustrates the use of a protective and releasing coating on the optical surfaces of the mold.
In this example, no hydrophobic top coat is used.
The composition of the releasing and protective coating was as follows:
Component
Parts by weight
PETA LQ (acrylic ester of
5.00
pentaerythritol)
Dowanol PnP
5.00
Dowanol PM
5.00
n-propanol
5.00
1360 (Silicone Hexa-acrylate, Radcure)
0.10
Coat-O-Sil 3503 (reactive flow additive)
0.06
Photoinitiator
0.20
The polycarbonate molds are cleaned using soap and water and dried with compressed air. The mold surface are then coated with the above releasing and protecting coating composition via spin coating with application speed of 600 rpm for 3 seconds and dry speed of 1200 rpm for 6 seconds. The coating was cured using Fusion Systems H+bulb at a rate of (5 feet per minute) 1.524 m/minute. A reverse stack of vacuum deposited AR coats is then applied directly on the above coated molds (without any hydrophobic top coat on the above coated molds) according to the general procedure described previously. Once AR coating deposition was finished, the molds were coated first with a hard coating composition n o 1 and then with an impact primer coating composition n o 2, cured, and lenses were cast from optical substrate composition n o 1.
The stack AR coating/hard coating/primer released well from the surface of the coated mold.
EXAMPLE 9
Example 8 is reproduced except that the mold releasing and protective coating composition was as follows:
Component
Parts by weight
PETA LQ (acrylic ester of
4.00
pentaerythritol)
Dowanol PnP
5.00
Dowanol PM
5.00
n-propanol
5.00
1360 (Silicone Hexa-acrylate, Radcure)
2.00
Surface active agent
0.06
Photoinitiator
0.20
and a hydrophobic top coat KP801 is used.
The whole stack top coat/AR coating/hard coat/primer released well from the coated polycarbonate mold and a lens having very good anti-abrasion, antireflective and impact properties was obtained.
EXAMPLE 10
Example 8 is reproduced except that the mold releasing and protective coating composition was as follows:
Component
Parts by weight
PETA LQ (acrylic ester of
5.00
pentaerythritol)
Dowanol PnP
5.00
Dowanol PM
5.00
n-propanol
5.00
Coat-O-Sil 3509 (reactive flow additive)
0.10
Photoinitiator
0.20
and a hydrophobic top coat KP801 is used.
The whole stack top coat/AR coating/hard coat/primer released well from the coated polycarbonate mold and a lens having very good anti-abrasion, antireflective and impact properties was obtained.
EXAMPLE 11
Example 8 is reproduced except that a hydrophobic top coat KP801 is used and that the molds are coated with the following release coating compositions according to the following protocole, before application of the subsequent coatings.
Mold coating composition A:
Deionized water at 60° C.
0.95
A-1100 (gamma aminopropyl trimethoxy silane)
0.50
Mold coating composition B:
Deionized Water at 60° C.
0.95
Dow Q9-6346 (3-trimethoxysilyl propyl octadecyl
0.50
dimethylammonium chloride)
The polycarbonate molds were cleaned using soap and water and dried with compressed air. The molds surfaces were treated by dip coating in the mold coating composition A first for 60 seconds then rinsed off by 60° C. deionized water; then they were coated by dip with mold coating composition B and also rinse off with deionized water at 60° C. The coating composition B was cured using Blue M convection oven at 80° C. for 15 min.
The whole stack top coat/AR coating/hard coat/primer released well from the coated polycarbonate mold and a lens having very good anti-abrasion, antireflective and impact properties was obtained.
EXAMPLE 12
Example 8 is reproduced except that the molds were coated with a fluorocarbon polymer layer as a releasing coating.
Polycarbonate molds were prepared by cleaning ultrasonically in warmed aqueous detergents, then rinsed and dried according to known art. The polycarbonate molds were then heated to 100° C. for a period of time from 0.1-3 hours, to fully dry the material.
The molds were then loaded in the vacuum chamber with a base vacuum capability of better than 0.1 Pa. The chamber is pumped to a high vaccum level. After an ion bombardment of the mold surface, fluoropolymer Teflon was evaporated onto the mold surfaces using either resistance or electron beam heating, to a thickness of 2.5 to 150 nm.
Alternatively, the fluoropolymer layer was applied to the mold surfaces prior to vacuum deposition by means of spin- or dip-coating, using a dilute solution of soluble fluoropolymers such as Teflon AF, Teflon PTFE FEP, or Teflon PTFE PFA. The thickness of these coatings was 30 to 200 nm.
After deposition of the fluoropolymer layer, the oxide anti-reflecting multilayer stack was deposited (in reverse of the normal order), using the process described above.
2 lenses were made, one with a hydrophobic top coat KP801M, and the other one without KP801M.
When used, KP801M hydrophobic material was evaporated on the fluoropolymer layer using resistance heating. Then, the AR coating SiO 2 /ZrO 2 /SiO 2 /ZrO 2 is deposited.
The layer vacuum deposited final was a thin SiO 2 layer after the stack is completed, to promote adhesion of the AR stack to the siloxane-based anti-scratch coating. This layer is not optically active, but is included only to enhance adhesion of the vacuum-deposited AR stack to the anti-scratch coating. Thereafter the other layers were deposited and the lenses cured according to the method described in example 8.
The whole stack AR coating/hard coat/primer or top coat/AR coating/hard coat/primer released well from the Teflon coated polycarbonate mold and a lens having very good anti-abrasion, anti-reflecting and impact properties was obtained.
EXAMPLE 13
Example 3 is reproduced, but using optical substrate composition n o 2 instead of optical substrate composition n o 1, which is then cured as follows:
The mold parts are taped in order to produce a cavity and filled using a syringe, with the optical substrate composition n o 2.
A pre-cure was made in 15 s using a iron doped mercury UV bulb supplied by IST, the intensity was 25-30 mW/cm 2 (measured 420 nanometer with OM 2 radiometer).
Curing was made in IST two side curing oven 2 minutes at 175 mW/cm 2 .
Then curing was achieved in a thermal dynamic air oven, at a temperature of 80° C. for 8 minutes.
The assembly was edged with the plastic molds in order to generate a clear interface to help molds taking a part.
The complete stack was transferred to the lens.
EXAMPLE 14
Example 13 was reproduced, but using optical substrate composition n o 3.
The complete stack was transferred to the lens.
EXAMPLE 15
Example 14 was reproduced but using an allylic formulation using a monomer supplied by PPG under CR607 trade name, catalyzed with 3% by weight of IPP (diisopropylperoxide) and cured using a thermal cycle rising the temperature from 35° C. to 85° C. in 16 hours.
The stack was once against transferred to the lens.
EXAMPLE 16
Example 13 was reproduced but using an optical substrate composition which comprises 52 g of 1,2-bis (2-mercapto ethyl thio)-3-mercaptopropane with KSCN catalyst 190 ppm mixed with 48 g of xylylene diisocyanate.
A gel is obtained at room temperature in 5 minutes, curing is achieved at 120° C. during 2 hours in air oven.
The transfer is made and a very good adhesion is found.
The performances of the lenses of examples 13 to 15 are given in Table II below.
TABLE II
Example
Bayer
Steel wool
Dry
Transmission
No.
abrasion test
test
adhesion
(%)
13
5.6
2
Medium
98.9
14
7.1
9
Good
97.7
15
6.2
0
Good
99.1
Bayer abrasion resistance was determined by measuring the percent haze of a coated and uncoated lens, before and after testing on an oscillating sand abrader as in ASTM F 735-81. The abrader was oscillated for 300 cycles with approximately 500 g of aluminum oxide (Al 2 O 3 ) ZF 152412 supplied by Specially Ceramic Grains (former Norton Materials) New Bond Street; PO Box 15137 Worcester, Mass. 01615-00137. The haze was measured using a Pacific Scientific Hazemeter model XL-211. The ratio of the uncoated lens haze (final-initial) is a measure of the performance of the coating, with a higher ratio meaning a higher abrasion resistance.
Steel wool scratch resistance was determined as follows:
The lens was mounted coated surface up with double sided tape on the end of a one inch (2.54 cm) diameter pivoting rod. Steel wool (000 grade) was then pressed against the coated surface with a five pounds (2.267 kg) weight as back-pressure. The lens was then oscillated for 200 cycles against the steel wool (one inch (2.54 cm) travel), and the haze measured. The difference in haze (final-initial) as measured on a Pacific Scientific Hazemeter model XL-211 is reported as the wool scratch resistance value.
Coating adhesion was measured by cutting through the coating a series of 10 lines, spaced 1 mm apart, with a razor, followed by a second series of 10 lines, spaced 1 mm apart, at right angles to the first series, forming a crosshatch pattern. After blowing off the crosshatch pattern with an air stream to remove any dust formed during scribing, clear cellophane tape was then applied over the crosshatch pattern, pressed down firmly, and then rapidly pulled away from coating in a direction perpendicular to the coating surface. Application and removal of fresh tape was then repeated two additional times; The lens was then submitted to tinting to determine the percentage adhesion, with tinted areas signifying adhesion failures.
Coating passes adhesion tests when percentage adhesion is more than 95%.
EXAMPLES 17 AND 18
These examples illustrate the use of an organic antireflecting coating in the process of the invention.
A spin coated, thermal or UV curable antireflective coating (AR) is deposited on the surface of a thermal plastic mold. The mold assembly is comprised of a concave and convex mold to form a lens. Subsequently, on each AR mold surface, a scratch resistant coating was applied and finally the impact resistant primer coating was deposited. The scratch resistant coating can be formulated to be UV curable or thermal curable. The impact resistant primer coating can be an UV curable coating or a latex thermal curable coating.
The thermal curable AR coating layers can be catalyzed by a metal complex via IR curing and contains nanoparticle colloids. The UV curable AR coating layers can be acrylic or epoxy or a mixture of both, curable by free radical or cationic or a combination of both, and containing nanoparticle colloids.
The UV curable scratch resistant coating can be UV curable acrylic coating, cationic, and/or a combination of cationic and free radical reaction containing nanoparticle colloids. Thermal curable scratch resistant coating can be catalyzed by a metal complex via infra-red curing. This coating also contains nanoparticle colloids.
The UV curable impact coating consists of the free radical curing of an unsaturated hydrocarbon, cationic curing of an oxirane, and the combination of cationic with free radical chemistry. Thermal curable impact coating can be made of acrylic latex or urethane latex and cured by convection heat or an infra-red source.
A coupling agent is used to enhance the chemical bonding between the coating layers and the substrate system.
Following is the summary of the chemistry and process:
AR Coating Layers:
Low Index Layer
Component
Parts
Glymo
18.6
0.1 N HCl
6.62
Dimethyldiethoxysilane
9.73
Colloidal silica Nissan MA-ST
60.1
Aluminum acetyl acetonate
2.40
Isopropyl alcohol
2.55
The coating is then diluted to 3.5% with Ethyl alcohol and surface active agent is added.
High index layer
Component
Parts
Glymo
4.01
0.1N HCl
2.03
Diacetone alcohol
9.65
Nissan HIT32M
32.17
Aluminum acetyl acetonate
0.54
Ethyl alcohol
54.47
A surface active agent is then added.
Nissan HIT 32M is a colloïd composite sol of TiO 2 /SnO 2 .
Impact primer coating: (UV curable acrylic).
Component
Parts
Diethylene glycol diacrylate (SR-344)
12.42
Aliphatic urethane triacrylate (EB-265)
16.87
n-Propanol
20.27
Dowanol PM
20.27
Dowanol PnP
20.27
Coupler
9.00
ITX
0.063
EXAMPLE 17
Hard Coating n o 1, Impact Primer Coating n o 1b
The low index layer was deposited onto the mold surface by spin coating at application speed of 900 rpm and spin off at 2500 rpms for 10 seconds. The coating was cured by Casso Lesco IR curing set at 385° C. (725° F.) for 1 minute. The high index layer was deposited onto the cooled mold under the same conditions as the low index layer. The thermal plastic mold was coated with Hard Coating n o 1, again, after cooling. Hard coating application speed was set at 400 rpm for 8 seconds and spin off speed at 800 rpm for 10 seconds. Hard coating cured by IR for 30 seconds with (725F) setting, using Lesco IR curing unit. The coated mold was allowed to cool to room temperature and Impact primer coating n o 6 was applied at the same speed and timing as mentioned above. Impact primer coating was cured by UV light, using Fusion system H bulb belt speed of 1,524 m/minute (5 feet per minute).
Final coating cure was achieved using Lesco IR curing unit set at 725 F for 30 seconds.
The coated Thermal plastic mold was assembled, filled with UV curable acrylic lens material (Optical substrate composition n o 1) and polymerized within 20 minutes. Upon disassembly of the plastic mold, all of the coatings were transferred to the finished lens.
Following is the performance result:
Bayer abrasion
Steel
Dry
Impact
Center
% T
test
wool test
adhesion
(mJ)
thickness
(hazegard)
1.93
1.49
Good
559.7
1.36 mm
95.0
Avg. % Transmission of an uncoated lens of the same substrate is 91.4%.
EXAMPLE 18
Thermal Curable, Urethane Latex W-234
Molds were coated with low and high index spin AR layers as in Example n o 17. The thermal plastic mold was coated with Hard coating n o 2. Hard coating application speed was 500 rpm for 8 seconds and spin off at 1200 rpm for 10 seconds. Hard coating precured in a thermal heated oven for 10 minutes at 80° C. The coated mold was allowed to cool to room temperature. Impact primer coating n o 2 was applied at the application speed 400 rpm for 8 seconds and spin off 1000 rpm for 10 seconds. Impact primer coating, precured at the same temperature and timing as the Hard coating.
Final coating curing was done in a thermal heated oven for 2 hours at 90° C.
The coated plastic mold was assembled, filled with UV curable acrylic (Optical substrate composition n o 1) lens material and polymerized within 20 minutes. Upon disassembly of the molds, all of the coatings transferred to the finished lens.
Following is the performance result:
Bayer abrasion Steel Center % T test wool test Dry adhesion Impact (mJ) thickness (hazegard) 1.94 1.74 Good 441 average 1.18 mm 94.9
Light Transmission Test
Transmission was measured using a BYK GARDNER Haze-guard plus hazemeter catalog n o 4725.
Impact Resistance Test
Impact energy was measured using a proprietary system. It can be measured by using the protocole of FDA drop ball test with increasing weights for the ball up to the breaking of the lens or the appearance of a visual crack, generally having the shape of a star, where the ball impacted. The corresponding energy is then measured.
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The invention relates to a method for forming from a mold optical articles. These methods are particularly useful in preparing ophthalmic articles such as ophthalmic lenses, having several optical coatings thereon. The invention also relates to ophthalmic articles produced by these methods.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a U.S. National-Stage entry under 35 U.S.C. §371 based on International Application No. PCT/EP2013/051483, filed Jan. 25, 2013, which was published under PCT Article 21(2) and which claims priority to German Application No. 10 2012 201 502.7, filed Feb. 2, 2012, which are all hereby incorporated in their entirety by reference.
TECHNICAL FIELD
The technical field relates to a liquid washing or cleaning agent with anionic and nonionic surfactants. The technical field also relates to a water-soluble package comprising a liquid washing or cleaning agent of this type.
BACKGROUND
It is increasingly often the case that delicate textiles, such as for example silk or microfibers, are processed into garments that can only be washed at 30 or 40° C. Furthermore, energy-saving washing at low washing temperatures is becoming a trend. However, the performance of washing agents on fat-containing soils declines as washing temperatures are lowered. A pretreatment of fat-containing soils is regarded as inconvenient by many consumers.
To increase the cleaning performance, in WO 2011/117079 A1, for example, the use of liquid, hydrophobic compounds in combination with unsaturated fatty acid(soap)s is proposed.
However, the need still exists to improve the cleaning performance of washing or cleaning agents, in particular on fat-containing soils.
Washing or cleaning agents are available to the consumer today in a wide variety of presentations. In addition to powders and granules, this range also comprises e.g. liquids, gels or single-dose packages (tablets or filled bags).
In particular, single-dose packages with liquid washing or cleaning agents are becoming increasingly popular; on the one hand they meet the consumer's desire for simplified dosing and on the other hand, more and more consumers prefer liquid washing or cleaning agents.
In the formulation of liquid washing or cleaning agents for packaging in water-soluble bags, it must be ensured in particular that the ingredients of the washing or cleaning agent do not already dissolve or partially dissolve the water-soluble envelope of the bag before it is used, thus leading to undesirable leakages.
Accordingly, it is at least one object herein to provide a liquid washing or cleaning agent with increased cleaning performance, in particular on fat-containing soils, which is also suitable for packaging in a water-soluble envelope. Furthermore, other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with the accompanying drawings and this background of the invention.
SUMMARY
In accordance with an exemplary embodiment, a liquid washing or cleaning agent comprises: an anionic surfactant neutralized with an amine; an alkoxylated oxo alcohol with 7 or 8 alkoxy units; and up to about 10 wt. % water, based on the total washing or cleaning agent.
In accordance with another exemplary embodiment, a water-soluble package contains a liquid washing or cleaning agent and a water-soluble envelope. The liquid washing or cleaning agent comprises: an anionic surfactant neutralized with an amine; an alkoxylated oxo alcohol with 7 or 8 alkoxy units; and up to about 10 wt. % water, based on the total washing or cleaning agent.
In accordance with a further exemplary embodiment, a method of cleaning a fat-containing soil from a cloth comprises applying a washing or cleaning agent to the soil on the cloth. The washing or cleaning agent comprises an anionic surfactant neutralized with an amine; an alkoxylated oxo alcohol with 7 or 8 alkoxy units; and up to about 10 wt. % water, based on the total washing or cleaning agent.
DETAILED DESCRIPTION
In an exemplary embodiment, a liquid washing or cleaning agent comprises:
a) an anionic surfactant neutralized with an amine,
b) an alkoxylated oxo alcohol with 7 or 8 alkoxy units and
c) up to about 10 wt. % water, based on the total washing or cleaning agent.
Surprisingly, it has been shown that the use of oxo alcohols with 7 or 8 alkoxy units as nonionic surfactants leads to liquid washing or cleaning agents with increased cleaning performance, in particular on fat-containing soils.
In an exemplary embodiment, the amine is chosen from choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine and mixtures thereof.
Neutralization with amines, unlike bases such as NaOH or KOH, does not lead to the formation of water. Thus, low-water washing or cleaning agents can be produced that are directly suitable for use in water-soluble bags.
In one embodiment, the neutralized anionic surfactant is chosen from neutralized alkylbenzenesulfonic acids, neutralized olefin sulfonic acids, neutralized C12-18 alkanesulfonic acids, neutralized sulfuric acid monoesters with fatty alcohols, neutralized fatty acids, neutralized sulfuric acid monoesters with ethoxylated fatty alcohols and mixtures thereof. These neutralized anionic surfactants exhibit a high cleaning performance on a large number of soils.
A particularly high cleaning performance on fat-containing soils is obtained with the use of C13-15 oxo alcohols with 7 EO, C13-15 oxo alcohols with 8 EO and mixtures thereof in the liquid washing or cleaning agents.
Another exemplary embodiment includes a water-soluble package, which contains a liquid washing or cleaning agent and a water-soluble envelope, wherein the liquid washing or cleaning agent contains
a) an anionic surfactant neutralized with an amine,
b) an alkoxylated oxo alcohol with 7 or 8 alkoxy units and
c) up to about 10 wt. % water, based on the total washing or cleaning agent.
In an embodiment, the water-soluble envelope contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble envelopes containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, in particular cold-water solubility.
Also provided herein is the use of a combination of anionic surfactant neutralized with an amine and an alkoxylated oxo alcohol with 7 or 8 alkoxy units in a liquid washing or cleaning agent, which contains up to about 10 wt. % water, based on the total washing or cleaning agent, to increase the cleaning performance on fat-containing soils.
In an exemplary embodiment, the liquid washing or cleaning agent contains an anionic surfactant neutralized with an amine and an alkoxylated oxo alcohol with 7 or 8 alkoxy units.
In another embodiment, the anionic surfactant neutralized with an amine is a neutralized alkylbenzenesulfonic acid, a neutralized olefin sulfonic acid, a neutralized C12-18 alkanesulfonic acid, a neutralized sulfuric acid monoester with a fatty alcohol, a neutralized fatty acid, a neutralized sulfuric acid monoester with an ethoxylated fatty alcohol or a mixture of two or more of these neutralized anionic surfactants. Among these neutralized anionic surfactants, neutralized alkylbenzenesulfonic acids, neutralized fatty acids and mixtures thereof are particularly suitable.
The content of anionic surfactant neutralized with amine is, for example, about 10 to about 50 wt. %, such as, about 15 to about 40 wt. %, based in each case on the total liquid washing or cleaning agent.
As surfactants of the sulfonate type, preferably C9-13 alkylbenzenesulfonates or mixtures of alkene- and hydroxyalkanesulfonates and disulfonates, as obtained, e.g., from C12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, are suitable. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
As alk(en)yl sulfates, the salts of the sulfuric acid semiesters of C12-C18 fatty alcohols, e.g., from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those semiesters of secondary alcohols of these chain lengths are suitable. For technical reasons relating to washing, the C12-C16 alkyl sulfates and C12-C15 alkyl sulfates, as well as C14-C15 alkyl sulfates, are suitable. 2,3-Alkyl sulfates are also suitable anionic surfactants.
Fatty alcohol ether sulfates, such as the sulfuric acid monoesters of the straight-chained or branched C7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with on average 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO, are suitable.
Other suitable anionic surfactants are soaps. Saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, are suitable, as well as in particular soap mixtures derived from natural fatty acids, for example coconut oil, palm kernel oil, olive oil or tallow fatty acids.
The anionic surfactants are present in the form of ammonium salts. The amine used for neutralization is, for example, choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, with monoethanolamine being particularly suitable.
In an exemplary embodiment, the liquid washing or cleaning agent contains an alkylbenzenesulfonic acid, in particular C9-13 alkylbenzenesulfonic acid, neutralized with monoethanolamine and/or a fatty acid neutralized with monoethanolamine.
In addition to the anionic surfactant neutralized with amine, the liquid washing or cleaning agents contain an alkoxylated oxo alcohol with 7 or 8 alkoxy units. Oxo alcohols are primary, in some cases branched, higher alcohols, which are obtained during oxo synthesis. In this process, oxo aldehydes or primary aldol condensation products thereof are converted to the corresponding oxo alcohols by catalytic hydrogenation.
A C13-15 oxo alcohol with 7 EO, a C13-15 oxo alcohol with 8 EO or a mixture of these two oxo alcohols is suitably employed in the liquid washing or cleaning agents, the use of a C13-15 oxo alcohol with 8 EO being particularly suitable.
The content of alkoxylated oxo alcohol with 7 or 8 alkoxy units is, for example, about 5 to about 35 wt. %, such as about 10 to about 25 wt. %, based in each case on the total liquid washing or cleaning agent.
In addition to the alkoxylated oxo alcohol with 7 or 8 alkoxy units, the liquid washing or cleaning agent can contain further nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
As alkoxylated fatty alcohols, preferably ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol are employed, in which the alcohol residue is linear. In particular, alcohol ethoxylates with 12 to 18 C atoms, for example from coconut alcohol, palm alcohol, tallow fatty alcohol or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol, are suitable. The preferred ethoxylated alcohols include e.g. C12-14 alcohols with 4 EO or 7 EO, C9-11 alcohol with 7 EO, C12-18 alcohols with 5 EO or 7 EO and mixtures thereof. The degrees of ethoxylation stated represent statistical averages, which for a specific product can be a whole or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be employed. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be employed. Furthermore, a mixture of a (relatively strongly) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as e.g. a mixture of a C16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO, is also suitable. The quantity of further nonionic surfactants is, for example, less than about 5 wt. %, for example, less than about 2 wt. %, such as less than about 1 wt. %, based in each case on the total quantity of liquid washing or cleaning agent.
The total quantity of anionic surfactant neutralized with an amine and an alkoxylated oxo alcohol with 7 or 8 alkoxy units in the liquid washing or cleaning agent is up to about 85 wt. %, for example about 40 to about 75 wt. %, such as about 50 to about 70 wt. %, based on the total liquid washing or cleaning agent.
The washing or cleaning agents are liquid. The washing or cleaning agents can contain water, in which case the content of water is less than about 10 wt. %, for example, less than about 8 wt. %, based in each case on the total washing or cleaning agent.
In addition to the anionic surfactant neutralized with an amine and an alkoxylated oxo alcohol with 7 or 8 alkoxy units, the washing or cleaning agent can contain further ingredients that further improve the application properties and/or the aesthetic properties of the washing or cleaning agent. In an exemplary embodiment, the washing or cleaning agent additionally contains one or more substances from the group of the builders, bleaching agents, enzymes, electrolytes, pH adjusting agents, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, anti-grays, shrinkage preventers, anti-wrinkle agents, dye transfer inhibitors, antimicrobial active substances, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, opacifiers, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, proofing and impregnating agents, skincare active substances, swelling and anti-slip agents, softening components and UV absorbers.
The liquid washing or cleaning agent can be filled into a water-soluble envelope and can thus be a constituent of a water-soluble package.
A water-soluble package contains, in addition to the liquid washing or cleaning agent, a water-soluble envelope. The water-soluble envelope is, for example, formed by a water-soluble film material.
These water-soluble packages can be produced either by vertical form fill seal (VFFS) methods or by thermoforming methods.
The thermoforming method generally includes forming a first layer from a water-soluble film material to create convexities for receiving a composition therein, filling the composition into the convexities, covering the convexities filled with the composition with a second layer of a water-soluble film material and sealing the first and second layers together at least around the convexities.
The water-soluble envelope, for example, is made from a water-soluble film material chosen from polymers or polymer mixtures. The envelope can be made of one layer or of two or more layers of the water-soluble film material. The water-soluble film material of the first layer and of the other layers, if present, can be the same or different.
The water-soluble package comprising the liquid washing or cleaning agent and the water-soluble envelope can have one or more chambers. The liquid washing or cleaning agent can be contained in one or more chambers, if present, of the water-soluble envelope. In an embodiment, the water-soluble package has two chambers. In this regard, the first chamber contains the liquid washing or cleaning agent and the second chamber contains a solid or liquid agent.
The water-soluble packages with one chamber can have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square or rectangular basic form.
In a water-soluble package with one chamber, the quantity of liquid washing or cleaning agent is, for example, the full or half dose required for a wash cycle. In a water-soluble package with multiple chambers, the quantity of total washing or cleaning agent is, for example, the full or half dose required for a wash cycle.
In another embodiment, the water-soluble envelope contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
Suitable water-soluble films for producing the water-soluble envelope, for example, are based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range of from about 10,000 to about 1,000,000 gmol-1, for example of from about 20,000 to about 500,000 gmol-1, for example of from about 30,000 to about 100,000 gmol-1, such as of from about 40,000 to about 80,000 gmol-1.
The production of polyvinyl alcohol generally takes place by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from corresponding polyvinyl acetate copolymers. In an embodiment, at least one layer of the water-soluble envelope comprises a polyvinyl alcohol of which the degree of hydrolysis is about 70 to about 100 mole %, for example, about 80 to about 90 mole %, for example about 81 to about 89 mole %, such as about 82 to about 88 mole %.
It is additionally possible to add a polymer that is selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid or mixtures of the above polymers, to a film material that is suitable for producing the water-soluble envelope.
Exemplary polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers in addition to vinyl alcohol. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
Likewise exemplary polyvinyl alcohol copolymers comprise an ethylenically unsaturated carboxylic acid, salt thereof or ester thereof in addition to vinyl alcohol. In an embodiment, these polyvinyl alcohol copolymers contain acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof in addition to vinyl alcohol.
Suitable water-soluble films for use in the envelopes of the water-soluble packages contemplated herein are films that are marketed by MonoSol LLC, e.g. with the name M8630, C8400 or M8900. Other suitable films include films with the name Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
EXAMPLE
Liquid washing or cleaning agents were produced by conventional and known methods and processes. In the following Table 1, the compositions of two washing or cleaning agents as contemplated herein, E1 and E2, and two washing or cleaning agents according to prior art, V1 and V2, are shown.
TABLE 1
Liquid washing or cleaning agents E1 and
E2, and V1 and V2 [all quantities are given in
wt. % of active substance, based on the composition]
Ingredients
E1
E2
V1
V2
C 10 -C 13 alkylbenzenesulfonic acid
21
21
21
21
C 13 -C 15 oxo alcohol with 8 EO
22.5
—
—
—
C 13 -C 15 oxo alcohol with 7 EO
—
22.5
—
—
C 12-18 fatty alcohol with 7 EO
—
—
22.5
—
C 12-18 fatty alcohol with 3 EO
—
—
—
22.5
C 12-18 fatty acid
17.5
17.5
17.5
17.5
Glycerol
13
13
13
13
1,2-Propanediol
13.5
13.5
13.5
13.5
Ethanol
3.26
3.26
3.26
3.26
Phosphonate
0.3
0.3
0.3
0.3
Monoethanolamine
6.4
6.4
6.4
6.4
Dyes, enzymes (cellulase, amylase &
0.8
0.8
0.8
0.8
protease), optical brightener, perfume
Water
1.74
1.74
1.74
1.74
To determine the cleaning performance, various fat-containing soils with a diameter of approx. 2 cm each were applied onto various cloths (polyester or cotton).
A domestic washing machine (Miele W 526) was then loaded with 3.5 kg of ballast laundry together with the soiled cloths. In addition, 35 g of the washing agent to be tested (E1, E2, V1 or V2) were metered in and washing was carried out at 40° C. After hanging the cloths to dry and mangling them, their remission was determined spectrophotometrically (Minolta CR200-1) (cf. Table 2). The stain removal was evaluated by means of the Y value.
TABLE 2
Degrees of whiteness (averages of 6 determinations)
E1
E2
V1
V2
Used frying fat/Ctn.
61.7
62.4
60.4
55.2
Lipstick no. 453 (L'Oreal)/Ctn.
46.2
44.4
44.1
33.3
Lipstick no. 83 (Jade)/Ctn.
45.1
43.8
42.6
32.7
Make up no. 40 (Sans Soucis)/Ctn.
53.3
51.4
48.1
32.7
Make up no. 45 (Jade)/Ctn.
41.5
41.4
40.3
37.3
Used lard/PE
68.2
67.3
64.7
57.6
Lipstick no. 83 (Jade)/PE
59.1
58.8
57.4
41.1
Ctn. = cotton, PE = polyester
The results clearly show that liquid washing or cleaning agents with alkoxylated oxo alcohols exhibit higher cleaning performance on fat-containing soils.
For the production of water-soluble packages with the washing or cleaning agents E1 and E2, a film of the M 8630 type (ex Monosol) with a thickness of 76 μm was drawn into a depression by means of a vacuum to form a convexity. The convexity was then filled with 30 ml of one of the liquid washing or cleaning agents E1 or E2. After covering the convexities filled with the agent using a second layer of a film of the M 8630 type, the first and second layers were sealed together. The sealing temperature was 150° C. and the sealing period 1.1 seconds.
After a 4, 8 and 12 weeks' storage period of the water-soluble packages with the washing or cleaning agents E1 or E2 under different climatic conditions, no dissolution or partial dissolution of the water-soluble envelope could be observed whatsoever. Moreover, no pores or holes, which would likewise lead to product discharge or leakages, could be found.
Water-soluble packages with the washing or cleaning agents E1 and E2 dissolved in wash cycles at temperatures in the range of 20 to 95° C. leaving no residue and displayed very good cleaning performance, in particular on fat-containing soils.
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The invention relates to a liquid detergent or cleaning agent, comprising a) an anionic surfactant neutralized with an amine, b) an alkoxylated oxo alcohol having 7 or 8 alkoxy units, and c) up to 10 wt. %, relative to the entire detergent or cleaning agent, of water. The liquid detergent or cleaning agent has very good cleaning performance toward soiling containing fat and can be a component of water-soluble packagings.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 11/895,673, filed Aug. 27, 2007, which is a continuation of U.S. patent application Ser. No. 10/657,672 filed Sep. 4, 2003. The disclosures of the above applications are incorporated herein by reference.
TECHNICAL FIELD
[0002] This invention relates to output regulators.
BACKGROUND
[0003] Output regulators are employed in numerous machines and devices including virtually every electronic device. An output regulator typically converts unregulated input power to one or more regulated outputs for supplying power to circuits within the machine or device. The regulated outputs are most commonly regulated voltage, but regulated current and regulated power may also be generated. The output regulator may be integrated into the machine or device, or the output regulator may be a separate assembly that is assembled to machine or device. Several characteristics of output regulators may be used to judge the quality of a particular design including operating characteristics such as power density, efficiency, output regulation, and transient response. Improvements in the operating characteristics of output regulators are desirable so that machines and devices that use output regulators may be improved such as by being made smaller, requiring less power, having improved accuracy and reliability, or having improved operation during transient conditions.
SUMMARY
[0004] In one aspect, a control system for controlling a multiphase output regulator having a regulated DC output and operating at a switching frequency. The multiphase output regulator including at least two switch arrays to generate individually controllable output phases that combine to form the regulated DC output. The control system comprising a digital controller operable at a sampling frequency greater than the switching frequency. The digital controller responsive to a sense signal corresponding to the regulated output, to generate array duty cycle signals to control each of the switch arrays. The digital controller to control the array duty cycle signals at the sampling frequency and to dynamically set a phase interval between each of the output phases.
[0005] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
[0006] FIG. 1 is a block diagram of an aspect of a multiphase output regulator.
[0007] FIG. 2 is a block diagram of an aspect of a multiphase output regulator.
[0008] FIG. 3 is a block diagram of an aspect of a switch assembly.
[0009] FIG. 4A is a graph of phase waveforms corresponding to aspect of a multiphase output regulator.
[0010] FIG. 4B is a graph of phase waveforms corresponding to aspect of a multiphase output regulator.
[0011] FIG. 4C is a graph of phase waveforms for a conventional multiphase output regulator.
[0012] FIG. 4D is a graph of phase waveforms corresponding to aspect of a multiphase output regulator.
[0013] FIG. 5 is a flow diagram of an operation for controlling a multiphase output regulator.
[0014] FIG. 6 is a block diagram of a digital controller for generating a duty cycle signal.
[0015] FIG. 7 is a graphical representation of voltage ranges spaced about a nominal output voltage, Vout.
[0016] FIG. 8 is a timing diagram of waveforms showing quantization error associated with an aspect of a digital controller.
[0017] Like reference symbols in the various drawings indicate like elements.
DETAILED DESCRIPTION
[0018] FIG. 1 shows a multiphase output regulator 10 for supplying regulated power to a load 12 . Although, the multiphase output regulator 10 is described as having a buck topology, any type of topology may be used such as boost, flyback (buck-boost), Cuk, Sepic, and Zeta. The multiphase output regulator 10 may include a power array 20 to convert an unregulated DC voltage, such as Vin, to multiple output phases 18 that have a dynamically controlled phase relationship. Each of the output phases 18 may include a variable pulse width power signal that may be skewed in time, relative to the other output phases by a phase interval. In addition, the quantity of active output phases may be dynamically controlled. For example, the power array 20 may generate up to “N” different output phases such as 8 output phases 18 . During one operating condition, 4 output phases may be active and spaced at 90 degree time intervals. Then, while the multiphase output regulator 10 operates, another of the output phases 18 may be activated and the 5 active output phases be dynamically controlled to be spaced at 72 degree time intervals.
[0019] The power array 20 may generate current sense signals, Is, corresponding to each of the output phases 18 . Multiple output filters 24 corresponding to the output phases 18 may filter the output phases 18 to generate filtered outputs 25 that may be combined to form a regulated output 26 . Each of the output filters 24 may include an output inductor and an output capacitor. By skewing two or more of the output phases 18 , the ripple voltage of the regulated output may be reduced, and the ripple frequency may be increased leading to a reduction in the size of the output filters. The regulated output 26 is preferably a DC voltage output and may be any output characteristic including voltage, current, and power. The unregulated voltage, Vin, may be any form of input power such as alternating current (AC) voltage and DC voltage. For an AC input voltage a rectification stage (not shown) may be included to convert the AC voltage to the DC input voltage, Vin. An output sensor 28 may sense the regulated output 26 and send a feedback signal 16 to a digital controller 14 . Any type of output sensor 28 may be employed to sense the output. The digital controller 14 may, in response to receiving input signals such as the feedback signal 16 , generate one or more control signals to drive the power array 20 . Other input signals may include the current sense signals Is from the power array 20 . The control signals in the digital controller 14 may include a duty cycle signal, a phase interval signal, and an inertializer signal. The duty cycle signal may control the operating frequency, variable frequency versus fixed frequency operation, the number of output phases generated and the duty cycle generated by the active output phases 18 . The phase interval signal may control the phase angle of each of the output phases 18 . The inertializer signal may control turn-on of the power array 80 to increase the current flowing through the output inductor to the steady-state level to reduce transients in the regulated output during turn-on. The digital controller 14 may generate drive signals based on the control signals to drive the power array 20 . The digital controller 14 may operate at a sampling frequency greater than the switching frequency of the multiphase output regulator. The digital controller 14 may operate at a sampling frequency that is greater than the switching frequency such as a factor of 32, although the frequency of the sampling frequency is non-limiting. The digital controller 14 may be implemented in any programmable digital device such as a real time digital signal processor.
[0020] FIG. 2 shows an aspect of a multiphase output regulator 50 for supplying power to a load 62 . The multiphase output regulator 50 may include a power array 52 having from two to “N” switch arrays 54 for generating phased outputs from a DC input voltage. Each of the switch arrays 54 may receive one or more control signals to control the operating characteristics of the switch arrays 54 such as duty cycle, operating frequency, enable/disable, and start-up operation.
[0021] FIG. 3 shows an aspect of a switch array 80 . The switch array 80 may generate a pulse width modulated output in response to one or more drive signals. A pair of power switches 82 and 84 may be connected in a half-bridge configuration between two voltage sources. The power switches 82 and 84 may be driven by the drive signals to operate in a switching mode to generate the pulse width modulated output. Any type of power switch may be used such as MOSFETs, BJTs, MCTs, IGBTs, and RF FETs. Each of the power switches 82 and 84 may comprise one or more parallel power switches.
[0022] Drivers 88 and 89 may buffer the drive signals from the digital controller 14 to the power switches 82 and 84 . Any type of driver may be used.
[0023] A current sense circuit 85 may sense current flowing to the output or through the power switches 82 and 84 . Any type of current sense circuit 85 may be used such as resistive, transformer-resistor, Hall effect, and sensing voltage across the channel of a FET device.
[0024] The power array 52 may include output filters 56 corresponding to each of the switch arrays 54 . The output filters 56 filter the phase outputs of the switch arrays to generate the regulated output. Each output filter 56 may include an output inductor 58 . A single output capacitor 60 is preferably connected to the combined output of the output filters 56 . However, the output capacitors 60 may be distributed so that each output filter 56 includes an output capacitor 60 .
[0025] A digital controller 64 may generate the control signals to control the flow of power through the power array 52 to the load 62 . The digital controller 64 may include a duty cycle controller 66 to determine, as a function of a feedback signal from the load 62 , a regulator duty cycle to maintain the regulated output in regulation. The feedback signal may sample any output characteristic such as voltage, current, and power. The duty cycle controller 66 may also control the duty cycle as a function of the current, Is, flowing through the output inductor 58 or the power switches 82 and 84 . The duty cycle controller 66 may implement either voltage mode control or current mode control. Also, the duty cycle controller 66 may implement fixed frequency or variable frequency operation. The duty cycle controller 66 may sample the feedback signal and Is at a sampling frequency greater than the switching frequency of the multiphase output regulator 50 .
[0026] Switch controllers 68 may determine and control the power array operating characteristics such as the quantity of phases to generate the duty cycle for each of the activated switch arrays 54 , and a phase interval between each of the activated output phases 54 , where the phase interval is the time offset between the leading edges or the trailing edges of the pulses for each of the output phases 54 that are active. Under steady-state operating conditions the phase interval as measured between the leading edges of the pulses or measured between the trailing edges of the pulses is approximately equal. There may be a one to one correspondence between the switch controllers 68 and the switch arrays 54 . However, the scope of the invention includes controlling either all or a subset of the switch arrays 54 with a single switch controller 68 . The drive signals for each of the switch arrays 54 may be set as a function of the duty cycle signal from the duty cycle controller 66 . Some of the other power array operating characteristics that the switch controllers 68 may determine and control include the quantity of switch arrays 54 to enable, and the switching frequency of the multiphase output regulator 50 , where the switching frequency is the frequency of the individual output phases 54 . The switch controllers 68 may determine the power array operating characteristics based on any regulator criteria such as output current, power switch current for any of the switch arrays, output inductor current, output voltage, output ripple voltage, input voltage, noise generation, and power consumption in discrete components, circuits, or the entire output regulator.
[0027] FIG. 4A shows waveforms of three of the N output phases 54 for an aspect of changing from 2 phase operation to 3 phase operation. The remaining output phases, φ 4 to φN remain inactive. The array controller 68 may enable phases φ 1 and φ 2 of the output phases 54 to each operate at a duty cycle of 33.3% with a phase interval of t 1 . The multiphase output regulator 50 may operate with only phases φ 1 and φ 2 active for any period of time. Then, the array controller 68 may enable phase φ 3 of the output phases 54 and set each of the output phases, φ 1 , φ 2 , and φ 3 to a duty cycle of 33.3% with a phase interval of t 2 . The array controller 68 dynamically changes the phase interval of the output phases 54 to adjust for increasing the number of active output phases 54 from 2 to 3.
[0028] The array controller 68 may also control the current flowing through individual ones of the output inductors 58 . In one aspect, when enabling one or more additional phase outputs, the array controller 68 may control the corresponding switch array 54 to ramp up the current flowing through the corresponding output inductor 58 to minimize the transient response time as the currents flowing through the output inductors 58 of the active output filters 56 settle out to steady-state levels.
[0029] FIG. 4B shows waveforms of the operation of an aspect of the multiphase output regulator 50 during an output load change. At time ta the output load, I load , increases, and the array controller 68 may set all or a subset of the output phases to 100% duty cycle to cause the output current to quickly increase, reducing transient changes in the output voltage. After a period of time, the array controller 68 may dynamically reintroduce the phase relationships between each of the output phases. For example, the array controller may control the leading edges of the drive signals to dynamically set the phase interval between each of the output phases. The trailing edges of the drive signals are then controlled to maintain the regulated output within the regulation limits. In another exemplary system, the array controller 68 may control the trailing to set the phase interval, and control the leading edges to maintain the regulated output in regulation. The array controller 68 may operate similarly when the output load, I load , decreases (not shown). Here, the array controller may set all or a subset of the output phases to 0% duty cycle to cause the output current to quickly decrease, reducing transient changes in the output voltage.
[0030] FIG. 4C shows waveforms of the operation of a conventional multiphase output regulator having four output phases. Conventional multiphase output regulators generally control only the trailing edge of the drive signals. The trailing edge is controlled to maintain the regulated output in regulation. The leading edges of the drive signals for each of the output phases are generally fixed in relation to each other. As the total quantity of output phases is changed, the phase relationship between the phases remains static. For example, in a conventional multiphase output regulator having four output phases, the output phases may be spaced apart by 90 degrees so that the leading edges occur at 0 degrees, 90 degrees, 180 degrees, and 270 degrees. When one of the output phases is disabled, the remaining output phases do not shift relative to each other so that the leading edges may occur at 0 degrees, 90 degrees, and 180 degrees. In addition, during a load change, the length of the conduction time for each of the pulses may be lengthened, but the time relationship between the leading edges is typically maintained static and the time relationship between the trailing edges is also typically maintained static.
[0031] In contradistinction, the phase interval of the multiphase output regulator 50 may be adjusted dynamically by controlling the leading or trailing edges of the drive signals. For example, when the quantity of output phases is changed, the phase interval between each of the output phases may be dynamically changed such as shifting the leading edges from 0 degrees, 90 degrees, 180 degrees, and 270 degrees, to 0 degrees, 120 degrees, and 240 degrees when one of four output phases is disabled.
[0032] FIG. 4D shows another aspect of the multiphase output regulator 50 . The array controller 68 may set multiple switch arrays to the same phase such as setting the output phase pairs φ 1 -φ 4 , φ 2 -φ 5 , and φ 3 -φ 6 to approximately the same duty cycle. The array controller 68 may also apply dithering to the active output phases. The array controller 68 may generate a minimum increment resolution of the duty cycle that is equal to “x 1 ”, and by applying dithering to an output phase or a complementary output phase, the average of the generated pulse may be stretched by any fractional portion of “x 1 ”. In one dithering method, a selected number of pulses within an output phase may be stretched by an integer “N” number of increments, and the remaining pulses within the output phase may be stretched by an integer “N−1” or “N+1” number of increments to generate a pulse that is fractionally stretched.
[0033] FIG. 5 shows an aspect of the operation of a multiphase output regulator. At step 100 , sense a regulated output of the multiphase output regulator. At step 102 , generate a digital feedback signal as a function of the regulated output. At step 104 , determine a duty cycle at which to convert power from an input source to the regulated output. Continuing to step 106 , determine a quantity of output phases to generate. At step 108 , determine a quantity of switch arrays to enable. One or more switch arrays may be used to generate each of the output phases. For example, two switch arrays may be used for each of four output phases leading to a total of eight switch arrays. Continuing to step 110 , determine an array duty cycle for each of the switch arrays based on the regulator duty cycle. At step 112 , determine a phase interval to separate the pulses of each of the output phases. The phase interval may be referenced to any portion of the output phase waveform such as the leading and trailing edges of the pulse. At step 114 , precondition the output inductor currents that correspond to the switch arrays that change operating state from either active to inactive, or from inactive to active. At step 118 , apply dithering to the active output phases.
[0034] FIG. 6 shows an aspect of a digital controller 200 . The digital controller 200 may include a duty cycle controller 202 to determine a duty cycle for operating the switch arrays 54 . The duty cycle controller 202 may include a duty cycle estimator 952 to generate nominal duty cycle signals and an adjust determiner 954 to determine an adjustment value, ADJ, to combine with the nominal duty cycle signals.
[0035] The duty cycle estimator 952 may generate nominal duty cycle signals, Up* and Down*, that correspond to nominal steady-state values from which to generate a current duty cycle for the switching regulator. The duty cycle estimator 952 may be used for generating nominal duty signals in operating states such as PWM, variable frequency, quasi-resonant mode, and energy saving discontinuous mode. However during a hysteretic control operating state, the duty cycle estimator 952 is preferably not used for computing the nominal duty cycle. Instead during hysteretic control, the duty cycle may be directly related to the error signal so that when the error signal is in one state the duty cycle is set to the ON state (up), and when the error signal is in the other state the duty cycle is set to the OFF state (down). The duty cycle estimator 952 may generate the nominal duty cycle signals as a function of input signals such as an error signal, a UD pulse, and a delay control. The error signal may represent the error between the regulated output and a reference. Power switches in the switching regulator may be operated at the current duty cycle to control the conversion of energy from an input source, Vin, to the load 212 . For example, in a switching regulator having a buck topology and fixed frequency operation, the nominal duty cycle signal Up* may be approximately equal to a value that corresponds to the ratio of the output voltage to the input voltage. In another aspect, the nominal duty cycle may be determined by computing a running average of the duty cycle over a predetermined quantity of switching cycles. In another aspect, the nominal duty cycle may be determined by incrementing or decrementing the prior nominal duty cycle based on the amplitude of the error signal. During fixed frequency operation, the combination of the nominal steady-state values may correspond to the total switching period of the switching regulator such as 1 usec for a 1 MHz switching frequency.
[0036] The adjust determiner 954 may determine an adjustment value, ADJ, to combine with the nominal duty cycle signals to generate adjusted duty cycle signals, Up and Down. The adjust determiner 954 may generate the adjustment value as a function of the error signal as well as other signals from the switching regulator. The adjust determiner 954 may generally be used for any operating state except hysteretic control. Since in the hysteretic control operating state, the duty cycle is either 100% ON or 100% OFF, no adjustment value is required. In one aspect, the adjustment value for the PWM state and the energy saving discontinuous mode may be computed as follows:
[0000] ADJ k =g ( e k )+ h (trend k )
[0000] Up k =Up*− ADJ k *FAC on
[0000] Down k =Down*+ ADJ k *FAC off
[0037] where FAC may be determined based on the nominal duty cycle,
[0000]
g
(
e
k
)
=
{
0
if
e
k
<
A
1
sign
(
e
k
)
*
Δ
1
if
A
1
≤
e
k
<
A
2
sign
(
e
k
)
*
Δ
2
if
A
2
≤
e
k
<
A
3
h
(
trend
k
)
=
{
0
if
trend
k
<
1
trend
k
if
trend
k
≥
1
trend
k
=
F
slope
*
e
k
-
e
k
-
n
_
[0038] where F slope is a constant, e k −e k-n is an average of the slope of the waveform where the slope is the error difference from the “n” prior cycles, where “n” is the number of samples in a switching period, and
[0039] A 1 , A 2 , and A 3 are defined in FIG. 7 which shows voltage levels of a voltage slicer for generating the error signal. The voltage levels may be selected to define voltage ranges that are approximately centered around a nominal voltage level for the output voltage, Vout.
[0040] Δ 1 and Δ 2 are loop gains which may be selected at the sampling rate and may have values based on the amplitude of the error signal. The values of the loop gains, Δ 1 and Δ 2 , may be selected to be related such as Δ 2 being approximately equal to two times Δ 1 . The loop gain of the digital controller may be changed adaptively at any rate up to and including the sampling rate. Each of the loop gains may be dynamically changed as a function of any parameter of the output regulator such as the voltage range of the error signal, the voltage range of the regulated output, and the duty cycle.
[0041] The loop compensation of the digital controller may be described by the ratio of g(e k ) to h(trend k ), which may be expressed generally as (A*e(k)/B*e′(k)). The loop compensation may be controlled at any rate up to and including the sampling frequency. In one aspect, the constant F slope may be adaptively changed to change the loop compensation. The loop compensation may be dynamically changed as a function of any parameter of the output regulator such as the voltage range of the error signal, the voltage range of the regulated output, and the duty cycle.
[0042] A combiner 956 may combine the nominal duty cycle signals with the adjustment value to generate the adjusted duty cycle signals. In one aspect, the adjusted duty cycle signals may be used as counter limits for generating a UD pulse.
[0043] One or more switch controllers 204 may receive the adjusted duty cycle signal and generate drive signals for controlling each of the switch arrays 54 of the power array 52 . Each of the switch controllers 204 may control the power array operating characteristics such as the quantity of output phases to generate, the quantity of switch arrays 54 to generate each output phase, and a phase interval between each of the activated output phases 54 , where the phase interval is the time offset between the leading edges of the pulses for each of the output phases 54 that are active. Each switch controller 204 may receive a current sense signal, CL_N, from a corresponding switch array 54 , and control the drive signals as a function of the current sense signal.
[0044] A counter 958 may generate the UD_D pulse as a function of a clock signal, CLOCK, and the adjusted duty cycle signals. The UD_D pulse preferably is a binary signal representing a varying on-time for driving the power switches of the switching regulator. The counter 958 may count a quantity of clock cycles set by the counter limits to generate the “on-time” and “off-time” of the UD_D signal. For example, the Up portion of the adjusted duty cycle signal may set the counter limit for the on-time and the Down portion of the adjusted duty cycle signal may set the counter limit for the off-time. Preferably, a single counter generates the UD_D signal in response to a single counter limit signal including both the Up and Down information. The UD_D pulse may include a quantization error related to the pulse resolution being limited by the frequency of the clock signal. FIG. 8 shows an example of quantization error in which a UD_D pulse 970 that is generated from a clock signal 972 and an adjusted duty cycle signal 974 may have a quantization error 976 related to the frequency of the clock signal.
[0045] A delay line 960 may generate drive signals, UD_A pulse, that finetune the pulse width of the UD_D pulse generated by the counter 958 to reduce the quantization error. The UD_A pulse preferably has an “on” level and an “off” level and may have a varying pulse width to represent an on-time for driving the power switches of the switch array 54 . The delay line 960 may, in response to receiving the UD_D pulse and a delay control signal, generate the UD_A pulse having a duty cycle that approximates the pulse width corresponding to the adjusted duty cycle signals. The delay line 960 may delay either edge of the UD_D pulse to generate the UD_A pulse. For example, in one aspect the UD_D pulse may be generated having a pulse width shorter than the corresponding adjusted duty cycle, and then the delay line 960 may delay the trailing edge to generate the UD_A pulse. In another aspect, the UD_D pulse may be generated having a pulse width longer than the corresponding adjusted duty cycle, and then the delay line 960 may delay the leading edge to generate the UD_A pulse.
[0046] A delay control 962 may generate the delay control signal as a function of the UD_D pulse and the adjusted duty cycle signals. The delay control signal may preferably be a multi-bit signal.
[0047] A phase controller 964 may monitor the UD_A pulse and in response control the counter 958 and the delay control 962 to set the phase characteristics of the power array 52 . The phase characteristics may include the quantity of output phases, the quantity of active switch arrays 54 per output phase, and the phase interval between output phases.
[0048] A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
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An output regulator includes a plurality of switch arrays. A controller enables selected ones of the plurality of switch arrays in response to a sense signal. The sense signal is based on an output of the output regulator. The controller generates drive signals to control the selected ones of the plurality of switch arrays. The controller adjusts first selected pulses in an output phase of the selected ones of the plurality of switch arrays based on a first pulse width. The controller adjusts second selected pulses in the output phase of the selected ones of the plurality of switch arrays based on a second pulse width greater than or less than the first pulse width.
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TECHNICAL FIELD OF THE INVENTION
[0001] This invention relates to a process for the recovery of minor components and refining of vegetable oils and fats from crude vegetable oils and fats, in particular, a process for the recovery of minor components and refining of vegetable oils and fats from seed oil, pulp oil and other vegetable matter.
BACKGROUND OF THE INVENTION
[0002] Crude palm oil contains less than 5% of free fatty acid (FFA). The main fatty acids are palmitic acid and oleic acid. During fractionation, fatty acid is slightly concentrated in the palm olein. Crude palm oil contains 600-1000 ppm of tocotrienol/tocopherol mixture. The tocotrienol presence in palm oil are γ-tocotrienol, α-tocopherol, α-tocotrienol and δ-tocotrienol in an approximate ratio of 5:2:2:1. Tocotrienol is also enriched in the palm olein during fractionation. Tocotrienol was claimed to be very effective in cholesterol lowering, preventing arteriosclerosis and stroke, inhibits breast cancer cells, protecting the skin against the effects of ultraviolet radiation and as powerful antioxidant.
[0003] Typical crude palm oil contains more than 4% of diglyceride. Diglyceride is considered undesirable as it affects crystallization during fractionation. Based on long term human study on feeding of diglycerides-rich cooking oil, diglyceride was said to be able to reduce serum triglycerides, increased serum high density lipoprotein (HDL)-cholesterol and reduction in plasminogen activator inhibitor.
[0004] Crude palm oil contains about 500-700 ppm of carotene. The main carotene components are β-carotene and α-carotene. During fractionation, carotene is concentrated in the olein (liquid) fraction. Crude palm olein can contain up to 1500 ppm of carotene whereas crude palm stearin (the solid fraction) has much lower carotene (as low as less than 200 ppm). Consumption of a mixture of natural carotene was claimed to provide protection towards free radical mediated degenerative diseases such as cancer and cardiovascular diseases. It was also claimed that α-carotene but not β-carotene inhibited liver carcinogenesis. It was also claimed that intake of palm carotene inhibits skin peroxidation induced by ultraviolet radiation.
[0005] There are patents describing the production of refined red palm oil from crude palm oil. These include U.S. Pat. No. 5,932,261 and Australian Patent Application No. P18770/88. All these patents involved molecular distillation of palm oil at relatively high temperature to remove the fatty acid.
[0006] There are also patents describing the production of carotene concentrate from crude palm oil. These include U.S. Pat. Nos. 5,157,132, 6,072,092, 5,019,668 and U.K Patent No. GB2160874A, GB2218989A and GB1515238. Again all these patents involved pretreatment to the free fatty acid, molecular distillation and followed by the process of post treatment such as using adsorbents.
[0007] This invention relates to the process of producing refined red oils and fats, carotene concentrate, distilled fatty acid, tocotrienol and sterol concentrate, and diglyceride from carotene-containing natural oils and fats and has particular but not exclusive application to the process of producing these products from crude palm oil and its fractionated products by first removing the polar components prior to transesterification and therefore no post-treatment is necessary after distillation.
[0008] This invention has many advantages. It can refine palm oil and palm oil fractionated products without destroying the carotene at a lower vacuum distillation temperature since the polar components including that of odoriferous materials and free fatty acid are removed by alcohol extraction prior to distillation. It also can refine crude palm oil or its fractions into the refined, bleached and deodorized (R.B.D) oils without using degumming agent such as phosphoric acid and deodorized at a significantly lower temperature as most of the free fatty acid and odoriferous materials have been removed.
[0009] This invention also enables transesterification to be carried out without pre-esterification of free fatty acid. It also enables production of carotene concentrate without the need of post-distillation treatment such as using adsorbent. As the polar components had been removed from the oil prior to transesterification, the transesterification reaction was carried out without interference from the unsaponifiable matter and carotene remained in the residue. The processes described in the present invention are simpler and cost-effective as compared to that described in other patents on carotene recovery from palm oil. This invention also enables the recovery of FFA, tocotrienol, tocopherol, sterol and diglyceride and other useful minor components of palm oil.
SUMMARY OF THE INVENTION
[0010] The object of the present invention is to provide a process for the recovery of minor components and refining of vegetable oils and fats from crude vegetable oils and fats without destroying naturally occurring components in the crude vegetable oils and fats.
[0011] Accordingly, there is provided a process for the recovery of minor components and refining of vegetable oils and fats wherein said process is:
[0012] A process for the recovery of minor components and refining of vegetable oils and fats without destroying naturally occurring components, said process comprising the steps of:
[0013] a) removal of polar components from the crude vegetable oils and fats using lower alkyl alcohol or any lower alkyl alcohol-water mixture;
[0014] b) removal of alcohol from the product obtained in step (a) by distillation;
[0015] c) addition of suitable quantity of bleaching earth to the product obtained in step (b) at normal bleaching temperature followed by filtration; and
[0016] d) deodourization of the product obtained in step (c) at a low temperature.
[0017] This invention will be clearly understood and apparent with reference to the detailed description which follows.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The features and details of the invention, either as steps of the invention or as combinations of parts of the invention will now be described. It will be understood that the particular embodiments of the invention are shown by way of illustration and not as limitations of the invention. The principle features of the invention may be employed in various embodiments without departing from the scope of the invention.
[0019] Carotene is non-polar in nature. It is freely soluble in oils and fats. Its solubility in lower alkyl alcohol is low. Natural oils and fats consist mainly of triglyceride, which also has low solubility in lower alkyl alcohol such as methanol and ethanol. Oils and fats are soluble in n-propanol, isopropanol and other lower alkyl alcohol. Addition of water or a mixture of these lower alcohol water mixtures can be used to form two phases in the presence of oils and fats.
[0020] By using polar solvent such as lower alkyl alcohol or lower alkyl alcohol-water mixture, the polar components such as FFA, tocopherol, tocotrienol, sterol, triterpene alcohol, mono-glyceride, di-glyceride, glycolipid and phospholipid can be extracted out from oils and fats, remaining the non-polar components such as carotene, squalene and triglyceride.
[0021] The oil or fat after lower alkyl alcohol extraction can be subjected to washing with water. Residual solvent and/or water can be vacuum distilled at a temperature less than 100° C. without destroying tocopherol and tocotrienol in the methanol extract. The mixture of FFA, tocopherol, tocotrienol, sterol, triterpene alcohol, mono-glyceride and di-glyceride can be used for their recovery.
[0022] A 1-liter crude palm olein of sample was vigorously stirred with methanol at oil to methanol ratios of 1:1, 1:2, 1:3 and 1:4. Table 1 summarizes the results
Weight of Oil: MeOH Carotene, MeOH ratio Extraction stages FFA, % ppm extract, g Initial 4.30 873 1:1 After 1 st extraction 2.56 870 25.3 1:1 After 2 nd extraction 1.67 875 18.5 1:1 After 3 rd extraction 0.98 873 14.8 1:1 After 4 th extraction 0.59 904 10.0 1:1 After 5 th extraction 0.33 889 7.8 1:1 After 6 th extraction 0.21 908 7.1 1:1 After 7 th extraction 0.16 906 6.9 1:1 After 8 th extraction 0.097 898 5.0 Initial 4.20 862 1:2 After 1 st extraction 1.82 864 41.2 1:2 After 2 nd extraction 0.73 875 22.6 1:2 After 3 rd extraction 0.32 902 15.2 1:2 After 4 th extraction 0.17 895 12.0 1:2 After 5 th extraction 0.076 896 8.7 Initial 4.26 857 1:3 After 1 st extraction 1.49 896 53.6 1:3 After 2 nd extraction 0.44 896 32.5 1:3 After 3 rd extraction 0.17 928 19.2 1:3 After 4 th extraction 0.052 937 14.2 Initial 4.22 895 1:4 After 1 st extraction 1.20 918 34.6 1:4 After 2 nd extraction 0.30 940 21.4 1:4 After 3 rd extraction 0.095 940 9.5
[0023] The solvent extraction can be carried out at room temperature (about 32° C.). It was observed that carotene content increases after removal of the polar materials. It is understood that other room temperatures can also be used. There is no advantage to carry out the extraction at the methanol refluxing temperature or other temperature between room temperature and methanol refluxing temperature. At methanol refluxing temperature, more neutral oil (triglyceride) was extracted and the carotene content is lower than that of the starting material indicating some deterioration of carotene under those conditions. Table 2 summarizes the methanol extraction that was carried out at the methanol refluxing temperature.
Weight of Oil: MeOH Carotene, MeOH ratio Extraction stages FFA, % ppm extract, g Initial 4.36 897 1:1 After 1 st extraction 2.64 864 27.0 1:1 After 2 nd extraction 1.66 874 25.5 1:1 After 3 rd extraction 0.96 861 12.6 1:1 After 4 th extraction 0.61 850 10.7 1:1 After 5 th extraction 0.34 827 8.8 1:1 After 6 th extraction 0.20 823 7.5 1:1 After 7 th extraction 0.12 815 7.2 1:1 After 8 th extraction 0.083 802 6.0 Initial 4.23 885 1:2 After 1 st extraction 1.71 898 51.4 1:2 After 2 nd extraction 0.75 871 29.6 1:2 After 3 rd extraction 0.28 894 26.6 1:2 After 4 th extraction 0.12 884 18.3 1:2 After 5 th extraction 0.042 860 8.6 Initial 4.26 892 1:3 After 1 st extraction 1.37 905 73.0 1:3 After 2 nd extraction 0.40 896 44.1 1:3 After 3 rd extraction 0.13 886 31.6 1:3 After 4 th extraction 0.038 880 17.0 Initial 4.18 904 1:4 After 1 st extraction 1.02 900 40.2 1:4 After 2 nd extraction 0.24 907 21.0 1:4 After 3 rd extraction 0.071 864 12.2
[0024] It is understood that other polar solvents such as other lower alkyl alcohols or their water mixture can also be used as solvent to extract components such as free fatty acid, tocopherol, tocotrienol, sterol, triterpene alcohol, mono-glyceride and di-glyceride) from natural oils and fats.
[0025] For lower alkyl alcohol with three or more carbons, such as iso-propanol and n-propanol, addition of water is necessary to form two phases with the oil. Table 3 revealed the effect of water content in isopropanol after the first extraction at room temperature, using the oil to solvent ratio of 1:2. The addition of water at 5% volume to isopropanol is preferred over the higher water content.
Carotene, Extraction solvent FFA, % ppm 5% water in iso-propanol 1.25 896 10% water in iso-propanol 1.42 847 15% water in iso-propanol 1.57 825 20% water in iso-propanol 1.87 835
[0026] The carotene-containing oil after the methanol extraction still contains about 10% methanol. The methanol can be removed by vacuum distillation at a temperature not more than the 65° C. (boiling point of methanol) and the product is refined red palm oil or refined red palm oil fractions such as refined red palm superolein, refined red palm olein and refined red palm stearin. It is understood that anti-oxidants, either natural or synthetic in origin or a combination of both can be added to the red palm oil or its corresponding fractionated products. It is also understood that anti-oxidants, either natural or synthetic in origin or a combination of both can be added to the carotene containing oil before distillation of methanol.
[0027] The subsequent carotene-containing oil can be used directly for esterification. In a preferred embodiment, transesterification with 6 molar volume of methanol in the presence of 0.5% sodium hydroxide as catalyst is used. It is understood that acid-catalyzed esterification or transesterification with other bases such as sodium methoxide or potassium hydroxide or at other suitable amounts of methanol and/or catalyst can also be used. It is also understood that small amount of vegetable oil such as sunflower oil can be added into the carotene-containing oil prior to distillation or in the residue receiving vessels for collecting the carotene concentrate.
[0028] Transesterification process is monitored by high-resolution gas liquid chromatography using Restek Rtx 65TG column with hydrogen as carrier gas. Glycerol-rich layer can be phased separated and drained continuously or when the reaction is toward completion. The reaction is complete when all the triglyceride and diglyceride peaks disappear in the chromatogram.
[0029] The methyl ester layer is centrifuged, with or without addition of small quantity of water to remove small quantity of soap and methanol.
[0030] The methyl ester layer is then vacuum distilled. In a preferred embodiment, the methyl ester is degassed in a thin film evaporator, and vacuum distilled less than 3 Pa and at less than 160° C. in two stages of short path evaporator. It is understood that degassing can also be carried with short path evaporator or other suitable vacuum distillation unit. It is also understood that distillation of methyl ester can be carried out with different number of evaporator stages. Carotene concentrate is collected as residue.
[0031] Methanol in the glycerol layer is distilled at less than 100° C., preferably under vacuum of less than 20,000 Pa. Glycerol is distilled at less than 160° C. under vacuum of 100 Pa. The methanol extract is distilled to remove the methanol. The residual methanol extract is then subjected to degassing and vacuum distillation in short path evaporators. FFA are distilled first, followed by tocotrienols, tocopherol and sterols, and finally diglycerides. In a preferred embodiment, FFA are distilled at about 200° C. under vacuum of 2 Pa, tocotrienol, tocopherol and sterol at less than 220° C. under vacuum of 0.1 Pa, and diglyceride at 271° C. under vacuum of 0.1 Pa.
[0032] After methanol removal, the oil after methanol extraction can be processed into R.B.D. oil by treatment with 0.5% of bleaching earth at 90 to 120° C. under partial vacuum, filter and deodorized at 170 to 240° C. under vacuum of 300 to 500 Pa. It is understood that higher dosage of bleaching earth and/or higher deodorization temperature can also be carried out. The oil refined using this process do not need degumming with phosphoric acid, uses less bleaching earth and deodorized at lower temperature as the process had already removed the fatty acid and odoriferous materials prior to refining.
[0033] After methanol removal, the oil after methanol extraction can be fractionated or further fractionated. Since most of the diglycerides and unsaponifiable matter have been removed prior to the fractionation process, the crystallization behavior is more predictable as compared to the conventional fractionation of palm oil.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0034] The present invention will now be further specifically described by the following examples. All parts and percentages are by weight unless otherwise stated.
EXAMPLE I
[0035] Polar materials were extracted from 1 L of crude palm superolein (with 4.20% FFA, 862 ppm of carotene and 5.7% diglyceride) by adding 2 L of methanol and the mixture was stirred vigorously at room temperature for 5 minutes in a suitable container such as 5-L conical flask. The mixture was transferred into a 5-L separating funnel and allowed to settle into two phases. The lower oil phase was collected and placed into a 5-L conical flask. The methanol layer was transferred into a 1-L evaporation flask and rotary evaporated at water bath temperature of 60° C. under vacuum. The yield of methanol extract was 41.2 g, consisting of 59.6% FFA, 1.2% of tocotrienols, tocopherol and sterols and 20.3% diglycerides.
[0036] The oil layer (the oil with 1.82% FFA and 864 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The second extraction process was repeated as described above. The yield of methanol extract was 22.6 g, consisting of 48.0% FFA, 1.6% tocotrienols, tocopherol and sterols and 24.6% diglycerides.
[0037] The oil layer (the oil with 0.73% FFA and 875 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The third extraction process was repeated as described above. The yield of methanol extract was 15.2 g, consisting of 26.1% FFA, 2.0% tocotrienols, tocopherol and sterols and 36.4% diglycerides.
[0038] The oil layer (the oil with 0.32% FFA and 902 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The fourth extraction process was repeated as described above. The yield of methanol extract was 12.0 g, consisting of 12.3% FFA, 1.6% tocotrienols, tocopherol and sterols and 34.6% diglycerides.
[0039] The oil layer (the oil with 0.17% FFA and 895 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The fifth and final extraction process was repeated as described above. The yield of methanol extract was 8.7 g, consisting of 5.3% FFA, 1.5% tocotrienols, tocopherol and sterols and 35.8% diglycerides.
[0040] The oil layer was rotary evaporated. The red palm superolein contained 0.076% FFA and 896 ppm of carotene and 2.8% diglyceride. The red palm superolein can be further subjected to thin film or short path evaporator to further remove traces of fatty acid and volatile matter.
EXAMPLE II
[0041] Polar materials were extracted from 1 L of crude palm oil (with 2.71% FFA, 577 ppm of carotene and 4.1% diglyceride) by adding 2 L of methanol and the mixture was stirred vigorously at 40° C. for 5 minutes in a suitable container such as 5-L conical flask. The mixture was transferred into a 5-L separating funnel and allowed to settle into two phases. The lower oil phase was collected and placed into a 5-L conical flask. The methanol layer was transferred into a 1-L evaporation flask and rotary evaporated at water bath temperature of 60° C. under vacuum. The yield of methanol extract was 29.3 g, consisting of 53.3% FFA, 1.2% of tocotrienols, tocopherol and sterols and 21.5% diglycerides.
[0042] The oil layer (the oil with 1.09% FFA and 599 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The second extraction process was repeated as described above. The yield of methanol extract was 19.2 g, consisting of 37.5% FFA, 1.6% tocotrienols, tocopherol and sterols and 33.8% diglycerides.
[0043] The oil layer (the oil with 0.53% FFA and 599 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The third extraction process was repeated as described above. The yield of methanol extract was 15.1 g, consisting of 20.9% FFA, 1.4% tocotrienols, tocopherol and sterols and 33.7% diglycerides.
[0044] The oil layer (the oil with 0.20% FFA and 604 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The fourth extraction process was repeated as described above. The yield of methanol extract was 9.4 g, consisting of 9.3% FFA, 1.3% tocotrienols, tocopherol and sterols and 34.8% diglycerides.
[0045] The oil layer (the oil with 0.09% FFA and 609 ppm carotene) which contained about 10% of methanol in it was further added with 2 L of methanol. The fifth and final extraction process was repeated as described above. The yield of methanol extract was 8.5 g, consisting of 5.8% FFA, 1.4% tocotrienols, tocopherol and sterols and 35.9% diglycerides. The oil layer was rotary evaporated. The red palm oil contained 0.043% FFA and 604 ppm of carotene and 1.7% diglyceride. The red palm olein can be further subjected to thin film or short path evaporator to further remove traces of fatty acid and volatile matter.
EXAMPLE III
[0046] Polar materials were extracted from 539 g of crude palm superolein (with 4.17% FFA, 804 ppm of carotene and 4.6% diglyceride) by adding 1 L of isopropanol added with 5% (v/v) of water and the mixture was stirred vigorously at room temperature for 5 minutes in a suitable container such as 5-L conical flask. The mixture was transferred into a 5-L separating funnel and allowed to settle into two phases. The lower oil phase was collected and placed into a 5-L conical flask. The isopropanol-water layer was transferred into a 1-L evaporation flask and rotary evaporated at water bath temperature of 70° C. under vacuum. The yield of isopropanol extract was 74.5 g, consisting of 20.8% FFA, 0.7% tocotrienols, tocopherol and sterols and 16.8% diglycerides.
[0047] The oil layer (the oil with 2.23% FFA and 894 ppm carotene) which contained about 10% of isopropanol/water in it was further added with 1 L of isopropanol added with 5% (v/v) water. The second extraction process was repeated as described above. The yield of isopropanol extract was 78.1 g, consisting of 9.9% FFA, 0.5% tocotrienols, tocopherol and sterols and 11.3% diglycerides.
[0048] The oil layer (the oil with 0.94% FFA and 981 ppm carotene) which contained about 10% of isopropanol in it was further added with 1 L of isopropanol added with 5% (v/v) water. The third extraction process was repeated as described above. The yield of isopropanol extract was 57.6 g, consisting of 4,1% FFA, 0.3% tocotrienols, tocopherol and sterols and 7.2% diglycerides.
[0049] The oil layer (the oil with 0.39% FFA and 1064 ppm carotene) which contained about 10% of isopropanol/water in it was further added with 1 L of isopropanol added with 5% (v/v) water. The fourth extraction process was repeated as described above. The yield of isopropanol extract was 43.2 g, consisting of 1.3% FFA, 0.2% tocotrienols, tocopherol and sterols and 4.7% diglycerides.
[0050] The oil layer (the oil with 0.12% FFA and 1138 ppm carotene) which contained about 10% of isopropanol/water in it was further added with 1 L of isopropanol with 5% (v/v) water. The fifth and final extraction process was repeated as described above. The yield of isopropanol extract was 41.0 g, consisting of 0.5% FFA, 0.1% tocotrienols, tocopherol and sterols and 3.1% diglycerides.
[0051] The oil layer was rotary evaporated. The red palm superolein contained 0.078% FFA, 1250 ppm of carotene and 0.3% diglyceride. The red palm superolein can be further subjected to thin film or short path evaporator to further remove traces of fatty acid and volatile matter.
EXAMPLE IV
[0052] Polar materials were extracted from 492 g of crude palm superolein (with 4.66% FFA, 820 ppm of carotene and 4.7% diglyceride) by adding 1L of 95% ethanol and the mixture was stirred vigorously at room temperature for 5 minutes in a suitable container such as 5-L conical flask. The mixture was transferred into a 5-L separating funnel and allowed to settle into two phases. The lower oil phase was collected and placed into a 5-L conical flask. The ethanol layer was transferred into a 1-L evaporation flask and rotary evaporated at water bath temperature of 70° C. under vacuum. The yield of ethanol extract was 22.9 g, consisting of 68.9% FFA, 1.2% of tocotrienols, tocopherol and sterols and 17.7% diglycerides.
[0053] The oil layer (the oil with 2.50% FFA and 852 ppm carotene) which contained about 10% ethanol in it was further added with 1 L of 95% ethanol. The second extraction process was repeated as described above. The yield of ethanol extract was 12.4 g, consisting of 46.8% FFA, 1.7% tocotrienols, tocopherol and sterols and 25.6% diglycerides.
[0054] The oil layer (the oil with 1.15% FFA and 863 ppm carotene) which contained about 10% of ethanol in it was further added with 1 L of 95% ethanol. The third extraction process was repeated as described above. The yield of ethanol extract was 9.2 g, consisting of 42.3% FFA, 1.7% tocotrienols, tocopherol and sterols and 28.7% diglycerides.
[0055] The oil layer (the oil with 0.65% FFA and 867 ppm carotene) which contained about 10% of ethanol in it was further added with 1 L of 95% ethanol. The fourth extraction process was repeated as described above. The yield of ethanol extract was 7.0 g, consisting of 29.3% FFA, 1.8% tocotrienols, tocopherol and sterols and 31.0% diglycerides.
[0056] The oil layer (the oil with 0.30% FFA and 888 ppm carotene) which contained about 10% of ethanol in it was further added with 1 L of 95% ethanol. The fifth extraction process was repeated as described above. The yield of ethanol extract was 7.3 g, consisting of 19.0% FFA, 1.7% tocotrienols, tocopherol and sterols and 35.8% diglycerides.
[0057] The oil layer (the oil with 0.17% FFA and 862 ppm carotene) which contained about 10% of ethanol in it was further added with 1 L of 95% ethanol. The sixth extraction process was repeated as described above. The yield of ethanol extract was 5.4 g, consisting of 9.9% FFA, 1.4% tocotrienols, tocopherol and sterols and 34.0% diglycerides.
[0058] The oil layer (the oil with 0.12% FFA and 871 ppm carotene) which contained about 10% of ethanol in it was further added with 1 L of 95% ethanol. The seventh and final extraction process was repeated as described above. The yield of ethanol extract was 4.7 g, consisting of 3.8% FFA, 1.5% tocotrienols, tocopherol and sterols and 39.3% diglycerides.
[0059] The oil layer was rotary evaporated. The red palm superolein contained 0.058% FFA, 854 ppm of carotene and 2.0% diglyceride. The red palm superolein can be further subjected to thin film or short path evaporator to further remove traces of fatty acid or volatile matter.
EXAMPLE V
[0060] The oil after final extraction was used for transesterification directly. 3.52 kg of crude palm superolein (carotene content 763 ppm) extracted similar to Example I. After the final extraction, the oil was reacted with 1 L of methanol in the presence of 17.6 g of sodium hydroxide. The reaction took place at the reflux temperature of methanol for 30 minutes. Gas chromatography revealed no trace of triglyceride or diglyceride, indicating that the reaction was completed. The mixture was transferred into a 5-L conical flask and allowed to settle. The lower glycerol layer was drained out. (0.82 kg, containing about 54% methanol). The upper methyl ester layer was washed ten times with one volume of water. The yield of methyl ester was 3.49 kg (99.1% yield). The carotene ester was also 763 ppm.
EXAMPLE VI
[0061] 24 kg of carotene-containing methyl ester (carotene 763 ppm) was fed into KD6 short path evaporator at the rate of 4.8kg per hour, degasser at 100 Pa, 120° C., short path evaporator at 0.8 Pa, 130° C., internal condenser at 12° C. Fatty acid methyl ester was collected as residue (95.8% yield) and carotene concentrate was collected as residue (4.3% yield, carotene content 1.56%).
EXAMPLE VII
[0062] 170.5 g of carotene-containing methyl ester (carotene 1.56%) was fed into KDL5 short path evaporator at the rate of 602 g per hour, short path evaporator at 6 Pa, 155° C., internal condenser at 20° C. Fatty acid methyl ester was collected as residue (81.6% yield) and carotene concentrate was collected as residue (18.4% yield, carotene content 8.6%).
EXAMPLE VIII
[0063] 4.1 kg of methanol extract (after rotary evaporation of methanol) was degassed using a KDL5 short path evaporator at the rate of 973 g per hour with evaporator at 110° C., 11700 Pa, internal condenser at 15° C. and liquid nitrogen cold trap. The yield of volatile in the cold trap was 0.8%, consisting of methanol and water. 3.7% of distillate, consisting of hydrocarbons and fatty acids were also obtained.
[0064] The degassed methanol extract was again fed into KDL5 short path evaporator at the rate of 955 g per hour, short path evaporator at 2 Pa, 195° C., internal condenser at 50° C. FFA was collected as distillate (48.2% yield).
[0065] The residue (51.8% yield) was fed again into the KDL5 short path evaporator at the rate of 955 g per hour, short path evaporator at 0.1 Pa, 220° C., internal condenser at 55° C. Tocopherol, tocotrienol, sterol and diglyceride were collected as distillate (10.5% yield). The composition of the distillate were α-tocopherol 1.26%, α-tocotrienol 0.92%, β-tocotrienol 2.27% and 6-tocotrienol 1.46%, campesterol 1.46%, stigmasterol 1.34% and β-sitosterol 4.80%, diglyceride 61.8%.
[0066] The residue (89.5% yield) consists of diglyceride 61.72% and the balance were triglyceride, was fed again into the KDL5 short path evaporator at the rate of 633 g per hour, short path evaporator at 0.1 Pa, 271° C., internal condenser at 60° C. Diglyceride was collected as distillate (70.5% yield). The composition of the distillate was mainly diglyceride (84.6%) with the balance as triglyceride.
EXAMPLE IX
[0067] 1 kg of refined red superolein obtained similar to Example I was divided into 3 equal portions. 0, 0.3 and 0.5% of bleaching earth (Pure-Flo M85/20) were added into the three portions respectively. The samples were bleached at 105° C. for 15 minutes under nitrogen blanket, filtered through Whatman No. 1 filter paper, and steam distilled at 240° C. for 60 minutes at 500 Pa vacuum. The refined palm superolein were determined for Lovibond colour in 133.35 mm (5¼ inch) cell and the readings were 3.6R, 2.8R and 2.6R respectively.
[0068] It should be understood that the preceding is merely a detailed description of certain preferred embodiments. It therefore should be apparent to those skilled in the art that various modifications and equivalents can be made without departing from the spirit and scope of the invention. It is intended to encompass all such modifications within the scope of the appended claims.
[0069] All references, patents and patent publications that are recited in this application are incorporated in their entirety by reference.
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The invention relates to a process for the recovery of minor components and refining of vegetable oils and fats from crude vegetable oils and fats. The said invention describes the following process:
A process for the recovery of minor components and refining of vegetable oils and fats from crude vegetable oils and fats without destroying naturally occurring components, said process comprising the steps of:
a) removal of polar components from the crude vegetable oils and fats using lower alkyl alcohol or any lower alkyl alcohol-water mixture;
b) removal of alcohol from the product obtained in step (a) by distillation;
c) addition of suitable quantity of bleaching earth to the product obtained in step (b) at normal bleaching temperature followed by filtration; and
d) deodorization of the product obtained in step (c) at a low temperature.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a photoelectric conversion apparatus having a logarithmic compression function.
[0003] 2. Related Background Art
[0004] A conventional photoelectric conversion apparatus for modulating electronic flash light from a camera has used a circuit as shown in FIG. 1. In FIG. 1, a photodiode 1 for receiving electronic flash light is connected to an operational amplifier 2 . An npn bipolar transistor 10 logarithmically compresses a photocurrent I p . An npn bipolar transistor 11 applies a gain to a logarithmically compressed signal to expand it. An integral capacitor 7 integrates an expansion current I. This photoelectric conversion apparatus further comprises a comparator 8 and monitoring voltage follower 9 .
[0005] Letting I p be the photocurrent of the photodiode 1 , an output V 1 from the logarithmic compression circuit is given by
V 1 = V c - kT q ln I p I s ( 1 )
[0006] where k is the Blotzmann constant, T is the temperature, q is the elementary charge, and I s is the reverse saturation current of a bipolar transistor Q 1 .
[0007] The output of the logarithmic compression circuit is connected to the emitter of an expansion transistor Q 2 . Letting V DAC be the base potential of the expansion transistor, the current I flowing through the expansion transistor Q 2 is given by
I = I s exp q ( V DAC - V 1 ) kT = I p exp q kT ( V DAC - V C ) ( 2 )
[0008] The expansion current I gains by the potential difference between V DAC and V c . For example, for V DAC −V c =18 mV, the expansion current is double the photocurrent I p .
[0009] However, the prior art adopts bipolar transistors as elements for logarithmically compressing, expanding, and integrating a current, so the following problems occur.
[0010] a. The bipolar technique is necessary, and is less compatible with a CMOS sensor (sensor manufactured by a CMOS process).
[0011] b. The cost is high in terms of the number of masks and the process.
SUMMARY OF THE INVENTION
[0012] It is the first object of the present invention to provide an apparatus which can be manufactured by a CMOS process.
[0013] It is the second object of the present invention to provide a multifunctional CMOS sensor capable of reducing the cost by integrating a modulated light circuit in another CMOS sensor, e.g., an autofocus sensor on a single chip.
[0014] To achieve the above objects, according to an aspect of the present invention, there is provided a signal processing apparatus comprising:
[0015] a photoelectric conversion element;
[0016] a compression device which logarithmically compresses an output from the photoelectric conversion element;
[0017] an expansion device which exponentially expands an output from the compression device; and
[0018] an integral device which integrates an output from the expansion device,
[0019] wherein a transistor which integrates logarithmic compression in the compression device and a transistor which performs exponential expansion in the expansion device are MOS transistors respectively.
[0020] According to another aspect of the present invention, there is provided a signal processing apparatus comprising:
[0021] a photoelectric conversion element;
[0022] a compression device which logarithmically compresses an output from the photoelectric conversion element; and
[0023] an integral device which integrates an output from the expansion device,
[0024] wherein a transistor which performs logarithmic compression in the compression device and a transistor which performs exponential expansion in the expansion device are MOS transistors respectively.
[0025] According to still another aspect of the present invention, there is provided a signal processing apparatus formed by a CMOS process on a single semiconductor substrate, comprising:
[0026] a modulated light circuit including:
[0027] a compression device which logarithmically compresses an output from a photoelectric conversion element;
[0028] an expansion device which exponentially expands an output from the compression device; and
[0029] an integral device which integrates an output from the expansion device,
[0030] wherein a transistor which performs logarithmic compression in the compression device and a transistor which performs exponential expansion in the expansion device are MOS transistors respectively; and
[0031] a focus adjustment circuit.
[0032] The above and other objects and features of the present invention will be apparent from the following description in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033] [0033]FIG. 1 is a circuit diagram showing the prior art;
[0034] [0034]FIG. 2 is a circuit diagram showing the first embodiment;
[0035] [0035]FIG. 3 is a circuit diagram showing the second diagram;
[0036] [0036]FIG. 4 is a block diagram showing the arrangement of the third embodiment;
[0037] [0037]FIG. 5 is a circuit diagram showing an autofocus circuit;
[0038] [0038]FIG. 6 is a block diagram showing the arrangement of the fourth embodiment; and
[0039] [0039]FIG. 7 is a circuit diagram showing a thermometer circuit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0040] [0040]FIG. 2 is a circuit diagram showing a photoelectric conversion apparatus as the first embodiment of the present invention. In FIG. 2, a photodiode 1 photoelectrically converts electronic flash light. An operational amplifier 2 is formed with a CMOS structure. An nMOS transistor 3 performs logarithmic compression, and operates in a subthreshold region. An nMOS transistor 4 performs expansion operation, and similarly operates in the subthreshold region. An operational amplifier 5 is formed with a CMOS structure, and a pMOS transistor 6 negatively feeds back a current to the operational amplifier 5 . An integral capacitor 7 integrates an expanded current, a comparator 8 compares the potential of an integrated charge with a reference potential V REF , and a voltage follower circuit 9 monitors the potential of the integral capacitor 7 .
[0041] When the gate voltage of the MOS transistor is a threshold voltage or less, a subthreshold current flows therethrough. This current value I D is given by
I D = I DD exp [ q nkT ( V G - V S - V T ) ] ( 3 ) I DD = W μ n C o nL ( nkT q ) 2 exp ( - 1 ) ( 4 )
[0042] where V G is the gate voltage, V D is the gate voltage, V s is the source voltage, V T is the threshold voltage, W is the gate width, L is the gate length, μn is the electron mobility, C o is the gate capacitance, and C D is the capacitance of the depletion layer, of which C o and C D are given by
n = C o + C D C o ( 5 )
[0043] In FIG. 2, when light is incident on the photodiode 1 , a photocurrent I p proportional to the light intensity is generated. An output from the logarithmic compression circuit is given by
V 1 = V C + V T + nkT q ln ( I p I DO ) ( 6 )
[0044] The photocurrent I p is logarithmically converted and output.
[0045] A source potential V 2 of an expansion nMOS transistor Q 4 is negatively fed back by the operational amplifier 5 and a pMOS transistor Q 5 , which operate to cause the potential V 2 to be equal to V DAC . Hence, a current I flowing through the expansion nMOS transistor Q 4 is given by
I = I DO exp [ q nkT ( V 1 - V DAC - V T ) ] ( 7 ) I = I p exp ( V c - V DAC nV T ) ( 8 )
[0046] Accordingly, the expansion current I gains by the potential difference between V DAC and V C .
[0047] The first embodiment can implement a modulated light circuit by only MOS transistors. The number of masks and the process cost can be reduced to attain a low-cost modulated light sensor.
[0048] The circuit of the first embodiment is constituted by nMOS transistors, but the same effects of the present invention can also be obtained with using pMOS transistors depending on the polarity of the photodiode. The photodiode may be formed on the same substrate or may be discretely externally connected.
[0049] [0049]FIG. 3 shows the circuit of a photoelectric conversion apparatus as the second embodiment of the present invention. In the second embodiment, only charge integration is performed without expansion of a logarithmically compressed signal.
[0050] The potential in an integral capacitor can be approximated by
V 2 = V C + nkT q ln ( q nkTC ∫ I p t ) ( 9 )
[0051] The potential V 2 is a logarithmically compressed value of the time integral value of the photocurrent I p .
[0052] The second embodiment enables simple integration which does not include expansion. Particularly when the precision can be poor, the number of circuits can be decreased to further reduce the cost.
[0053] [0053]FIG. 4 shows the arrangement of a multifunctional CMOS sensor as the third embodiment of the present invention. In the third embodiment, a modulated light circuit is integrated on the same substrate as an autofocus sensor.
[0054] [0054]FIG. 4 shows an example of an autofocus circuit block 31 . A modulated light circuit 32 is identical to each of those described in the first and second embodiments. A communication circuit 33 communicates with an external CPU. A control circuit 34 controls each internal circuit of the IC. An analog circuit 35 is formed with an auto gain control circuit, amplifier circuit, intermediate power supply, band gap circuit, or the like. A multiplexer circuit 36 selects and externally outputs each output. An externally-connected photodiode 37 is used as a photodiode for the modulated light circuit.
[0055] In the third embodiment, all the circuits are manufactured by a CMOS process, which can implement a low-cost multifunctional CMOS sensor.
[0056] The autofocus sensor and modulated light sensor, which are provided separately in the prior art, can be integrated into one, thereby reducing the cost and size of the camera.
[0057] [0057]FIG. 5 shows the arrangement of a multifunctional CMOS sensor as the fourth embodiment of the present invention. In the fourth embodiment, a thermometer circuit is further integrated in the arrangement of the third embodiment.
[0058] As can be understood from equations (8) and (9), an output from the modulated light sensor changes depending on the temperature owing to the temperature dependency of the threshold value V T . To modulate light at high precision requires correction by the temperature, so that the temperature must be accurately measured. FIG. 6 shows an example of the thermometer circuit using the temperature characteristics of the diode. In the fourth embodiment, since the thermometer is formed on the same substrate as the modulated light circuit, the temperature can be accurately measured. Since no other chip is required, an increase in cost can be suppressed.
[0059] The fourth embodiment can implement at a low cost a multifunctional CMOS sensor capable of high-precision light modulation and autofocusing.
[0060] As has been described above, a logarithmic compression circuit and expansion/integration circuit can be achieved by a CMOS process, so that a lower-cost photoelectric conversion apparatus and modulated light circuit than the prior art can be attained.
[0061] The modulated light circuit can be integrated in a CMOS sensor such as a CMOS autofocus sensor, and thus a small-size, low-cost camera having a small number of components can be obtained.
[0062] Many widely different embodiments of the present invention may be constructed without departing from the spirit and scope of the present invention. It should be understood that the present invention is not limited to the specific embodiments described in the specification, except as defined in the appended claims.
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There is provided a signal processing apparatus including a photoelectric conversion element, a compression device which logarithmically compresses an output from the photoelectric conversion element, an expansion device which exponentially expands an output from the compression device, and an integral device which integrates an output from the expansion device, wherein a transistor which performs logarithmic compression in the compression device and a transistor which performs exponential expansion in the expansion device are MOS transistors respectively.
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FIELD OF THE INVENTION
This invention relates generally to the field of personal security devices, and, more particularly, to a hand-held device which is a combination keyring and personal security device wherein the personal security device includes a pressurized shriek and offensive odor dispenser. The personal security device also includes a flash-type light and mechanical whistle.
BACKGROUND OF THE INVENTION
Personal security devices have been in existence for some time and are constantly being improved as technology advances. Early security devices typically included a whistle or some type of flashing light which could be actuated by a trigger switch. The alarm means of other earlier security devices include a container having a quantity of air under pressure which emits a piercing sound when released. Personal security devices of this type are intended primarily to scare a would-be attacker away by drawing attention to the scene of the attack.
The development and then successful use of tear gas and other liquid irritants by law enforcement agencies has prompted a change in the design of personal security devices to incorporate such substances. While liquid irritants enable a victim to at least momentarily incapacitate an assailant, a major concern in the design of personal security devices incorporating these substances is the avoidance of accidental discharge. Considering the unpleasant effects of tear gas or other irritants and the fact that purchasers of personal security devices are generally not trained in their use, such devices need to be simple to operate and should provide means to prevent accidental discharge.
Several patents are directed to this general problem as shown, for example, in U.S. Pat. No. 3,794,791 to Thomson. This patent discloses a personal security device which includes a flashlight, a tear gas or liquid spray dispenser and a whistle all contained within a single elongated housing. The flashlight is actuated when a trigger is moved forwardly and the tear gas or liquid dispenser and whistle are actuated when the trigger is pushed downwardly from such forward position. This two-stage motion of the trigger mechanism purportedly minimizes the possibility of accidental release of the tear gas. U.S. Pat. No. 4,223,804 to Morris teaches a personal security device having a flashlight and liquid or tear gas dispenser. Morris includes a pivoted trigger engageable with a pivoted arm to actuate the tear gas dispenser. In the normal closed state, the trigger forms a part of the housing aligned over the exit of the tear gas or liquid dispenser and thus protects the dispensing nozzle from inadvertent actuation. When the trigger is depressed, it moves away from the exit of the tear gas dispenser and at the same time releases the tear gas. Combinations of flashlights and compressed liquid or air-warning devices may also be found in U.S. Pat. Nos. 2,782,748 to Zegarowitz, 4,247,844 to Zapolski and German Pat. No. 1,915,045 to Dallmer.
Although each of the devices disclosed in the patents identified above purport to eliminate the problem of accidental discharge of the compressed gas or liquid they contain, it is believed that a problem of accidental discharge may still exist. In each design, the trigger mechanism which releases the compressed liquid or gas could be exposed and activated by contact with objects in a coat pocket or a woman's purse, for example. In addition, a limitation of such devices is that they would not typically be carried by the user in the hand or coat pocket but would be left in a purse or bag. It is believed that in many purse snatchings, muggings, rapes or assults there may not be sufficient time to reach into a purse, locate a security device and then use it before being attacked.
It has therefore been an object of this invention to provide a personal security device having an offensive odor or other irritant dispensing means actuated by a trigger, which trigger is completely covered in the closed position of a two-section telescoping housing to prevent accidental discharge of the irritant.
It is another object of this invention to provide a personal security device which is simple to operate and would typically be carried in the hand or a coat pocket for ready access at times when an attack would be most likely.
SUMMARY OF THE INVENTION
These and further objects are accomplished with a personal security device according to this invention which is a combined keyring and personal security device. The security device consists of an inner housing which telescopes inwardly and outwardly from an outer housing. A keyring is releasably mounted at one end of the outer housing, and a whistle is preferably formed at the other end of the device in the inner housing. Contained within the inner housing there is an aerosol canister of compressed gas which includes an offensive odorous gas or liquid. When the gas is released from the canister by a trigger normally protected against actuation by the housing, the pressurized gas emits a shrieking offensive noise as well as releases the offensive odor. The pressurized gas may also contain a suspension of paint or stain with which to spray and identify an attacker. The housing also contains a conventional flash cube of the kind commonly used in cameras and a mechanical whistle.
The keyring is so constructed relative to the housing that the keyring may be easily separated from the housing. One common time for an attack is when a person is opening his or her door and has the door key in the lock. Because the keyring is easily separable from the security device housing, the device may be quickly separated if necessary and the door key and attached keyring left in the door, freeing the security device for instant use.
In the non-operating or closed position of the security device, the inner housing is disposed within the outer housing and the device functions primarily as a keyring although the mechanical whistle formed in the inner housing may be used if desired. To operate the pressurized gas container or canister and flash bulb, the inner housing is telescoped outwardly from the outer housing. This uncovers the aperture in the outer housing and exposes an opening in the base of the inner housing in which a finger may be inserted to activate the canister trigger. By depressing the trigger, the canister is moved axially within the inner housing which activates the flash cube creating a temporarily blinding light, as discussed below. In addition, the contents of the canister are released as the trigger is depressed to further discourage a would-be attacker from an assault.
The telescoping structure of this invention provides much more protection from accidental discharge of the pressurized gas than prior art devices. In addition, since the security device has a secondary function of acting as a keyring, it is more likely to be carried or stored in a readily accessible location by the user than prior art designs which are intended for use only as security devices. In addition, the personal security device of this invention incorporates these advantages into a structure which is economical and practical to manufacture.
DESCRIPTION OF THE DRAWINGS
The structure, operation and advantages of this invention will become apparent upon consideration of the following description taken in conjunction with the accompanying drawings wherein;
FIG. 1 is a perspective view of a preferred embodiment of this invention in a closed position;
FIG. 2 is the personal security device of FIG. 1 in an extended or open position;
FIG. 3 is an exploded, perspective view of the personal security device herein showing each of the elements; and
FIG. 4 is a cross-sectional view in full elevation taken generally along line 4--4 of FIG. 2.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, the personal security device of this invention is depicted generally with the reference number 11. Security device 11 comprises a two-piece housing assembly, including an outer housing 13 and an inner housing 15. The outer housing 13 is generally rectangular in shape having an open end 14 to receive the inner housing 15 and a closed end 16 formed with a pair of spaced ears 17 and 18. A T-shaped bar 19 is slid between ears 17, 18 and then twisted 90° to lock it into place within ears 17, 18 as shown in FIGS. 3 and 4. A keyring 21 is connected to bar 19 to receive automobile, dwelling and other keys. Although the keyring 21 is shown as being detachably connected to outer housing 13, it could be fixed thereto in a conventional manner.
The outer housing 13 also includes an opening 23 covered with a clear material such as glass or plastic which is aligned with the flashing portion of the alarm means herein as discussed below. An inner slot 25 and outer slot 26 are formed in the side of outer housing 13 and are adapted to receive the raised portion 27 of a spring lock 29 which is mounted to the side of inner housing 15 as shown in FIG. 3. The slots 25, 26, in cooperation with spring lock 29, define the open and closed positions of security device 11. The device 11 is placed in a closed, locked position by sliding inner housing 15 within outer housing 13 such that the raised portion 27 of the spring lock 29 engages the inner slot 25. This locks the inner housing 15 in place within the outer housing 13. The inner housing 15 is placed in an extended position for operation of the protection means of device 11 by disengaging raised portion 27 from the inner slot 25 and moving inner housing 15 outwardly until the raised portion 27 engages the outer slot 26. This locks the inner housing 15 in an extended position relative to the outer housing 13 as shown in FIG. 2.
In the extended position of inner housing 15, the primary protection means of security device 11 are exposed for operation. The inner housing 15 is generally rectangular in shape having a top surface 28, two side sections 30, 32 and an open bottom forming a hollow interior 33. One end of the inner housing 15 includes a whistle 31 and the other end 34 is closed except for at least three arcuate openings 36 which are concentrically spaced about a central opening 35. A conventional flash cube 37, having a projection 38, is snap fitted to the closed end 34 of inner housing 15 such that the projection 38 engages the central opening 35. The flash cube 37 is formed with at least three conventional electrical contacts 40 which align with the arcuate openings 36 in closed end 34.
A platform 39 is disposed between the end 34 of inner housing 15 and a raised lip section 41 which extends continuously along the interior of top surface 28 and side section 30, 32. The platform 39 is formed with a series of spaced prongs 43 which align with the arcuate openings 33 in the closed end 34 of inner housing 15. The prongs 43 are slightly different in length for purposes to become apparent below. A spring 55 is disposed between the platform 39 and the inner housing end 34 which holds the platform 39 in place within the inner housing interior 33.
The opposite side of the platform 39 is formed with a curved section 45 which receives one end of a canister 47. A second curved section 46 is mounted to inner housing 15 and spaced from curved sections 45 so that together the curved section 45, 46 hold canister 47 in place within the inner housing interior 33. The canister 47 contains a fine suspension or liquid or solvent such as tear gas, dye, or an odorous substance contained in a pressurized gas. When the canister 47 is opened the escaping compressed gas emits a loud shriek or harsh noise. The end of canister 47 opposite platform 39 includes a trigger 49 having an aperture 51, which trigger 49 is operable to release the contents of canister 47 through aperture 51. A generally circular opening 53 is formed in the top surface 28 of inner housing 15 above the aperture 51, to direct the contents of canister 47 toward a particular target.
As mentioned above, the security device of this invention provides numerous improvements over prior art designs. Such improvements may be best illustrated by a discussion of the operation of security device 11. In the closed position, with inner housing 15 disposed within outer housing 13, the security device 11 functions primarily as a keyring. The trigger 49 which releases the contents of canister 47 is completely covered by the outer housing 13 with the device 11 in the closed position. The provision of spring lock 29 which locks the inner housing 15 into outer housing 13 assures that there is little chance of an inadvertent or accidental actuation of trigger 49 by random objects in a woman's purse, for example, or by simply touching the outer surface of device 11 when reaching for another object. The spring lock 29 must first be depressed and the inner housing 15 extended to activate the protection means of device 11, as discussed more fully below. Thus, the trigger mechanism for the container is completely enclosed and protected by the housing of the device.
In addition, it is apparent that for personal security devices to be effective, they must lend themselves to ready availability in case of emergency. Devices which are intended only for personal security and have no other function may be expected to be stored in a purse or a handbag under normal circumstances. The security device 11 differs from such designs in that it also acts as a keyring for automobile and residential keys so that it will normally be in one's hand when walking to the car or residence which are times when attacks seem to commonly occur.
With the security device 11 in hand, it may be quickly made operational by depressing the raised portion 27 of spring lock 29 so that it disengages inner slot 25, and then moving the inner housing 15 outwardly relative to the outer housing 13 until the raised portion 27 is locked into the outer slot 26. With the inner housing 15 in an extended position, an opening 55 is provided into the inner housing interior 33 allowing one to place a finger on the canister trigger 49. See FIG. 4. As the trigger 49 is depressed, two things happen. First, the canister 47 slides axially a short distance within the inner housing 15 along curved sections 45, 46 thereby moving the platform 39 toward the closed end 34 of inner housing 15. The prongs 41 of the platform 39 are moved through arcuate openings 33 and engage the electrical contacts 40 formed in flash cube 37. As mentioned above and shown in FIG. 3, the prongs 41 are of slightly different length so that as they engage the flash cube contacts 40, the four individual bulbs of the flash cube 37 are activated sequentially rather than simultaneously. This has the effect of producing a prolonged flash which is seen by a would-be attacker through the clear opening 23 in the outer housing 13 which opening 23 aligns with flash cube 37 with the inner housing 15 in an extended position. Virtually simultaneously with the activation of flash cube 37, the trigger 49 causes the contents of canister 47 to be released through aperture 51 and then outwardly through the opening 53 in the upper surface 28 of inner housing 15. As shown in FIG. 4, the canister 47 moves a slight axial distance within inner housing 15 before aperture 51 aligns with the inner housing opening 53. If desired, the whistle 31 may also be utilized before or after the trigger 49 is actuated.
It is anticipated that the combination of the flash cube 37, the canister 47 containing a pressurized offensive odorous liquid and shriek, and the whistle 31 provide at least reasonable security for a variety of situations. For example, the whistle 31 could be useful in instances where an assault is anticipated but has not yet occurred or if an attack on another is being witnessed by the user of security device 11. Where a would-be attacker approaches a potential victim at close range, the security device 11 may be used to temporarily impair and disuade the attacker by spraying the attacker with an offensive odorous liquid and actuating a shriek upon actuating trigger 49. In both instances, the secondary use of security devide 11 as a keyring provides a reason for the user to have the device 11 in hand or within easy access under normal circumstances so that enough time is available for the device 11 to be used should the need arise.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
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A personal security device is disclosed which comprises a trigger actuated aerosol canister contained in a two-piece telescoping housing. The canister contains a pressurized offensive odor containing gas such as mercaptoethanol which, when ejected from the canister, emits a loud shrieking noise. Additionally, the gas may, as an additional additive, contain a suspension of fine solid or liquid particles of paint or stain so that the device when actuated, discourages a potential rapist or attacker with offensive odor and noise and also identifies him with a stain. In one preferred embodiment, the telescoping housing also includes a flash-type light which is actuated by the same triggers which actuate the canister. The telescoping housing has a key ring attached at one end and may also have a mechanical whistle at the other end.
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BACKGROUND OF THE INVENTION
It is known, as shown in U.S. Pat. Nos. 3,420,308, 3,893,717, and 4,422,507 to support an inner member in a well from an outer member by means of a resilient expandable and contractible locking support element. However, the annular space between the inner and outer tubular members in a well in which the necessary load bearing surfaces must be provided is limited.
The present device is directed to various improvements in an assembly for connecting inner and outer tubular members together by means of a resilient expandable and contractible locking support element mounted on the inner tubular member which is biased radially outwardly but free to expand and contract radially until it engages a mating profile in the outer tubular member. After engagement a releasable means permits the locking support element to move axially with respect to the inner tubular member to a locked expanded position and support the weight of the inner tubular member on the outer tubular member. By providing two or more coacting load bearing shoulders between the inner tubular member and the locking support element and two or more coacting load bearing shoulders between the outer tubular member and the locking support element a greater area of load bearing surfaces can be provided in a limited annular space.
SUMMARY
The present invention is directed to a load supporting or hanger assembly for releasably connecting inner and outer tubular members, such as casings or other well members, together. The assembly includes a resiliently expandable and contractible locking support element radially and axially movable on the inner tubular member for engagement with the outer tubular member. Two or more load bearing support shoulders and locking surfaces are provided between the inner member and locking support element, positioned for aligning and guiding the locking support element from a contracted non-engaging position to an expanded and locked engaged position, and two or more load bearing support shoulders are provided between the locking support element and the outer tubular member.
Still a further object of the present invention is the provision of a releasable holding means for initially preventing axial movement of the locking support element with respect to the inner member until the locking support element expands and engages the outer member. The releasable means may be positioned above, below or intermediate the ends of the locking support element.
Yet a further object is wherein the locking support element may be an integral member or a plurality of separate members and can be resiliently biased by various types of springs.
Still other and further objects, features and advantages will be apparent from the following description of presently preferred embodiments of the invention, given for the purpose of disclosure and taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view, partly in cross section, of five pipe or casing strings with each inner string supported on the next outer string and with the two inner most strings supported by the assembly of the present invention including an expandable and contractible locking support element with multiple load bearing support shoulders on both the inner and outer surface of the locking support element,
FIGS. 2A, 2B and 2C are fragmentary elevational views, partly in cross section, of the assembly of the present invention showing three positions of the locking support element as the inner tubular member is being run in an outer tubular member with FIG. 2A showing the locking support element of the hanger in the collapsed or contracted position,
FIG. 2B shows the locking support element expanded into engagement with the mating grooved profile in the outer tubular member,
FIG. 2C shows the expanded locking support element in an expanded and locked supporting position,
FIGS. 3A, 3B and 3C are fragmentary elevational views, partly in cross section of two prior art assemblies and an embodiment of the present invention, respectively, shown for comparison purposes, and with each of the locking support elements in its expanded and locked load bearing position,
FIG. 3A is a prior art assembly showing a locking support element with a single load bearing shoulder and locking surface with respect to it and an inner hanger body and a single load bearing support shoulder between it and the outer hanger body,
FIG. 3B is another prior art assembly with one support shoulder between the locking support element and the inner hanger body but with two locking surfaces between the locking support element and the inner pipe hanger body and three support shoulders between the locking support element and the outer hanger body,
FIG. 3C is a fragmentary elevational view, partly in cross section, of one version of the present invention showing multiple load bearing support shoulders and locking surfaces between the locking support element and the inner pipe hanger and multiple support shoulders between the locking support element and the outer pipe hanger,
FIG. 4A is a fragmentary elevational view, partly in cross section, of another embodiment of the present invention, showing the locking support element consisting of separate multiple stacked C-ring elements and in its locked load bearing position,
FIG. 4B is a perspective view of the locking support element shown in FIG. 4A, showing two of the C-ring elements separated from the main cluster of the locking support element,
FIG. 5 is a perspective, partly exploded, elevational view of an alternate locking support element construction consisting of multiple individual elements or dogs attached to a circular C-shaped spring that supports the multiple elements and also provides the outward radial bias for the elements, and
FIG. 6 is a perspective elevational view of still another locking support element design of the present invention where collet fingers provide the outward radial bias for the locking support elements and also includes the release means to permit axial movement of the locking support element with respect to the inner hanger body.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
While the present invention will be described, for purposes of illustration only, as used in a mudline casing hanger assembly, the present well suspension assembly is also useful in other applications in suspending an inner tubular member from an outer tubular member in a well such as subsea wellheads, through bore surface well heads, and downhole well tools such as line hangers and well packers.
Referring now to FIG. 1, a mudline or downhole casing support system is shown having a plurality of concentric casing strings, here shown as five, with each inner string supported on the next outer string. The inner most casing string 180 is supported from the next outer casing string 182 by one embodiment of the well suspension assembly of the present invention. Similarly, casing 182 is likewise supported by an assembly of the present invention from the next outer casing string 184. However, casing string 184 and casing string 186 are each supported on the next outer casing string by outward radially extending shoulders 188 and 189, respectively, resting on inwardly radially extending shoulders 190 and 191, respectively, of the next outer casing string.
One embodiment of the present invention, such as the well suspension assembly between the casings 182 and 184, will be described in which the inner casing 182 is connected to an inner tubular member or inner casing hanger 10 which is adapted to be connected to and released from an outer tubular member or the casing hanger 12 connected to the casing 184.
Referring now to the drawings and particularly FIGS. 2A, 2B and 2C, an inner casing hanger 10 is shown which is desired to be connected to and releasable from an outer casing hanger 12, both of which are tubular members in which the inner casing hanger 10 may be supported, suspending a string of casing in a well, from the outer casing hanger 12. The casing hanger assembly 10 generally includes a plurality of load bearing or support shoulders 15 and annular recesses 14 in its outer peripheral surface for carrying an expandable outwardly biased and resiliently contracting locking support element, generally indicated by the reference numeral 16. The locking support element 16, a resiliently expandable and contractible C-shaped ring circumscribing inner casing hanger 10, is normally biased and urged to an expanded position but will yieldingly collapse into the recesses 14 when the casing hanger 10 is being run inside a restricted diameter such as well casing 184 as shown in FIG. 2A.
When the inner casing hanger 10 is opposite the outer casing hanger 12, as shown in FIG. 2B, the locking support element 16 includes a plurality of outwardly and downwardly facing load bearing or support shoulders 20, 22 and 24, which expand into mating notches or grooves 26, 28, 30 on the inner periphery of the outer casing hanger 12.
Each of the grooves 26, 28 and 30 includes a mating load bearing shoulder. Grooves 26 each include a load bearing shoulder 32, grooves 28 each include a load bearing shoulder 34 and groove 30 includes a load bearing shoulder 36. At least one of the upwardly facing and mating load bearing shoulders should be of an angle such as substantially right angles to the axis of the casing shown by shoulders 32 in grooves 26, in order to provide a substantially positive stop against further downward movement of the locking support element 16 when engaged with mating load bearing shoulders 20 on the locking support element 16.
As shown in FIG. 2B, as the inner hanger 10 is lowered, its weight is transferred to the top of expanded locking support element 16 by means of a release ring 42 that is attached to inner casing hanger 10 by means of one or more shear pins 44. When the load between the release ring 42 and the top of the locking support element 16 exceeds the strength of the shear pins 44, they shear, permitting the inner hanger 10 to move down with respect to both the release ring 42 and the locking support element 16, until upwardly facing load bearing shoulders 38 on the inside diameter of locking support element 16 engage coacting downwardly facing load bearing shoulders 40 on shoulders 15 on the outside diameter of inner hanger 10 as shown in FIG. 2C. These mating shoulders 38 and 40 (as well as the other load bearing support shoulders described) may be at right angles to the axis of the hanger or may be at any angle that provides mating load bearing shoulders as shown in FIGS. 2A, 2B and 2C. The weight of the inner casing 182 attached to inner casing hanger 10 is now supported on load bearing shoulders 40 which in turn bear against the upwardly facing load bearing shoulders 38 on locking support element 16 which in turn is supported by its outwardly and downwardly facing support shoulders 20, 22 and 24 bearing against the upwardly facing load bearing surfaces 32, 34 and 36 at the bottom of circumferential grooves 26, 28 and 30 respectively on the inside of outer hanger body 12. When the elements are in this supported position inwardly facing locking surfaces 46 and 47 of locking support element 16 bear against outwardly facing locking surfaces 52 and 53, respectively of load bearing shoulders 15 on inner casing hanger 10 thereby forcing the locking support means 16 to remain expanded into engagement with the grooves 26, 28 and 30 in outer casing hanger 12. Downwardly facing tapered surfaces 60 are provided on the load bearing shoulders 15 of inner casing hanger 10 for forcing the locking support element 16 to move radially outward in the event the normal outwardly biasing forces acting on locking support element 16 are not sufficiently strong to force the support shoulders 20, 22 and 24 completely into the grooves 26, 28 and 30. These grooves may contain materials such as formation cuttings, mud or cement which must be displaced.
An outwardly and downwardly facing surface 62 is provided on lower most shoulder 24 on locking support element 16 for forcing the entire locking support element 16 to collapse as it is lowered (FIG. 2A) into a reduced diameter section in the outer casing 184 such as might be encountered when running through blow out preventers and well head assemblies connected to the outer casing. This lower shoulder 24 is normally longer than the other support shoulders 20 and 22 to assure that locking support element 16 will not expand into the grooves in casing hanger 12 until all shoulders and grooves are matching. Also by having different length lower support shoulders 24 and mating grooves 30 and by having the shortest length groove in an upper casing hanger 12, a locking support element 16 with a lower support shoulder 24 longer than the length of the key groove 30 in upper outer casing hanger 12 will pass through the upper casing hanger 12 without expanding into its support grooves but will expand only into a casing hanger 12 with mating grooves. If desired, this key effect to permit running an inner casing hanger 10 through an upper casing hanger 12 could also be achieved by staggering the spacing between the other support shoulders so that only matching assemblies will mate together.
To disconnect the inner casing hanger 10 from the outer casing hanger 12, it is only necessary to pull up on the inner hanger body 10 which moves it axially with respect to expanded locking support element 16 until an upper horizontal surface 64 of outwardly protruding shoulder 66 on inner hanger body 10 engages the bottom most surface 68 on locking support element 16 which is the same relationship as shown in FIG. 2B. Continued upward movement of the inner hanger assembly causes the downwardly tapering shoulders 70 on locking support element 16 to force the entire locking support element 16 into a collapsed position as shown in FIG. 2A when these shoulders 70 engage a reduced diameter, thereby permitting upward removal of the inner casing and hanger assembly 10 from the outer casing hanger assembly 12.
Referring now to FIGS. 3A, 3B and 3C, an embodiment of the present invention, shown in FIG. 3C, is compared with prior art structures of FIGS. 3A and 3B. FIG. 3A is generally similar to U.S. Pat. No. 3,420,308; FIG. 3B is generally similar to a commercial embodiment of U.S. Pat. No. 3,893,717. Similar parts in FIGS. 3A, 3B and 3C that correspond to parts in FIGS. 2A, 2B and 2C are similarly numbered with the addition of the suffix "A", "B" and "C", respectively.
The problem in well suspension assemblies is that the annular space between the inner tubular member and the outer tubular member, T in FIG. 3A, and t in FIGS. 3B and 3C, is quite limited and it is therefore difficult to design a suspension assembly having the necessary load bearing shoulders with areas sufficient to carry heavy loads.
The assembly shown in FIG. 3A has one load bearing shoulder 100 and one locking surface 118 on the outer circumference of inner hanger body 10A and one load bearing shoulder 102 at the bottom of groove 104 in the inner circumference of outer casing hanger 12A and a locking support element 16A with one upwardly facing load shoulder 106 and one downwardly facing load bearing shoulder 108. Assuming that the strength of all of the materials is equal, it can be seen that the areas of the load bearing surfaces must also be substantially equal, so that radial distance "B" is approximately equal to radial distance "A". If clearance "C" is equal to 1/3 "A" then it can be seen that the radial distance "D" of recess 110 must be equal to 11/3 "A" in order to permit locking support element 16A to collapse to the outside diameter of 10A and that the total radial distance T from the bottom of recess 110 to the outer diameter of groove 104 must equal 32/3 "A".
Now referring to FIG. 3B, the number of load bearing shoulders between locking support element 16B and outer hanger 12B has been increased to three and there are two locking surfaces 120 and 122 on inner hanger body 10B. Since the materials used in FIGS. 3A, 3B and 3C are the same strength then it is apparent that the radial length of "a" of shoulder 112 need only be approximately 1/3 the length of "A" of shoulder 102 in FIG. 3A. The radial distance "d" of recess 114 must be equal to "a" plus "C", each of which equals 1/3 "A", so that "d" equals 2/3 "A" and "t" equals 21/3 "A". Thus it can be seen that the assembly in FIG. 3B has approximately the same strength as the assembly in FIG. 3A but its total radial distance "t" is only 7/11 that of "T".
FIG. 3C is a modified version of the present invention with the locking support element 16C fully expanded into grooves in outer hanger body 12C and locked into this expanded position by mating locking surfaces 47C and 53C, 119 and 121, and 123 and 125, and with the release ring 42C located in a recess 116 in the lower most key shoulder 24C of locking support element 16C which in this case does not transmit any load to the outer hanger 12C. In the design shown in FIG. 3C, radial distances "a", "C", "B", "d" and "t" are the same as those shown in FIG. 3B while "e" is equal to "a". However, there are six grooves with load bearing shoulders in the outer hanger body 12C and six corresponding load bearing shoulders (including shoulder 54) with locking surfaces on the inner hanger body 10C and the locking support element 16C has internal and external load bearing shoulders that mate with all of these shoulders thereby providing twice the load bearing surface area as shown in FIG. 3B and thus twice the load carrying capacity. Although six sets of load bearing shoulders are shown in FIG. 3C, it is apparent that the number could be varied to provide any desired load carrying capacity. The load carrying capacity of the invention shown in FIG. 3C could also be increased about fifty percent by increasing the radial distance "t" to "T" (FIG. 3A) thereby permitting a corresponding increase in load bearing surface areas.
The present invention therefore provides a well suspension system which increases the load carrying capacity by providing two or more load bearing shoulders and locking surfaces between the inner member 10 and the locking support element 16 and two or more load bearing shoulders between the locking support element 16 and the outer member 12. The load bearing shoulders may be formed by individual circular or continuous single or multiple helical surfaces.
Referring now to FIGS. 4A and 4B, an alternate design for the locking support element 16, shown as 16D, consists of multiple individual nested units which when nested together provide an assembly that functions like one piece locking support element 16. As shown in FIGS. 4A and 4B, the top ring 140 and bottom ring 142 are different from the intermediate rings 144. Each ring contains the load bearing shoulders to mate with the shoulders in the outer hanger body 12 and on the inner hanger body 10. In addition, each upper ring has an inner downwardly protruding tang 146 that mates on the inside of an upwardly protruding tang 148 on each lower ring. The length of these tangs is such that they will remain engaged even if two adjacent rings are separated as far as possible when installed on the inner hanger body 10. This design permits the number of support shoulders on the locking support element 16D to be easily varied. FIG. 4B is an exploded view of the locking support element assembly 16D showing how the individual rings can be stacked and the number of intermediate rings varied to provide any desired number of support shoulders on the locking support element assembly 16D. If desired, the rings can be keyed to permit orientation with respect to each other.
The locking support element 16D in FIG. 4B has slots 150 milled longitudinally on its outside surface. These slots provide a by-pass for fluid flow and also permit varying the spring force of the support element. This same construction can be used in a single piece locking support element 16 as shown in FIG. 1. In addition, longitudinal slots may be milled on the outside of the hanger body 10 as shown by the dotted line 152 in FIGS. 4A and 1 in order to provide an additional by-pass for fluid flow.
Referring now to FIGS. 5 and 6, still other alternate designs for locking support element 16 are shown. The locking support element 16E shown in FIG. 5 consists of individual elements 192, each of which has a groove or slot 194 through which a support spring 196 may be passed. Thus the individual elements 192 are held together on the support spring 196 which also provides a radial outward bias force on each element. This locking support element 16E functions in the same fashion as the element 16 shown in FIGS. 1, 2A, 2B and 2C. The individual elements 192 could also be contained in a cage and have individual spring elements to drive them outward.
FIG. 6 shows still another design for a locking element shown as 16F, where the outward radial bias on the individual locking elements 200 is provided by a collet-spring force acting through spring fingers 206. This collet design may include the same release means as shown in FIGS. 2A, 2B, 2C and 3C, or if desired, the shear pins 44F may be installed directly in the base of the collet design shown in FIG. 6.
The present invention, therefore, is well adapted to carry out the objects and attain the ends and advantages mentioned as well as others inherent therein. While presently preferred embodiments of the invention are given for the purpose of disclosure, numerous changes in the details of construction and arrangement of parts may be made which will readily suggest themselves to those skilled in the art and which are encompassed within the spirit of the invention and the scope of the appended claims.
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An assembly for connecting an inner and an outer tubular member to and from each other in a well. A resiliently expandable and contractible locking support element is carried by and is axially slidable on the inner member. Two or more radially outwardly extending and downwardly facing load bearing support shoulders and peripheral locking surfaces are positioned on the inner member and coact with inwardly facing load bearing shoulders and locking surfaces on the locking support element. Two or more radially outwardly facing load bearing support shoulders on the locking support element coact with mating load bearing support shoulders on the inside of the outer tubular member. A release initially prevents axial movement of the locking support element on the inner member and may be positioned above, below or intermediate the ends of the locking support element. The locking support element may be an integral unit or a plurality of multiple separate units. The locking support element may be biased outwardly by various types of spring devices.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 11/108,420, filed Apr. 18, 2005, now pending, which is a continuation-in-part of U.S. application Ser. No. 10/641,842, filed on Aug. 15, 2003, now abandoned.
1. FIELD OF THE INVENTION
[0002] This invention is related in general to the field of maintenance management systems. In particular, the invention comprises utilizing a set of procedures for addressing maintenance issues.
2. DESCRIPTION OF THE PRIOR ART
[0003] In many industries, such as strip-mining activities, it is common to use heavy equipment to facilitate acquiring, moving, and placing large and heavy items. In the strip-mining industry, heavy equipment may include dozers, drills, haul trucks, loaders, and shovels.
[0004] A dozer is a tracked or wheeled piece of equipment that moves earth with a large blade to clear or level areas. A drill is another tracked piece of equipment utilized to create holes, usually for the placement of explosives, utilizing rotation or percussion. Haul trucks carry waste and ore material between locations at the mine site. Often, these trucks operate in a cycle of loading, hauling, dumping, and returning for the next load. Loaders are rubber-tired pieces of equipment used to move rock and load trucks. Shovels are similar to loaders, however they are usually larger and are tracked vehicles. Shovels are generally either powered by diesel engines or large electric motors.
[0005] Strip-mines and similar industrial locations are stressful environments for these heavy pieces of equipment. Some equipment, such as drills, may experience extreme use resulting in severe stress and strain on both static components (frames, superstructure, and undercarriage) and moving parts (engines, motors, gears, shafts, and hoses). The mine can be a very hostile environment for all equipment. There are severe loading issues for all mine equipment. Other equipment, such as haul trucks, may be utilized in a near-constant cycle (load, haul, dump, return) that results in steady and persistent wear in some components and unpredictable wear in other components. Temperatures in these environments may also be extreme and can vary greatly over a period of hours or months. There are numerous reasons that equipment breaks down. Some of the principal reasons include, use of equipment beyond its design, operator abuse, poor design, manufacturer defects, poor or incorrect maintenance, wear-out, accident, etcetera. Dust and dirt can also accumulate on moving parts and result in excessive and premature wear. Impurities, including water, fuel, dust, and dirt, may be inadvertently introduced into lubricating fluids, resulting in additional wear.
[0006] This wear on both static and dynamic parts often leads to failure of an equipment component. Failure is characterized by the termination of the ability of the equipment to perform its required function to a set standard. Failure results in downtime, which is calculated as the measurement of time the equipment is unavailable to fulfill its performance requirements divided by its intended utilization period.
[0007] Because the cost of heavy equipment is very high, any downtime decreases the return on investment for the associated equipment. The impact of a failure may be higher in hidden costs (i.e., production losses) than the actual repair capital costs of the equipment. An equipment's reliability is measured as a probability that it will perform satisfactory for a given period of time, under specified operating conditions, and its mean time between failure (“MTBF”) is a measure of its uptime (the opposite of downtime) in a given period of time divided by the number of failures in that time period. For these reasons, downtime is carefully tracked and extraordinary measures are employed to prevent or minimize it, as much as possible.
[0008] Maintenance activities are performed to ensure equipment performs its intended function, or to repair equipment which has failed. Preventive maintenance entails servicing equipment before it has failed by replacing, overhauling, or remanufacturing components at fixed intervals, regardless of their condition. Periodic maintenance, such as scheduled replacement of components or lubricants, is performed at regular intervals based on either use or time.
[0009] Predictive maintenance is a strategy based on measuring the condition of equipment in order to assess whether it will fail during some future period, and then taking appropriate action to either prevent the failure or make allowance for the anticipated equipment downtime. One method of implementing predictive maintenance is termed Oil Analysis, whereby lubricants (including hydraulic fluid and engine oil) are sampled and subjected to a variety of tests. These tests are designed to identify contaminants, such as water, fuel, and dust, and measure lubricant viscosity.
[0010] Data from a piece of equipment may be transmitted from the field to the maintenance office or to a service center or off-site original equipment manufacturer (“OEM”) facility for analysis, referred to as remote condition monitoring. Remote condition monitoring may be utilized for failure reporting, or to report the status of the equipment such as time-in-use or lubricant levels. Another method of maintenance planning is to employ trend analysis, whereby predictive maintenance tools analyze the equipment's operating conditions and estimate the potential wear and failure cycle of the equipment. These preventative and predictive maintenance programs are designed to facilitate the implementation of planned maintenance, whereby maintenance tasks are organized to ensure they are executed to incur the least amount of downtime at the lowest possible cost.
[0011] The effectiveness of these maintenance strategies is measured by the mean time between failure (“MTBF”), the equipment uptime divided by the number of failures in a particular period of time. Another measurement tool of maintenance effectiveness is the mean time to repair (“MTTR”). However, the MTTR can be influenced by additional factors, such as failure response time, spare parts availability, training, location, and weather. Once a failure has occurred, failure analysis may be performed to determine the root cause of the failure, develop improvements, and eliminate or reduce the occurrence of future failures.
[0012] Maintenance tasks are generally managed through the use of work orders, documents including information such as description of work, priority of work, job procedure, and parts, material, tools, and equipment necessary to complete either a preventative maintenance or repair task. Work order requests are proposals to open work orders and submitted to persons authorized to generate work orders.
[0013] Once a failure has occurred, or is eminent, a piece of equipment may generate an alarm or an indication that the equipment is being utilized outside its operating profile. Alarms and indications may be generated by on-board sensors, OEM monitoring systems, or trend analysis. Additionally, equipment operators and maintenance technicians may initiate an alarm or notification during an operational pre-inspection or based on equipment performance. If an operator does not have the authority to issue an alarm or notification, the condition may be communicated to a maintenance analyst, who, in turn, generates an alarm or notification.
[0014] The problem with the current state of alarm handling is that alarms are not handled in an organized manner or, in many cases, not at all. Alarms may not be discovered until failure because there is no formal process for handling the alarms, and if there is a process for reviewing this information they are typically ineffective because of the large number of alarm events. After problem identification, there are often several different procedures in place to handle them. The response to an alarm will often include different people who apply their own methods for handling it. This leads to an inconsistency in how the alarm is handled and a corresponding degradation in the efficiency and effectiveness of the alarm handling process. Therefore, it is desirable to provide a consistent, effective, and efficient method for handling alarms, indications, and notifications which can be tracked, measured, and improved upon.
SUMMARY OF THE INVENTION
[0015] This invention is based on utilizing an Interactive Maintenance Management System (“IMMS”) to establish a procedure for handling each alarm, indication, and notification that occurs. For the purposes of this application, an alarm is a notification of a problem or abnormal event. The alarm handling procedure begins at the piece of heavy equipment (“Equipment”), when the alarm is generated, and continues through the workflow timeline of the maintenance department, until the cause of the alarm has been addressed. All alarms which are generated will be handled by this system. Variations in the maintenance management process may be dictated by the severity of the associated alarm.
[0016] Once an alarm has been generated, it is transmitted from the equipment to a central computer over a communications network, such as a site-wide radio network. The central computer analyzes the received alarm and establishes a Priority based on the severity of the alarm. The alarm is routed to the appropriate responsible maintenance personnel, if required.
[0017] Some routed alarms require a response from the appropriate maintenance personnel. If so, the IMMS will wait for an acknowledgment. If no acknowledgment is received, the IMMS will forward the alarm to the next person on a notification list. Once an alarm has been received by a maintenance personnel, he analyzes any supporting information to determine whether the alarm is valid. If the alarm is determined to be invalid, it is either managed or dismissed. Alternatively, this may be done by a computerized routine.
[0018] In one scenario, once an alarm has been determined to be valid, a plan of action (“Plan”) is generated and the sent to a responsible Supervisor, along with the alarm and supporting information. The supervisor then assigns and forwards the Plan to a maintenance technician who then completes the necessary work.
[0019] One aspect of this invention is a method of maintaining and repairing Equipment in an efficient and cost-effective manner utilizing algorithms. Another aspect of the invention is to provide a means for tracking, measuring and improving the maintenance management system. It is still another objective to provide a maintenance system in which generated alarms are not ignored, overlooked, or misplaced. Additionally, the most severe alarms should be addressed first in an expeditious manner.
[0020] Various other purposes and advantages of the invention will become clear from its description in the specification that follows and from the novel features particularly pointed out in the appended claims. Therefore, to the accomplishment of the objectives described above, this invention comprises the features hereinafter illustrated in the drawings, fully described in the detailed description of the preferred embodiments and particularly pointed out in the claims. However, such drawings and description disclose just a few of the various ways in which the invention may be practiced.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 is an illustration of an overview of the Interactive Maintenance Management System (“IMMS”), according to the invention.
[0022] FIG. 2 is a flow chart illustrating an overview of the method of alarm Handling, according to the invention.
[0023] FIG. 2(A) is a flow chart illustrating the first variation of the analysis process step, indicated in FIG. 2 .
[0024] FIG. 2(B) is a flow chart illustrating the second variation of the analysis process step, indicated in FIG. 2 .
[0025] FIG. 2(C) is a flow chart illustrating the third variation of the analysis process step, indicated in FIG. 2 .
[0026] FIG. 2(D) is a flow chart illustrating the fourth variation of the analysis process step, indicated in FIG. 2 .
[0027] FIG. 2(E) is a flow chart illustrating the fifth variation of the analysis process step, indicated in FIG. 2 .
[0028] FIG. 2(F) is a flow chart illustrating the sixth variation of the analysis process step, indicated in FIG. 2 .
[0029] FIG. 2(G) is a flow chart illustrating the seventh variation of the analysis process step, indicated in FIG. 2 .
[0030] FIG. 3(A) is a flow chart illustrating the first variation of the set snooze criteria action, indicated in FIG. 2 .
[0031] FIG. 3(B) is a flow chart illustrating the second variation of the set snooze criteria action, indicated in FIG. 2
[0032] FIG. 3(C) is a flow chart illustrating the third variation of the set snooze criteria action, indicated in FIG. 2
[0033] FIG. 3(D) is a flow chart illustrating the fourth variation of the set snooze criteria action, indicated in FIG. 2
[0034] FIG. 3(E) is a flow chart illustrating the fifth variation of the set snooze criteria action, indicated in FIG. 2
[0035] FIG. 3(F) is a flow chart illustrating the sixth variation of the set snooze criteria action, indicated in FIG. 2
[0036] FIG. 3(G) is a flow chart illustrating the seventh variation of the set snooze criteria action, indicated in FIG. 2
[0037] FIG. 3(H) is a flow chart illustrating the eighth variation of the set snooze criteria action, indicated in FIG. 2
[0038] FIG. 3(I) is a flow chart illustrating the ninth variation of the set snooze criteria action, indicated in FIG. 2
[0039] FIGS. 4(A)-4(F) are flowcharts illustrating a similar but alternate embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0040] As a general overview of the invention, FIG. 1 shows an Interactive Maintenance Management System (“IMMS”) 10 . A piece of heavy equipment 12 is located at a strip mine 14 . A central computer 16 is located at a central office 18 , along with a transceiver 20 of the communications network. Another transceiver 22 is located at each piece of equipment 12 . Additionally, an alarm generator 24 is located on the equipment 12 . Additionally, a maintenance department 26 is provided as a location for servicing and repairing the equipment 12 .
[0041] Numerous technical and administrative positions are necessary to facilitate the operation of the IMMS. The equipment operator can be a key part of the condition monitoring and alarm generation system, in that he can detect equipment deterioration and abnormal conditions which are not detected by on-board sensors. A maintenance dispatcher is the person responsible for ensuring good communication between maintenance and administrative personnel. Equipment problems are communicated to the maintenance dispatcher and he, in turn, passes the information to the shop maintenance supervisor, typically over voice radio. When the shop maintenance supervisor verifies that a repair has been completed, he informs the maintenance dispatcher that the equipment is no longer down. The responsibilities of the maintenance dispatcher may alternatively be handled by an operations dispatcher, or a secondary operations dispatcher, depending on the size of the mining operation and its operational configuration.
[0042] In the preferred embodiment of the invention, alarms (notifications of problems or abnormal events) may be categorized at one of three different priority levels. The highest level of alarm, level 1, is typically associated with equipment which is experiencing downtime. Additionally, this alarm level may indicate a problem which raises safety concerns or may lead to potential equipment damage. Level 2 alarms are those generated when equipment may be functioning, but prolonged use may result in component failure. Nuisance alarms are considered level 3 and represented those which may be disregarded. An example of a level 3 Alarm is one generated by a faulty sensor.
[0043] A key person in the efficient operation of the IMMS is the maintenance assistant. It is his role to analyze alarms, establish an alarm priority and recommend a job action plan. Additionally, the maintenance assistant ensures that appropriate supporting information is passed on with the alarm.
[0044] The shop maintenance supervisor prioritizes and assigns tasks to shop maintenance technicians who, in turn, affect the actual repair of the equipment, once it has been delivered to the maintenance department 26 . Shop maintenance technicians perform scheduled repairs, such as oil changes and engine overhauls, and unplanned maintenance due to equipment failure.
[0045] Some repairs do not require the facilities of the maintenance department 26 . Additionally, in some circumstances, equipment which is experiencing a failure may not be able to be moved to the maintenance department. In those circumstances, a field maintenance technician performs unplanned repairs and service on-site. These field maintenance technicians generally visit the maintenance department only to get parts, material, tools, and equipment necessary to effect repairs on the equipment.
[0046] The field maintenance supervisor prioritizes and assigns the job repairs tasks to the field maintenance technicians. Additionally, they coordinate activities with the maintenance dispatcher and shop maintenance supervisor.
[0047] The maintenance department is supported by a team of administrative and engineering staff. The maintenance analyst researches all available data, including equipment history, trend data, and real-time data, to handle level 2 alarms that are non-critical. These problems generally require a more careful and long-term troubleshooting approach, as these problems are generally not as straightforward and obvious as those generating level 1 alarms. One responsibility of the maintenance analyst is to identify trends or re-occurring problems.
[0048] The maintenance engineer is responsible for developing maintenance programs and supporting the day-to-day engineering needs of the maintenance department. Their job requires extensive use of remote condition monitoring and a review of maintenance history. Maintenance planners are responsible for short and long-term planning of maintenance tasks. It is the responsibility of the planners to schedule planned maintenance. Overseeing the IMMS is the maintenance superintendent. It is his/her job to establish the goals of the maintenance department and evaluate the effectiveness of the IMMS.
[0049] An overview of the operation of the IMMS 10 is illustrated in the flow-chart of FIG. 2 . Initially, an alarm is received 102 at the central office 18 by the central computer 16 . Alarms may be generated in numerous ways. The first is a signal originating from the alarm generator 24 , located on the equipment 12 . An onboard monitoring system generates an alarm based on an abnormal event occurring on the equipment. Alternatively, an embedded device, programmable logic controller (“PLC”), or other computerized system monitors equipment operating and/or production parameters from one or more sensor or monitoring system. Production parameters from mine management systems would include data such as excavation records (i.e., equipment id, operator id, location, activity times, payload, material type, material characteristics, etcetera), dump records (equipment id, operator id, location, activity times, payload, material type, material characteristics, etcetera), equipment status time (i.e., ready time, delay time, standby time, breakdown time, etcetera). When one or more parameters exceeds an established threshold, an alarm is generated.
[0050] Additionally, alarms may be generated utilizing off-board computer based on sensory input from OEM monitoring systems, third-party monitoring systems, sensors, data acquisition systems, supervisory control and data acquisition (SCADA) production data from mine management systems, maintenance history from work order management system, and health information from predictive maintenance database based on fixed or configurable single parameter or multi-parameter thresholds. Various third-party predictive maintenance technology suppliers store their data in a database or other electronic medium. Predictive maintenance technology includes areas such as vibration analysis, fluids analysis (i.e., oil analysis), ultrasonic analysis, ultrasonic testing, infrared analysis, eddy current analysis, mag-particle analysis, etcetera. Another means for generating an Alarm is through the use of remote condition monitoring. Additionally, maintenance or operational personnel may enter the alarm directly into the central computer 16 , based on input from equipment operators, field maintenance technicians, or pre-shift inspections. Yet another method of generating alarms is through the use of enterprise resource planning (“ERP”) systems. ERPs are integrated information system that serve all departments within an enterprise. Evolving out of the manufacturing industry, ERP implies the use of packaged software rather than proprietary software written by or for one customer. ERP modules may be able to interface with an organization's own software with varying degrees of effort, and depending on the software, ERP modules may be alterable via the vendor's proprietary tools as well as proprietary or standard programming languages. An ERP system can include software for manufacturing, order entry, accounts receivable and payable, general ledger, purchasing, warehousing, transportation and human resources.
[0051] Alarms are received as data packets, e.g., a block of data used for transmission in packet-switched systems. Once an alarm has been received 102 , the event that generated the alarm and associated information is stored in database 104 . Data such as time, date, an abnormal event identifier, equipment identifier, location, equipment operator, operational status, action, alarm snapshot, and production information may be stored in a database along with the alarm. Once the alarm has been stored in the database, the alarm is examined to determine whether the alarm should be snoozed in step 106 . Here, snoozing an alarm indicates that the alarm notification is temporarily turned off, pending attention at a later time. Once an alarm is snoozed, a status identifier of the alarm is set to “snoozed.” If the status of the alarm is “snoozed,” the IMMS algorithm is terminated in step 108 , if not the algorithm proceeds to the analysis process in step 110 . Either an analyst or a computational routine validates the alarm and determines an appropriate response to the event. The analysis process 110 can be simple or complex and is examined in more detail below.
[0052] The next step of the process is to snooze alarm in step 112 . In this phase, a logical operator determines if the alarm requires snoozing or should be prevented from entering the analysis process 110 . A logical operator represents a decision process wherein a condition is evaluated for true (yes) and false (no). Traditional boolean logical operators can be used in the evaluation (and, or, xor, not, etc. etera). If snoozing of the alarm is not necessary, the algorithm terminates in step 114 , else notification of the event is suppressed until such time as the snooze criteria are violated. In set snooze criteria 116 , the alarm is snoozed based on such factors as time, occurrence frequency, minimum allowable system or component health factors, predefined events, minimum allowable system or component health factor, and other user definable criteria. A minimum allowable system or component health factor is the minimum level of which a system or component is still considered in good health. The factor may be based on a single parameter or a compilation of multiple parameters from various sources. Sources of parameters include OEM monitoring systems, predictive databases, mine management systems, ERP, SCADA, etcetera. The factor is established either by pre-set configurations or manually be the user.
[0053] The next evaluation is whether snooze criteria has been violated in step 118 . Another logical operator evaluates whether the snooze criteria have been violated and, if so, advances the algorithm to snooze released in step 120 . Violations of the snooze criteria is based on factors such as time, occurrence frequency, minimum allowable system or component health factor, predefine event (i.e., completion of repair, component change-out, etcetera), and user defined criteria. The algorithm then terminates in step 122 .
[0054] FIG. 2(A) illustrates the optional step of display for action or information 130 , followed by the analysis of alarm 132 . The alarm is displayed in a common job queue or sent directly to one or more individuals. Individuals are defined in the distribution list for that event. Analysis 132 is the process of validating the alarm and, either through analysis or the utilization of a computational routine, determining the appropriate action. The algorithm illustrated in FIG. 2(B) builds on these steps by adding the create repair record 134 decision point, the create repair record 136 action, the snooze alarm 138 , and the terminate 140 action. In the create repair record 134 decision point, a logical operator evaluates whether the alarm includes the criteria for creation of a repair record. If so, the algorithm returns to step 112 of FIG. 1 . The criteria for creation of a repair record may be related to consequences of failure (potential repair costs, production losses, or safety implications if the system goes to failure), availability of maintenance personnel, availability of facilities, production requirements, planned maintenance activities, confidence in diagnosis of problem, parts availability, etcetera. The criteria may be evaluated manually or through a computerized routine. A repair record is created in step 136 . A logical operator then evaluates whether the alarm meets the criteria to be snoozed. Is so, the algorithm returns to step 112 of FIG. 1 , else the algorithm terminates 140 .
[0055] A third variation of the analysis process 110 is illustrated in FIG. 2(C) . After the analysis of alarm 132 , the decision point of ignore alarm 142 is encountered, wherein a logical operator evaluates whether the alarm meets the criteria to be ignored. If so, the algorithm advances to the documentation reason 144 action, wherein the user enters the appropriate information to document why the alarm is being ignored, and then terminates 146 . If not, the algorithm advances to the create repair record 134 decision point, the create repair record 136 action, the snooze alarm 138 , and the terminate action of step 140 . FIG. 2(D) is a fourth variation of the analysis process 110 . The send to analyst 148 decision point is evaluated by a logical operator to determine whether the alarm should be sent to an Analyst. If not, the algorithm terminates 150 , else returns to step 130 of FIG. 2(B) . In FIG. 2(E) , the output of the send to analyst 148 decision point is sent to step 130 of FIG. 2(C) .
[0056] In FIG. 2(F) , the algorithm is sent to step 148 of FIG. 2(D) and the send to third party 152 decision point, where a logical operator evaluates whether notification of the alarm should be sent to third party outside maintenance organizations such as OEMs, distributors, solutions centers, or predictive maintenance contractors. Solutions centers is a generic name for an outside organization that provides a mix of consulting or analysis services. In this case, the solution center would receive a packet of data concerning an abnormal event, analyze the data, and provide feedback if required. If so, this branch of the algorithm enters the package and send to third party 156 action step and terminates 158 . The algorithm of FIG. 2(G) is similar to that of FIG. 2(F) with the algorithm being sent to step 148 of FIG. 2(E) .
[0057] The many variations of set snooze criteria 116 are illustrated in FIGS. 3(A)-3(I) . In FIG. 3(A) , the set snooze criteria 116 comprises the select snooze duration based on time 160 action, wherein the alarm is snoozed based on a fixed period of time selected either manually or by a computational device. In FIG. 3(B) , this action is replaced by the select snooze duration based on abnormal event frequency 162 , wherein the alarm is snoozed based on a fixed occurrence rate selected either manually or by a computational device. Alternatively, the set snooze criteria 116 can be replaced by select parameter(s) to monitor and rule(s) to establish severity limits 164 (FIG. 3 (C)), select events to act as triggers 166 (FIG. 3 (D)), or select user defined criteria to act as trigger 168 ( FIG. 3(E) ). In step 164 , the alarm is snoozed based on the component, sub-system, or system health. An example of a component is a fuel pump, a sub-system may be fuel delivery system, and an example of a system is an engine. A system is defined as a group of related components that interact to perform a task. A subsystem can be defined as follows: A unit or device that is part of a larger system. For example, a disk subsystem is a part of the computer system. The bus is a part of the computer. A subsystem usually refers to hardware, but it may be used to describe software. A component can be defined as an element of a larger system. A hardware component can be a device as small as a transistor or as large as a disk drive as long as it is part of a larger system. Thresholds are defined by upper limits, lower limits, and rate of change limitations for individual sensors, multiple sensors, OEM monitoring systems, or other predictive maintenance systems, established either by an analyst or by a computational device.
[0058] The select event to act as trigger 166 step snoozes an alarm based on the occurrence of one or more events. One or more operational, administrative, and maintenance actions can be selected as triggers for the release of the snooze, selected by either an analyst or a computational device. Administrative events are those related to management of people or facilities. For example, the maintenance shop or wash bay becomes available or a specific skilled maintenance technician starts work. Maintenance events are related to the execution of the maintenance process. The select user defined criteria to act as trigger 168 step snoozes an alarm based on user established criteria. This user-established criteria may include production/operation/logistics based factors (i.e., number of gallons of fuel consumed, material moved, operational cycles completed, distance traveled, operating hours, work performed, etc. etera).
[0059] FIG. 3(F) introduces step snooze based on time 170 and add snooze criteria 172 decision points. In step 170 , a logical operator evaluates whether the alarm meets established criteria based on time. If true, the algorithm proceeds to select snooze duration based on time 160 , else it proceeds to step 162 . Step 172 utilizes a logical operator to evaluate whether the alarm requires additional snooze criteria to complement any already selected.
[0060] The algorithm of FIG. 3(G) is similar to that of FIG. 3(F) , but introduces snooze based on frequency 174 , which utilizes a logical operator to evaluate whether the alarm meets the criteria to be snoozed based on occurrence rate. FIG. 3(H) introduces snooze based on severity 178 , wherein a logical operator evaluates whether the alarm meets the criteria to be snoozed based on the health status of a component, sub-system, or system. Finally, FIG. 3(I) introduces Snooze Based on Event 182 , which uses a logical operator to evaluate whether the alarm meets the criteria to be snoozed based on the occurrence of a defined event. An event 182 is an action initiated either by the user or the computer. A similar but alternate embodiment of the invention is illustrated in the flow charts of FIGS. 4(A)-4(F) .
[0061] Others skilled in the art of handling alarms may develop other embodiments of the present invention. The embodiments described herein are but a few of the modes of the invention. Therefore, the terms and expressions which have been employed in the foregoing specification are used therein as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding equivalents of the features shown and described or portions thereof, it being recognized that the scope of the invention is defined and limited only by the claims which follow.
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An Interactive Maintenance Management System (“IMMS”) ( 10 ) is an alarm handling system (FIG. 2 ) for handling alarms ( 102 ) that indicate present or imminent equipment failure. The IMMS ( 10 ) may be utilized in industrial situations, such as strip-mines ( 14 ), to reduce equipment ( 12 ) downtime and reduce or prevent equipment failure. The IMMS ( 10 ) utilizes a flexible response system to track, analyze, and improve performance of the alarm handling system.
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This application claims foreign priority based on Japanese application no. JP2004-227908, filed on Aug. 4, 2004, the contents of which is incorporated herein in its entirety. This priority claim is being made concurrently with the filing of this application.
BACKGROUND
1. Technical Field
The present invention relates to techniques for preventing a discharge lamp from being continuously applied with excessive power more than necessary due to failure in a load when the discharge lamp is turned on from a cold state.
2. Background Art
When a discharge lamp is used for car illumination, light flux must be rapidly increased after the discharge lamp is turned on, so that a transient power control is conducted to supply larger power immediately after the discharge lamp is lit than the power applied for a normal lighting situation, and further, to reduce the applied power over time.
For example, for a metal halide lamp with rated power of 35 W, when lighting is started from a state in which its light emitting tube is cold (so-called “cold start”), the power is controlled such that approximately 60 to 80 W of power is transiently applied to the lamp. Then, the applied power is gradually reduced based on a control value calculated in accordance with the state of the lamp (mainly, a lamp voltage) and an elapsed time from the power-on time to eventually converge the power to the rated value.
Power loss of a lighting circuit increases as larger power is outputted. When large power is applied to a lamp, as with the cold start, a large loss occurs, which increases the amount of generated heat.
In a related art lamp lighting process, even if increased power is temporarily applied in a transient period, the transient period lasts for several seconds, so that the lighting circuit has sufficiently durable specifications with respect to heat-resisting designs of the lighting circuit. Even so, measures should be taken for a possible failure in a load.
For example, in the event of a leak or submergence of a bulb, troubles caused by manufacturing-related faults and aging deterioration (an excessively small amount of mercury, a reduction in inner pressure of an arc tube, and the like), a failure in a lamp, and the like, or when an accident brings about an equivalence to a parallel circuit of a lamp and a low resistor in a lamp connector, a lamp voltage detected by a detector circuit included in a lighting circuit indefinitely remains low, possibly resulting in continuous application of excessive power to the lamp.
In the related art (for example, see Laid-open Japanese Utility Model Registration Application No. 7-8997), a discharge lamp is monitored for power supplied thereto, such that the power supply to the discharge lamp is shut off when the discharge lamp is supplied with power that exceeds the power that should be supplied after the discharge lamp has been lit. Alternatively, when there is a function of determining whether a lamp voltage falls within a normal range in a static light condition determined from information on a detected lamp voltage, the lamp voltage equal to or lower than a predefined reference value is regarded as a failure in lighting, and the power supplied to the discharge lamp can be shut off to protect the circuit.
However, the related art techniques have problems of insufficient measures for protecting circuits from heat generated by a failed load, an increased cost therefor, and the like.
For example, when a high-frequency switching scheme is employed to reduce the size of a lighting apparatus having a fly-back type DC-DC converter circuit, continued application of excessive power, in the event of a failure, can directly lead to thermal runaway, thermal destruction, and the like, due to a reduced thermal capacitance of the overall apparatus.
SUMMARY
It is therefore an object of the invention to take measures to circuit protection by reducing maximum applied power (allowable upper limit value) over time in a discharge lamp lighting apparatus for preventing continued application of excessive transient power to the lighting apparatus in the event of a failure in a load. However, exemplary embodiments of the present invention are not required to achieve this object or any other objects, and may also achieve objects other than this object.
The invention provides a lighting apparatus for a discharge lamp which is configured to reduce power applied to the discharge lamp over time after it is applied with initial maximum power exceeding the rated power in a transient period from the time the discharge lamp is lit from a cold state to the time the discharge lamp reaches a static lighting state. The lighting apparatus includes a maximum power regulator circuit for regulating the applied power in the transient period such that the applied power does not exceed an upper limit power line which is reduced over time after the application of the initial maximum power.
Additionally, the invention provides an apparatus for preventing initial maximum from exceeding a maximum value during a transient period when a discharge lamp is started from a cold start until a stable operation period. The apparatus includes a power conversion circuit that converts a received input into a desired output, a control circuit that generates a power control signal in response to a voltage level signal and a current level signal measured at the desired output, the control circuit comprising a power processing unit that generates at least one first output current based on at least one of the voltage level signal, the current level signal and a first reference voltage, and a maximum power regulator circuit that generates a second output current based on a timing signal and one of a second reference voltage and a power supply signal. The apparatus also includes a starting circuit coupled between the power conversion circuit and the lamp, that outputs power to the lamp during the transient period.
Thus, in the transient power control, the invention can prevent the application of excessive transient power from continuing for a time more than necessary in the event of a failure in a load, thus limiting the amount of generated heat and preventing thermal destruction and the like.
The invention can take sufficient circuit protection measures by preventing thermal detrimental effects resulting from the continuous application of transient power to the discharge lamp.
The lighting apparatus may further comprise a DC-DC converter circuit for converting a received DC input voltage to a desired DC voltage, and a control circuit for controlling the power applied to the discharge lamp. The control circuit may include an error processing unit, and a control signal generator responsive to a signal from the error processing unit for generating a control signal which is sent to the DC-DC converter circuit. The error processing unit receives a reference signal at one input, and an output signal of the maximum power regulator circuit multiplexed on a power control signal, which is calculated based on information on a detected voltage or current associated with the discharge lamp, at the other input. With the foregoing configuration, the lighting apparatus of the invention can reduce the allowable upper limit value for the power applied to the discharge lamp over time without involving a complicated control scheme, a significant increase in cost, and the like.
For example, when the power value regulated by the upper limit power line is reduced over time in accordance with an exponential function or a linear function, the circuit configuration will be effectively simplified.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an exemplary, non-limiting basic configuration.
FIG. 2 illlustrates a change in transient power applied to a lamp over time.
FIG. 3 illustrates an exemplary, non-limiting circuit configuration of a main portion.
FIG. 4 illustrates an exemplary, non-limiting configuration of a maximum power regulator circuit.
FIG. 5 illustrates another exemplary, non-limiting configuration of a maximum power regulator circuit.
DETAILED DESCRIPTION
FIG. 1 illustrates an exemplary, non-limiting basic configuration of a discharge lamp lighting apparatus 1 .
DC voltage from a DC power supply 2 is supplied to a DC-DC converter circuit 4 through a noise filter circuit, not shown, by turning on a lighting switch 3 .
The DC-DC converter circuit 4 receives a DC input voltage from the DC power supply 2 , and converts the received DC input voltage to a desired DC voltage. For example but not by way of limitation, a fly-back type DC-DC converter can be used for the DC-DC converter circuit 4 . In a circuit configuration having a transformer T and a switching element SW on the primary side of the transformer T, the switching element SW is driven by a control signal So from a control circuit 8 , later described.
A DC-AC converter circuit 5 is provided for converting an output voltage of the DC-DC converter circuit 4 to an AC voltage that is supplied to a discharge lamp 6 . For example but not by way of limitation, in a circuit configuration of H-bridge (or full bridge), four semiconductor switches sw 1 -sw 4 are used to make two arms, and driving circuits are included for driving the switching elements on the respective arms independently of each other. The AC voltage is outputted by complementarily controlling on/off the two pairs of switching elements.
A starting circuit 7 is provided for generating a high voltage pulse signal (starting pulse) to start the discharge lamp 6 . This signal is multiplexed on the AC voltage outputted from the DC-AC converter circuit 5 , and the resulting multiplexed signal is applied to the discharge lamp 6 . In this example, the starting circuit 7 is implemented by a trigger transformer, a cylister, a capacitor, or the like.
The control circuit 8 has a power control unit for controlling the power supplied to the discharge lamp 6 . For example but not by way of limitation, in a transient period from lighting of the discharge lamp 6 started in a cold state to the static lighting state, the power control unit controls the power such that the power applied to the discharge lamp 6 is reduced over time after application of initial maximum power exceeding the rated power. As a result, the discharge lamp 6 transitions to a static lighting state.
A detector unit 9 is disposed after the DC-DC converter circuit 4 for acquiring detected signals of a lamp voltage and a lamp current or a voltage and a current corresponding thereto. As the detector unit 9 sends a lamp state detection signal (see a voltage detection signal “VL” and a current detection signal “IL”) to the control circuit 8 , the control circuit 8 sends a control signal (labeled “So”) to the DC-DC converter circuit 4 to control an output voltage of the DC-DC converter circuit 4 . More specifically, the generated control signal So is sent to the switching element SW of the DC-DC converter circuit 4 for driving control. Switching control schemes used in this embodiment include, for example, a PWM (pulse width modulation) scheme, and PFM (pulse frequency modulation) scheme, but are not limited therero.
The control circuit 8 is provided with a maximum power regulator circuit 8 a for regulating the power applied to the discharge lamp 6 in a transient period until the discharge lamp 6 reaches the stable static lighting state so as not to exceed an upper limit power line, which is reduced over time after the initial maximum power has been applied. Thus, the maximum power regulator circuit 8 a regulates the maximum power value (allowed upper limit value) in accordance with the lapse of time, to prevent the continued application of excessive power to the discharge lamp 6 longer than necessary when a load fails.
FIG. 2 illustrates a change in the applied power Pw over time from power-on at a cold start, where the horizontal axis represents the time “t” and the vertical axis represents the applied power “Pw.” “Po” on the vertical axis indicates the initial maximum power supplied to the discharge lamp for a period “0≦t≦To”. While To is assumed to be a fixed value, To can be made longer if a longer unlit time is present before the discharge lamp is lit. “Pc” indicates the rated power.
Curves Ga, Gb, Gc, Gd in the graph represent a difference in changes in the applied power over time due to the differences among respective discharge lamps. Variations are recognized in the change in the applied power from a difference in a lamp state and the like related to individual discharge lamps.
However, the maximum allowable value (or an upper limit value), which decreases in accordance with an elapsed time, can be defined with respect to the change in the power applied to each discharge lamp. Curves M 1 , M 2 in the graph indicate upper limit power lines (or allowable maximum power lines), which should not be exceeded by the varying power in a lighting state of the discharge lamp.
The curve M 1 represented by a dotted line shows an upper limit power line, which exponentially decreases as the time elapses after To. The curve M 2 represented by a one-dot chain line shows an upper limit power line, which levels off after it linearly decreases as the time elapses after To.
Such an upper limit power line can be defined by statistically examining changes in the power applied to discharge lamps. The transient power applied to the lamp is regulated by the maximum power regulator circuit 8 a so as not to exceed the upper limit power line (e.g., M 1 or M 2 ).
In the transient power control at a cold start, complete measures can be taken for heat generation by reducing the allowable upper limit value for the applied power over time, and by regulating the transient power applied to the lamp so as not to exceed the allowable upper limit value indicated by the upper limit power line, even if a discharge lamp is connected to the lighting circuit.
FIG. 3 is a diagram for describing an exemplary configuration of main circuits including the DC-DC converter circuit 4 and control circuit 8 . “Vin” shown in FIG. 3 indicates a DC input voltage to the DC-DC converter circuit 4 , and “Vout” indicates a DC output voltage of the DC-DC converter circuit 4 .
A capacitor 11 is disposed on the primary side of a transformer 10 . A leading end of a primary winding 10 p is coupled to an end of the capacitor 11 , while a trailing end of the primary winding 10 p is connected to a switching element 12 (N-channel FET in this example).
A rectifying diode 13 and a smoothing capacitor 14 are disposed on the secondary side of the transformer 10 . The leading end of a secondary winding 10 s is coupled to a connection point of the primary winding 10 p with the switching element 12 , and the trailing end of the secondary winding 10 s is connected to an anode of the diode 13 . One end of the capacitor 14 is connected to a cathode of the diode 13 , and its terminal voltage is outputted to a subsequent circuit (DC-AC converter circuit) as Vout.
In this exemplary, non-limiting embodiment, the control circuit 8 comprises a power processing unit 15 , an error processing unit 17 , and a control signal generator unit 18 . The power processing unit 15 comprises a first processor 15 a , a second processor 15 b , and an offsetting circuit 15 c.
The first processor 15 a generates an output current (labeled “i 1 ”) in accordance with the voltage detection signal VL acquired, for example but not by way of limitation, from the output of the DC-DC converter circuit 4 , and comprises a function generator circuit that receives VL (the type of function may be arbitrary). The output of the first processor 15 a is sent to the error processing unit 17 through a resistor R 1 .
The second processor 15 b generates an output current (labeled “i 2 ”) in accordance with the current detection signal IL acquired, for example but not by way of limitation, by a lamp current detecting resistor disposed subsequent to the DC-DC converter circuit 4 , and comprises a function generator circuit which receives IL (the type of function may be arbitrary). The output of the second processor 15 b is sent to the error processing unit 17 through a resistor R 2 .
As represented by the symbol of a regulated voltage source in FIG. 3 , the offsetting circuit 15 c sends a reference voltage “Eref” to the error processing unit 17 through a resistor R 3 (see an output current “i 3 ”).
The maximum power regulator circuit 8 a sends its output to the error processing unit 17 through a resistor R 4 (see an output current “i 4 ”) in order to prevent detrimental effects caused by an increased power loss and generated heat when excessive transient power is continuously applied by the output of the power processing unit 15 . However, the maximum power regulator circuit 8 a does not affect the relationship with the output of the power processing unit 15 in normal power control.
Accordingly, the error processing unit 17 is supplied, at one input thereof, with an output signal (i 4 ) of the maximum power regulator circuit 8 a multiplexed on the power control signals (i 1 -i 3 ) that are calculated based on information on the detected voltage or current associated with the discharge lamp. Specifically, the first processing unit 15 a , second processing unit 15 b , offsetting circuit 15 c , and maximum power regulator circuit 8 a are arranged in parallel, and weighted additions are performed in accordance with weighting coefficients determined by the respective resistances of the resistors R 1 -R 4 , to send control signals of the respective components (the sum total of respective output currents) to the error processing unit 17 .
In this exemplary, non-limiting embodiment, the control signal is input to a negative input terminal of an error amplifier that forms part of the error processing unit 17 , and a positive input terminal of the error amplifier is supplied with the reference voltage “Vref” indicated by the symbol of a regulated voltage source (control is conducted to reduce the power supplied to the discharge lamp as the control signal has a higher level).
An output signal of the error processing unit 17 is sent to the control signal generator 18 , which generates the aforementioned control signal So. For example but not by way of limitation, in the PWM scheme, the control signal generator 18 includes a PWM comparator and the like, and an error signal from the error processing unit 17 is supplied to the comparator. The comparator is also supplied with a ramp wave at a frequency, and generates an output signal at a duty ratio that varies in accordance with the result of a comparison between the levels of the inputs. The output signal is supplied to the switching element 12 .
In the PFM scheme, the error processing unit 17 generates an output signal, the frequency of which varies in accordance with an error signal from the error processing unit 17 , and supplies this output signal to the switching element 12 .
FIG. 4 illustrates an exemplary, non-limiting configuration of the maximum power regulator circuit 8 a . An operational amplifier 19 is supplied with the reference voltage “Vref” at its non-inverting input terminal. The operational amplifier 19 has an output terminal connected to an anode of a diode 20 .
The diode 20 has a cathode coupled to an inverting input terminal of the operational amplifier 19 and also coupled to a capacitor 22 through a resistor 21 .
An emitter-grounded NPN transistor 23 is supplied at its base with a signal (hereinafter labeled “STo”) from a circuit (timer circuit or the like), not shown, through a resistor 24 . The transistor 23 has a collector coupled to the output terminal of the operational amplifier 19 . Until a time (the aforementioned “To”) elapses after the power is turned on, the signal STo is set to H (high) level, causing the transistor 23 to transit to the on position to forcedly bring the output signal of the operational amplifier 19 to L (low) level.
After the lapse of the time To, as the signal STo changes to L level to cause the transistor 23 to transit off, a charging operation is started on the capacitor 22 through the resistor 21 .
A subsequent operational amplifier 25 has a non-inverting input terminal coupled to one end of the capacitor 22 . The operational amplifier 25 has an output terminal coupled to an anode of a diode 26 , which has a cathode connected to an inverting input terminal of the operational amplifier 25 , and to the resistor R 4 .
In the foregoing configuration, the transistor 23 remains on while the signal STo is at H level, so that the capacitor 22 is prohibited from being charged. However, as the signal STo goes to L level after the lapse of the time To, the transistor 23 transits to the off position to charge the capacitor 22 . In other words, the voltage on the capacitor 22 exponentially increases over time (since the upper limit power line is in an opposite-phase relationship with the change, the upper limit power line exponentially decreases over time).
A time constant circuit including the resistor 21 and capacitor 22 (CR integrator circuit) may be used to reduce the circuit scale.
FIG. 5 shows an exemplary, non-limiting configuration of the maximum power regulator circuit 8 A. In this exemplary, non-limiting embodiment, the operational amplifier 25 is coupled to a circuit using PNP transistors 27 , 28 , 29 and transistors 30 , 31 which make up a current mirror circuit.
The PNP transistor 27 has its emitter connected to a power supply line 32 at a voltage (Vcc), and its collector grounded through a resistor 33 .
The collector-grounded PNP transistor 28 has its base connected to the collector of the transistor 27 , and its emitter connected to bases of the transistors 27 , 29 .
The PNP transistor 29 has its base connected to the base of the transistor 27 , and its emitter connected to the power supply line 32 . Then, the transistor 29 has its collector grounded through a capacitor 34 .
The emitter-grounded NPN transistor 30 is supplied with the signal STo at its base through a resistor 35 , and the transistor 30 has a collector connected to a base of the transistor 31 through a resistor 36 .
The PNP transistor 31 has its emitter connected to the power supply line 32 , and its collector connected to the bases of the transistors 27 , 29 .
The operational amplifier 25 has its non-inverting input terminal connected (or coupled, as in the present application, “connected” and “coupled” are used interchangeably to refer to either the direct or indirect electrical connection of elements) to a capacitor 34 and to the collector of the transistor 29 . Then, the operational amplifier 25 has an output terminal connected to the anode of the diode 26 which has the cathode connected to an inverting input terminal of the operational amplifier 25 and to the resistor R 4 .
In the foregoing configuration, the transistors 30 , 31 remain on while the signal STo is at H level, so that the capacitor 34 is prohibited from being charged. However, as the signal STo goes to L level after the lapse of the time To, the transistors 30 , 31 turn off, thus charging the capacitor 34 with a corrector current of the transistor 29 . In other words, a charging operation is performed with a constant current, so that the voltage on the capacitor 34 linearly increases over time (since the upper limit power line is in an opposite-phase relationship with the change, the upper limit power line linearly decreases over time).
According to the configuration described above, the upper limit power line is set at a level slightly higher than a time varying maximum power value in the transient power control in consideration of variations in change over time of the applied power due to differences among individual discharge lamps, thus avoiding a power supply exceeding the upper limit power line for any load condition. In this way, sufficient measures can be taken to heating of the lighting apparatus to support a reduction in size of the lighting apparatus.
It will be apparent to those skilled in the art that various modifications and variations can be made to the described preferred embodiments of the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover all modifications and variations of this invention consistent with the scope of the appended claims and their equivalents.
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In a discharge lamp lighting apparatus, in a transient period from the time a discharge lamp is lit in a cold state to the time the discharge lamp reaches a static lighting state, the power applied to the discharge lamp is reduced over time after an initial maximum power that exceeds the rated power. A maximum power regulator circuit is provided to regulate the applied power in the transient period such that the applied power does not exceed an upper limit power line M1 or M2 that is reduced over time after the application of the initial maximum power. In this way, the application of excessive transient power is prevented from continuing longer than necessary in the event of a failure in a load, thus limiting the amount of generated heat and preventing thermal destruction.
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BACKGROUND
[0001] The present invention relates to a system for vaporizing effluent discharged from a compressor.
[0002] Compressors are used to compress gas for use in various processes. Some compressors use oil as a lubricant and a coolant during compressor operation. The oil lubricates and seals the compressor and carries away excess heat during use. A small portion of the oil is typically discharged with the flow of compressed gas that is discharged from the compressor. In compressor systems that compress air, the air is typically drawn from the atmosphere and therefore contains at least some water vapor. During the compression process, some of this water vapor can condense out of the compressed air and be carried out of the air compressor with the small quantity of oil, especially in applications where the compressed service air is cooled prior to discharge.
SUMMARY
[0003] In one construction of an air compressor system, the system includes a compressor having an intake end and a discharge end, the compressor operable to draw in atmospheric air at the intake end and to discharge a flow of compressed air from the discharge end, the flow of compressed air including a flow of entrained water vapor and lubricant. Additionally, the system includes a separator operable to remove a portion of the entrained water vapor and lubricant from the flow of compressed air, with the separator discharging a flow of dry compressed air and a flow of effluent which includes the separated water vapor and lubricant. Further, the system includes an electric heater configured to receive the removed effluent from the separator at an entrance to the electric heater and to vaporize the removed effluent.
[0004] In another construction of an air compressor system, the system includes an oil-flooded compressor having an intake end for the intake of air and a discharge end from which a compressed air stream with entrained effluent exits the compressor. Additionally, the system includes an electric motor coupled to the compressor and operable to drive the compressor. Further, the system includes an after cooler coupled to the discharge end of the compressor and operable to cool the compressed air stream and effluent to condense a portion of the effluent and a moisture separator coupled to a discharge end of the after cooler and configured to remove a portion of the condensed entrained effluent from the compressed air stream. Even further, the system includes an electric pass-through heater configured to receive the removed effluent from the moisture separator, and configured to vaporize the removed effluent.
[0005] Another construction provides a method of operating an electrically-powered air compressor. The method includes powering an oil-flooded compressor with an electric motor, the compressor producing a flow of compressed air and effluent, the effluent including compressed water vapor and oil, cooling the flow of compressed air and effluent to condense a portion of the effluent, and separating the flow of compressed air and effluent into a flow of dry compressed air and a flow of condensed effluent. The method further includes heating the flow of condensed effluent in an electrically-powered heater to vaporize the effluent and discharging the vaporized effluent to the atmosphere.
[0006] Other aspects of the invention will become apparent by consideration of the detailed description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a schematic illustration of a condensate vaporization system.
[0008] FIG. 2 is a flow chart illustrating a method of operating the condensate vaporization system of FIG. 1 .
[0009] Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having” and variations herein are meant to encompass the items listed thereafter and equivalents thereof as well as additional items.
DETAILED DESCRIPTION
[0010] FIG. 1 schematically illustrates a compressor system 5 , including a condensate vaporization system 10 and a particulate removal system 15 , for producing a compressed gas stream and for removal of entrained effluent from the compressed gas stream to produce a stream of clean compressed gas that contains minimal moisture and lubricant. Effluent is generally defined as a mixture of water and oil (i.e., primarily water with a small amount of entrained lubricant), and is essentially the liquid medium that resides downstream of an aftercooler in a compressor system. Before proceeding further, it should be noted that the present system can be used to compress many different gases. However, for clarity, the system will be described herein as it applies to an air compressor system. The compressor system 5 includes a compressor 14 , a motor 18 , an aftercooler heat exchanger 22 , a controller 50 , a compressor temperature sensor 58 , a compressor pressure sensor 62 , an ambient air temperature sensor 66 , and an ambient air relative humidity sensor 68 . The particulate removal system 15 of the compressor system 5 includes a separator 26 and first and second filters 30 , 34 . The condensate vaporization system 10 of the compressor system 5 includes an electric heater 38 , and a heater temperature sensor 54 .
[0011] In the illustrated construction, the compressor 14 is an oil flooded screw compressor. The compressor 14 includes a compressor air inlet 70 open to the atmosphere. The compressor 14 further includes a compressor discharge end 78 . The motor 18 couples to the compressor 14 and is operable to drive the compressor 14 . In the illustrated construction, the motor 18 is an electric motor that electrically couples to a power source (not shown). In other constructions the motor 18 can be another prime mover operable to drive the compressor 14 .
[0012] The aftercooler 22 includes an aftercooler inlet 82 that receives a flow of compressed air from the compressor 14 and an aftercooler outlet 86 where the cooled compressed air is discharged. Additionally, the aftercooler 22 fluidly couples to a cooling source with a cooling fluid (e.g., air, coolant, water) that passes through the aftercooler 22 such that the cooling fluid thermally communicates with compressed air that is within the aftercooler 22 between the aftercooler inlet 82 and the aftercooler outlet 86 .
[0013] The aftercooler 22 discharges the cooled flow of compressed air to the separator 26 (e.g., a moisture separator or water separator). The separator 26 includes a separator inlet 90 , a first separator outlet 94 , and a second separator outlet 98 . The second separator outlet 98 couples to a discharge line 110 .
[0014] Downstream of the aftercooler 22 are the first and second filters 30 , 34 . In the illustrated construction, the first and second filters 30 , 34 are coalescing filters. In other constructions, other types of filters can be used to remove excess liquid from the compressed air. Further, in some constructions more than two filters, or fewer filters can be utilized, or no filters may be utilized.
[0015] Each filter 30 , 34 has a filter inlet, an air outlet, and a condensed effluent outlet. The air outlet of the first filter 30 fluidly couples to the second filter 34 . The air outlet of the second filter 34 is connected to other downstream components that ultimately lead to a point of use. For example, a storage tank or large manifold could be connected to the filter 34 to hold a quantity of compressed air for use as may be required. The condensed effluent outlets of the first and second filters 30 , 34 couple to the discharge line 110 .
[0016] The discharge line 110 includes an orifice 114 which is arranged such that all condensed effluent flowing through the discharge line 110 passes through the orifice 114 . The discharge line 110 fluidly couples the separator 26 and the first and second filters 30 , 34 to the electric heater 38 . The electric heater 38 (e.g., an electric pass-through heater or tankless water heater) includes a heater inlet 126 and a heater outlet 130 . Further, the electric heater 38 electrically couples to the power source (not shown). In the illustrated construction, the heater outlet 130 is open to the atmosphere.
[0017] The controller 50 is preferably a microprocessor-based controller that electrically couples to the compressor 14 and the electric heater 38 to control various operational parameters of both the compressor 14 and the electric heater 38 . Further, the controller 50 electrically couples to the compressor temperature sensor 58 , the compressor pressure sensor 62 , the ambient air temperature sensor 66 , the ambient air relative humidity sensor 68 , and the heater temperature sensor 54 .
[0018] The compressor temperature sensor 58 and compressor pressure sensor 62 couple to the compressor 14 . For example, the sensors 58 , 62 may be disposed in a compressor discharge line or downstream of the compressor 14 to directly measure the temperature and pressure of the compressed air exiting the compressor 14 . The sensors 58 , 62 generate temperature and pressure signals indicative of the measured temperature and pressure of the compressed air and transmit the temperature and pressure signals to the controller 50 . The ambient air temperature sensor 66 and the ambient air relative humidity sensor 68 couple to the compressor 14 near the compressor air inlet 70 . The sensors 66 , 68 generate temperature and relative humidity signals indicative of the measured temperature and relative humidity of the ambient air entering the compressor 14 and transmit the temperature and relative humidity signals to the controller 50 . Based on the signals from the sensors 58 , 62 , 66 , 68 , the controller is configured to utilize a predictive algorithm to “ready” (e.g., preheat or otherwise adjust the temperature and/or energy flow in anticipation of a change in conditions) the electric heater 38 and prepare the electric heater 38 to vaporize effluent. The heater temperature sensor 54 couples to the electric heater 38 . For example, the heater temperature sensor 54 may be disposed inside a discharge line of the electric heater 38 to directly measure the temperature of the vaporized effluent exiting the electric heater 38 . The heater temperature sensor 54 generates a temperature signal indicative of a measured temperature of the vaporized effluent and transmits the temperature signal to the controller 50 .
[0019] The signals from the compressor pressure sensor 62 , the compressor temperature sensor 58 , the ambient air temperature sensor 66 , the ambient air relative humidity sensor 68 , and the heater temperature sensor 54 are used in determining how the compressor 14 and/or electric heater 38 are operated. In other constructions, the operation of additional components can be determined by the signals from the sensors 54 , 58 , 62 , 66 , 68 (e.g., the motor 18 or the power source). Further, in alternative constructions, additional sensors 54 , 58 , 62 , 66 , 68 may be utilized in similar positions as those described above, or in additional positions in and around the compressor 14 and the electric heater 38 . In preferred constructions, the sensors 54 , 58 , 62 , 66 , and 68 transmit analog or digital signals to the controller 50 .
[0020] The flowchart of FIG. 2 illustrates operation of the condensate vaporization system 10 starting with block 200 . The power source provides power to the motor 18 , which drives the compressor 14 . The compressor 14 intakes air through the compressor air inlet 70 from the surrounding atmosphere. Further, in the illustrated embodiment, a pump (not shown) provides oil to the compressor 14 . The compressor 14 compresses the air, and directs the air outward through the compressor discharge end 78 . During the compression process, oil is used to seal the compressor 14 and to cool the compressor 14 . As air is discharged, a small portion of oil is entrained with the air. In addition, the compression process can cause some moisture to condense within the air stream. The compressed air directed outward from the compressor 14 includes this water vapor, oil vapor, and oil additive vapors in the form of an entrained effluent.
[0021] The aftercooler 22 receives the compressed air at the aftercooler inlet 82 and cools the air (see block 204 ) by allowing thermal communication between the compressed air and the cooling fluid. Cooling the compressed air condenses a first portion of the entrained effluent. The aftercooler 22 then directs the compressed air and the first portion of condensed effluent through the aftercooler outlet 86 to the separator inlet 90 .
[0022] The separator 26 separates the first portion of the condensed effluent from the compressed air and directs the first portion through the second separator outlet 98 to the discharge line 110 (see block 208 ). The separator 26 then directs the compressed air through the first separator outlet 94 to the first and second filters 30 , 34 .
[0023] In the illustrated construction, the first filter 30 separates a second portion of condensed effluent from the compressed air. The second portion of condensed effluent passes to the discharge line 110 . The compressed air passes to the second filter 34 . The second filter 34 separates a third portion of condensed effluent from the compressed air. The third portion of condensed effluent passes to the discharge line 110 . The compressed air exits out of the particulate removal system 15 in the form of dry compressed air. In preferred constructions, the air is heated after exiting the filters to assure that the air temperature is well above the air's dew point temperature. Generally, dry compressed air has a dew point at least 20 degrees below the discharge temperature of the air. The first, second, and third portions of condensed effluent pass through the discharge line 110 and through the orifice 114 . The condensed effluent (e.g., the first, second, and third portions) then pass through the heater inlet 126 to the electric heater 38 . The orifice 114 , in some constructions, is selected specifically to control the amount of compressed air lost and to allow the condensate to escape at the rate accumulated. In other embodiments, a check valve or pressure reducing valve may be used to decrease the pressure of the condensed effluent. The power source powers the electric heater 38 to heat the condensed effluent in the electric heater 38 . The electric heater 38 heats the condensed effluent to a temperature at which water, as well as some additional effluent constituents, will vaporize. A temperature control can also be employed to limit the temperature and to control vaporizing of the effluent constituents as desired (see block 212 ). In other constructions, additional electric heaters may be included to provide additional heating to the condensed effluent. Further, the additional heaters may be arranged with the electric heater 38 , downstream of the discharge line 110 , either in series or in parallel. The vaporized effluent then passes through the heater outlet 130 to the atmosphere (see block 216 ).
[0024] Referring again to FIG. 1 , the controller 50 controls the amount of electricity provided to the electric heater 38 by the power source. The compressor temperature sensor 58 detects the temperature of the compressor 14 and sends compressor temperature measurements to the controller 50 . The compressor pressure sensor 62 detects the pressure in the compressor 14 and sends compressor pressure measurements to the controller 50 . The ambient air temperature sensor 66 detects the temperature of the ambient air entering the compressor 14 and sends the ambient air temperature measurements to the controller 50 . The ambient air relative humidity sensor 68 detects the relative humidity of the ambient air entering the compressor 14 and sends the ambient air relative humidity measurements to the controller 50 . The heater temperature sensor 54 detects the temperature of the electric heater 38 and sends heater temperature measurements to the controller 50 .
[0025] The controller 50 receives the compressor temperature measurements, the compressor pressure measurements, the ambient air temperature measurements, the ambient air relative humidity measurements, and the heater temperature measurements. Based on one or more of these measurements, the controller 50 determines and controls the amount of electricity that is provided to the electric heater 38 to ensure that the condensed effluent within the electric heater 38 is fully vaporized. Further, based on the signals from the sensors 58 , 62 , 66 , 68 , the controller 50 may utilize a predictive algorithm to “ready” (e.g., preheat or otherwise adjust the temperature and/or energy flow in anticipation of a change in conditions) the electric heater 38 and prepare the electric heater 38 to fully vaporize the condensed effluent for a given demand (i.e., kilowatt input or heat load). Further, the ambient temperature and relative humidity measurements allow the controller 50 to determine the total amount of water coming into the system to better estimate the amount of heat required to fully vaporize the effluent.
[0026] Various features and advantages of the invention are set forth in the following claims.
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An air compressor system includes a compressor having an intake end and a discharge end, the compressor operable to draw in atmospheric air at the intake end and to discharge a flow of compressed air from the discharge end, the flow of compressed air including a flow of entrained water vapor and lubricant. The system further includes a separator operable to remove a portion of the entrained water vapor and lubricant from the flow of compressed air, the separator discharging a flow of dry compressed air and a flow of effluent which includes the separated water vapor and lubricant. Further, the system includes an electric heater configured to receive the removed effluent from the separator at an entrance to the electric heater and to vaporize the removed effluent.
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BACKGROUND OF THE INVENTION
Hydrogen is a vital raw material or reducing agent for the fertilizer, substitute natural gas production, oil refining, chemical, and food and materials processing industries. Currently hydrogen is produced by reforming of natural gas, petroleum or coal, by partial oxidation of hydrocarbons or by electrolysis of water. The first two methods consume natural resources and the last method is capital intensive, costly and inefficient. Direct thermal decomposition of water requires impractically high temperatures for significant yields of hydrogen and oxygen and engenders the problem of preventing the oxygen and hydrogen from recombining when the product gases are cooled down for storage and/or distribution.
It has long been known that it is theoretically possible to produce oxygen and hydrogen from water by introducing heat and water into a closed thermochemical cycle involving intermediate chemical compounds. Calculations for such cycles suggest that they can be more efficient in the consumption of process heat than is water electrolysis.
The Euratom Mark I process is one such closed thermochemical cycle which uses intermediate calcium, bromine and mercury compounds and process heat at temperatures exceeding 700° C. As is indicated in U.S. Pat. No. 3,821,358, mercury is highly volatile and its loss to the surrounding atmosphere would pose a significant ecological and health hazard.
Other cycles involve dilute water solutions and serious problems of energy consumption to effect the product separations required. Very high efficiencies during such product separations are required if overall process efficiencies are to be competitive with electrolysis. In such cycles much heat is consumed heating and evaporating solvent water.
It is an object of this invention to provide a closed cycle thermochemical process which presents fewer product separation problems, involves no heating or evaporative separations of dilute solutions of salts, has cycle thermal efficiencies higher than that of electrolysis, and is adaptable to process heat which can be provided by any source of high temperature heat such as nuclear fusion or fission reactors or solar energy collection and concentration systems.
SUMMARY OF THE INVENTION
The closed cycle thermochemical process embodying the present invention requires the use of a halogen which can be either chlorine or bromine. When chlorine is used the oxygen and hydrogen chloride producing sub-cycle entails two chemical reactions. When bromine is the halogen used the oxygen and hydrogen bromide producing sub-cycle entails three chemical reactions.
When the halogen is chlorine, the process includes the steps of (a) decomposing a metal trichloride, selected from the group consisting of samarium, europium and ytterbium trichlorides, at a temperature sufficient to produce a metal dichloride and chlorine gas; (b) removing the chlorine formed during said decomposition; (c) bringing the chlorine into contact with a metal oxide at a temperature sufficient to produce a metal chloride and oxygen, the metal oxide being selected from a group consisting of magnesium, nickel, cobalt and yttrium oxides; (d) removing and collecting the oxygen produced during the chlorine-metal oxide reaction; (e) hydrolyzing the metal chloride formed during the reaction of step (c) at a temperature sufficient to produce the metal oxide used during step (c) and hydrogen chloride gas; (f) reacting the hydrogen chloride produced by the reaction step (e) with the metal dichloride produced by step (a) at a temperature sufficient to produce a metal trichloride and hydrogen gas; (g) removing and collecting said hydrogen gas; and (h) decomposing said trichloride as recited in step (a), and repeating the cycle.
When the halogen is bromine, the process includes the steps of (a) decomposing a metal tribromide, selected from the group consisting of vanadium and chromium tribromides, at a temperature sufficient to produce a metal dibromide and bromine gas; (b) removing the bromine formed during said decomposition; (c) bringing the bromine in contact with a metal oxide at a temperature sufficient to form a higher valence metal oxide and a metal bromide, the metal oxide being selected from a group consisting of manganese and cobalt oxides; (d) removing the metal oxide and metal bromide products of the reaction of step (c) and separating them; (e) removing said metal oxide; (f) decomposing the metal oxide at a temperature sufficient to produce a lower valence metal oxide and oxygen gas; (g) removing and storing said oxygen; (h) removing the metal bromide separated in step (d); (i) hydrolyzing the removed metal bromide at a temperature sufficient to produce a metal oxide and hydrogen bromide; (j) collecting the metal oxides produced by steps (f) and (i) and reacting them with bromine as recited in step (c); (k) reacting the hydrogen bromide produced by the reaction of step (i) with the metal dibromide produced in step (a) at a temperature sufficient to produce a metal tribromide and hydrogen gas; (l) removing and collecting said hydrogen gas; and (m) decomposing said tribromide as recited in step (a) and repeating the cycle.
Other objects of this invention will appear in the following description and appended claims, reference being had to the accompanying drawings forming a part of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow diagram of the process embodying the present invention when chlorine is the halogen employed; and
FIG. 2 is a flow diagram of the process embodying the present invention when bromine is the halogen employed.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Chlorine Cycles
Referring to FIG. 1, beginning with reactor 10, chlorine gas is produced by thermally decomposing a trichloride compound according to the endothermic reaction (s means solid phase, g means gas and l means liquid):
2RCl.sub.3 (1)→2RCl.sub.2 (1)+ Cl.sub.2 (g)
where R can be any one of the lanthanide metals samarium, europium or ytterbium. The reaction temperatures depend on the metal R used and are for equilibrium constants, K, equal to 1 and 100; approximately:
______________________________________ K = 1 K = 100______________________________________samarium 1700° C. 2850° C.europium 850° C. 1300° C.ytterbium 1050° C. 1700° C.______________________________________
Lower temperatures at equal yields are possible if the reaction proceeds in a partial vacuum. Chlorine gas from reactor 10 is conducted to reactor 12 where it is reacted with a metal oxide to produce a metal chloride and oxygen according to the exothermic reaction: ##EQU1## where the metal Q can be any one of the metals magnesium, nickel, cobalt or yttrium and the approximate reaction temperature and formula subscript x depends upon which metal is employed as follows for equilibrium constants, K, equal to 1 and 100:
______________________________________ K = 1 K = 100______________________________________magnesium x = 0 400° C. 150° C.nickel x = 0 800° C. 400° C.cobalt x = 0 900° C. 450° C.yttrium x = 2 250° C. 50° C.______________________________________
The oxygen 13 produced in reactor 12 is drawn off and stored for use. The metal chloride produced in reactor 12 is transported to reactor 14 where water 16 is introduced to produe the metal oxide for the reaction of reactor 12 and hydrogen chloride gas by the endothermic hydrolysis reaction: ##EQU2## where the approximate reaction temperatures and formula subscript x depend on the metal Q used as follows for equilibrium constants, K, equal to 1 and 100:
______________________________________ K = 1 K = 100______________________________________magnesium x = 0 500° C. 900° C.nickel x = 0 700° C. 1150° C.cobalt x = 0 750° C. 1200° C.yttrium x = 2 450° C. 750° C.______________________________________
The metal oxide produced in reactor 14 is transported to reactor 12 previously described. The hydrogen chloride gas is conducted to reactor 18 where it is reacted with the metal dichloride produced in reactor 10 to produce a metal trichloride and hydrogen gas 19 by means of the exothermic reaction:
2HCl(g)+ 2RCl.sub.2 (s)→2RCl.sub.3 (s)+ H.sub.2 (g)
where the metal R can be samarium, europium or ytterbium. The reaction temperatures depend upon the metal R and are for equilibrium constants, K, equal to 1 and 100; approximately:
______________________________________ K = 1 K = 100______________________________________samarium 900° C. 700° C.europium 50° C. less than 25° C.ytterbium 400° C. 300° C.______________________________________
The reaction temperatures can be raised in order to increase reaction rates, at the same yields, when the hydrogen chloride reactant gas pressure is increased.
The trichloride product compound produced in reactor 18 is transported to reactor 10 previously described. The hydrogen gas 19 is drawn off for storage or use.
Process heat 20 is introduced to reactor 10 and thence to reactor 14 to supply the endothermic reaction heat required by these reactions. Otherwise waste heat contained within the exhaust heat 22 can be used to evaporate the feedstock water 16 and for power production.
Thermal efficiencies for the twelve separate cycle compositions which are possible range from 0.622 to 0.817. Thermal efficiency is defined as the ratio of the heat of dissociation of liquid water (68.32 kcal per mole) to the externally supplied process heat required for the cycle. Exothermic reaction heat is assumed to be used internally when reaction temperatures permit it. The maximum efficiencies calculated in this manner for the various combinations of metal Q and metal R are given in the following table:
______________________________________ Maximum cycle thermalMetal Q Metal R efficiency______________________________________Mg Sm .700Mg Eu .815Mg Yb .684Ni Sm .700Ni Eu .817Ni Yb .622Co Sm .700Co Eu .734Co Yb .622Y Sm .700Y Eu .817Y Yb .698______________________________________
Bromine Cycles
Referring to FIG. 2, beginning with reactor 24, bromine gas is produced by thermally decomposing a tribromide compound according to the endothermic reaction:
2RBr.sub.3 (s)→2RBr.sub.2 (s)+ Br.sub.2 (g)
where the metal R can be vanadium or chromium and the approximate temperatures of the reaction depend upon the metal R as follows for equilibrium constants, K, equal to 1 and 100:
______________________________________ K = 1 K = 100______________________________________vanadium 650° C. 900° C.chromium 750° C. 1000° C.______________________________________
Lower temperatures with equal yield are possible if the reaction takes place in a partial vacuum. Bromine gas from reactor 24 is conducted to reactor 26B where it is reacted with a metal oxide to produce a higher valence metal oxide and a metal bromide according to the exothermic reaction:
(x+1)QO (s)+ Br.sub.2 (g)→Q.sub.x O.sub.x.sub.+1 (s)+ QBr.sub.2 (1)
where the metal Q can be manganese or cobalt and where the reaction temperature and subscript x depend upon the metal Q employed and are for equilibrium constants, K, equal to about 1:
______________________________________manganese x = 1; about 700° C.cobalt x = 3; about 700° C.______________________________________
The metal bromide and higher valence metal oxide products formed in reactor 26B are transported to the separator 28. The metal bromide is separated from the metal oxide by a suitable means such as by flotation upon a liquid having a specific gravity between that of the metal bromide and that of the metal oxide. When the metal Q is manganese a suitable liquid is molten copper bromide, CuBr. When the metal Q is cobalt a suitable liquid is molten silver chloride, AgCl.
The metal oxide is transported from separator 28 to reactor 26A where it is thermally decomposed by the endothermic reaction:
Q.sub.x O.sub.x.sub.+1 (s)→xQO(s)= 1/2O.sub.2 (g)
where the metal Q is manganese or cobalt and the subscript x and the approximate reaction temperatures depends upon the metal Q and are for equilibrium constants, K, equal to 1 and 100:
______________________________________ K = 1 K = 100______________________________________manganese x = 1; 950° C. 1650° C.cobalt x = 3; 900° C. 1250° C.______________________________________
The oxygen 29 produced in reactor 26A is drawn off for storage or use. The lower valence metal oxide produced in reactor 26A is transported to reactor 26B where it is reacted with bromine as previously described.
Hydrogen bromide is produced by hydrolysis of the metal bromide produced in reactor 26B, separated by separator 28 and transported to reactor 30 for that purpose. The feedstock water in the form of steam 32 is fed to reactor 30 where it reacts with the metal bromide according to the endothermic hydrolysis reaction:
H.sub.2 O(g)+ QBr.sub.2 (s)→ QO(s)+ 2HBr(g)
where the metal Q is manganese or cobalt as before. Temperatures for this reaction depend upon the metal Q used and are for equilibrium constants, K, equal to 1 and 100: approximately:
______________________________________ K = 1 K = 100______________________________________manganese 1100° C. 2000° C.cobalt 1050° C. 2050° C.______________________________________
The metal oxide produced in reactor 30 is transported to reactor 26B where it is reacted with bromine gas as described previously. The hydrogen bromide gas is conducted to reactor 34 where it is reacted with the metal dibromide, which is produced in reactor 24 and transported to reactor 34 for the exothermic reaction:
2HBr(g)+ 2RBr.sub.2 (s)→2RBr.sub.3 (s)+ H.sub.2 (g)
The metal tribromide is transported to reactor 24 for thermal decomposition as previously described. The hydrogen 35 is drawn off for storage or use. The reaction temperatures depend upon the metal R which can be either vanadium or chromium and are for equilibrium constants greater than 1:
______________________________________vanadium 25° C. to 50° C.chromium 50° C. to 100° C.______________________________________
These reaction temperatures can be increased to improve reaction rates at the same hydrogen yield if the hydrogen bromide reactant gas pressure is increased.
Process heat 36 is introduced to reactor 30 and thence to reactor 24 to provide the endothermic heat for the chemical reactions which take place within. Heat contained in the exhaust heat 38 can be used to evaporate the feedstock water 32 and to generate power.
The maximum thermal efficiencies of the four possible bromine cycles formed by use of different combinations of the metals Q and R range from 0.603 to 0.818. Calculated thermal efficiencies for the four bromine cycles are given in the following table:
______________________________________ Maximum cycle thermalMetal Q Metal R efficiency______________________________________Mn V .818Mn Cr .638Co V .620Co Cr .603______________________________________
The above described chlorine and bromine cycles possess several inherent advantages in common including:
1. The hydrogen and oxygen product gases are produced in separate reactors having only one other product which is in a condensed phase. This facilitates the product gas separations.
2. The reactions which produce the hydrogen are exothermic. Thus these reactions are facilitated by decreasing reaction temperature and can be reacted at the lowest temperature having feasible reaction rates.
3. The reactions which produce hydrogen are facilitated by increasing the pressure of the hydrogen halide reactant gas. Thus high reaction rates and high conversions at temperatures higher than some of the relatively low equilibrium temperatures cited are possible if the reactant gas is compressed.
In addition to the above advantages held in common the chlorine cycles possess the advantages that the reactions which produces oxygen are exothermic and facilitated by reactant chlorine gas compression. Thus high reaction rates and high conversions at temperatures lower than those indicated for these reactions are possible if reactant chlorine gases are compressed. Further, the highest temperature reaction is that involving thermal decomposition of a metal trichloride which is facilitated by a partial vacuum. This reaction temperature can be lowered if desired at the expense, however, of added work. Some of the internally generated exothermic reaction heat is available to perform this work.
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A process is disclosed which produces hydrogen and oxygen from water by means of a multi-step, closed, thermochemical cycle. Hydrogen and oxygen are produced at separate stations. Hydrogen and a halogen are produced by a sub-cycle involving transition metal or lanthanide compounds (depending on the halogen) and a hydrogen halide. Oxygen and the hydrogen halide are produced in a sub-cycle involving magnesium or transition metal compounds (depending on the halogen), the halogen and water. When the halogen is chlorine the transition metals in the oxygen producing sub-cycle can be nickel, cobalt, or yttrium and the lanthanide metals in the hydrogen producing sub-cycle can be samarium, europium, or ytterbium. When the halogen is bromine, the metals in the oxygen producing sub-cycle can be manganese or cobalt and the metals in the hydrogen producing sub-cycle can be vanadium or chromium.
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RELATED APPLICATION(S)
[0001] The present application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 60/828,458, filed Oct. 6, 2006.
FIELD OF THE INVENTION
[0002] The present invention relates to prosthetic annuloplasty rings for effecting and maintaining a mitral or tricuspid repair.
BACKGROUND OF THE INVENTION
[0003] Repair of the mitral and tricuspid valves is a steadily growing and vital part of cardiac surgery. Experience has shown that effecting and maintaining a mitral or tricuspid repair requires a prosthetic annuloplasty ring. A major goal of a ring is to restore the shape of the annulus to its normal geometry. In mitral regurgitation, the annulus often becomes circular. The ring should restore the normal “D” shape. Fully flexible rings or bands do nothing to correct the shape of the pathologic mitral annulus. Only rigid or semi-flexible rings mold the shape of the mitral annulus.
[0004] One of the most common causes of a failed valve repair is dehiscence of the ring from the annulus. For the mitral annulus, dehiscence almost invariably occurs along the posterior portion of the ring, since this is the area of the annulus where size reduction and increased stress occurs.
SUMMARY OF THE INVENTION
[0005] Briefly, and in accordance with the foregoing, embodiments of the present invention provide prosthetic annuloplasty rings which are configured to minimize the likelihood of dehiscence while maintaining the shape of a healthy valve annulus.
[0006] In one embodiment, the present invention provides a saddle-shaped annuloplasty ring with a 4:3 ratio between the transverse dimension and vertical dimension for repairing the mitral valve. The ring is shaped and configured such that it closely mimics the geometry of a healthy mitral annulus. Preferably, the ring includes trigone markings to aid the surgeon with regard to correct positioning. The ring includes a core, an outer band and a cover. The core may be formed of titanium which provides that the ring is rigid. Alternatively, the core may be formed of a more flexible metal, such as Elgiloy or Nitinol, which would provide that the ring is semi-flexible, in which case preferably the ring is provided as being 20% more rigid in the vertical compared to the transverse dimension.
[0007] Preferably, the outer band comprises silicon rubber, and the cover comprises polyester cloth. Additionally, the width of the outer band is desirably greater in the posterior region of the ring than at the anterior region. This facilitates the placement of overlapping sutures of the posterior annulus to provide extra security against ring dehiscence.
[0008] Also disclosed is a tricuspid ring which is configured to minimize the likelihood of dehiscence while maintaining the shape of a healthy valve annulus. The ring is not complete in the 10% of the circumference around the anteroseptal commissure. This prevents suture injury to the conduction system. The ring may have a somewhat spiral shape that mimics the shape of the healthy tricuspid annulus, and the posterior half of the posterior annulus as well as the septal annulus slope down, preferably by about 4 mm. The ring includes a core which is formed of a semi-flexible material, such as Elgiloy or Nitinol, thereby providing that the ring is semi-flexible rather than rigid, which should decrease the odds of dehiscence. The width of an outer band of the ring is greatest in the septal region, thereby allowing overlapping sutures at the septal annulus to allow better anchoring of the ring.
[0009] A further understanding of the nature and advantages of the present invention are set forth in the following description and claims, particularly when considered in conjunction with the accompanying drawings in which like parts bear like reference numerals.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The organization and manner of the structure and operation of the invention, together with further objects and advantages thereof, may best be understood by reference to the following description taken in connection with the accompanying drawings wherein like reference numerals identify like elements in which:
[0011] FIG. 1 is a top plan view of a mitral annuloplasty ring which is in accordance with an embodiment of the present invention:
[0012] FIG. 2 is a side view of the annuloplasty ring shown in FIG. 1 ;
[0013] FIGS. 3A , 3 B and 3 C are cross-sectional views of the annuloplasty ring shown in FIG. 1 , taken along lines A-A, B-B and C-C, respectively, of FIG. 1 , where a core of the ring is a formed metal ring;
[0014] FIGS. 4A , 4 B and 4 C are cross-sectional views of the annuloplasty ring shown in FIG. 1 , taken along lines A-A, B-B and C-C, respectively, of FIG. 1 , where a core of the ring is a round wire;
[0015] FIGS. 1 ′, 2 ′, 3 A′, 3 B′, 3 C′, 4 A′, 4 B′ and 4 C′ correspond to FIGS. 1 , 2 , 3 A, 3 B, 3 C, 4 A, 4 B, and 4 C, respectively, but show preferred dimensions, in millimeters;
[0016] FIG. 5 is a top plan view of a tricuspid annuloplasty ring which is in accordance with an embodiment of the present invention;
[0017] FIG. 6 is a side view of the annuloplasty ring shown in FIG. 5 ;
[0018] FIGS. 7A and 7B are cross-sectional views of the annuloplasty ring shown in FIG. 5 , taken along lines A-A and B-B, respectively, of FIG. 5 , where a core of the ring is a round wire;
[0019] FIGS. 8A and 8B are cross-sectional views of the annuloplasty ring shown in FIG. 5 , taken along lines A-A and B-B, respectively, of FIG. 5 , where a core of the ring is a formed metal ring; and
[0020] FIGS. 7 A′, 7 B′, 8 A′, and 8 B′ correspond to FIGS. 7A , 7 B, 8 A and 8 B, respectively, but show preferred dimensions, in millimeters.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] While this invention may be susceptible to embodiments in different forms, there are shown in the drawings and will be described herein in detail, specific embodiments with the understanding that the present disclosure is to be considered an exemplification of the principles of the invention, and is not intended to limit the invention to that as illustrated.
[0022] FIG. 1 is a top plan view of a mitral annuloplasty ring 10 which is in accordance with an embodiment of the present invention, while FIG. 2 is a side view. The ring 10 is configured to minimize the likelihood of dehiscence while maintaining the shape of a healthy valve annulus. The ring 10 is a saddle-shaped ring (described below) with a 4:3 ratio between a transverse dimension (identified with reference numeral 12 in FIG. 1 ) and vertical dimension (identified with reference numeral 14 in FIG. 1 ). The reader will note that the vertical dimension is as viewed in plan view with an anterior side 28 up, though it is not oriented in this way in the drawings. The ring 10 is shaped and configured such that it closely mimics the geometry of a healthy mitral annulus. Preferably, an exterior surface 16 of the ring 10 includes trigone markings 18 , 20 to aid the surgeon with regard to correct positioning. The trigone markings 18 , are located at the junction of the anterior region 28 and the side regions 32 , 33 . Preferably, the range of ring sizes varies from a transverse internal diameter of 24-36 mm. The size needed is determined by measuring the area of the anterior leaflet with templates corresponding to the various ring sizes.
[0023] FIGS. 3A , 3 B and 3 C are cross-sectional views of the ring 10 taken along lines A-A, B-B and C-C, respectively, of FIG. 1 . As shown, the ring 10 consists of a core 22 , an outer band 24 and a cover 26 .
[0024] In a first embodiment of the present invention, the core 22 is formed of titanium which provides that the ring 10 is rigid. Alternatively, the core 22 may be formed of a more flexible metal which would provide that the ring 10 is semi-flexible rather than rigid. In this sense, the term “semi-flexible” refers to annuloplasty ring materials that are somewhat rigid but do flex due to the natural forces after implant. Semi-flexible means not as rigid as titanium, but more rigid than “fully flexible” rings made of, for example, silicone. Specifically, in a second embodiment of the present invention the core 22 is made of Elgiloy, and in a third embodiment of the present invention the core 22 is made of Nitinol. Regardless of what the core 22 is comprised of, preferably the outer band 24 comprises silicon rubber, and the cover 26 comprises polyester cloth. Although not specifically shown, the ring 10 may also include a barium impregnated string to render the ring radiopaque.
[0025] FIG. 3A provides a cross-sectional view of an anterior region 28 of the ring 10 , while FIG. 3B provides a cross-sectional view of a posterior region 30 , and FIG. 3C provides a cross-sectional view of side regions 32 and 33 , which are identical in cross-section. In a “saddle-shaped” ring, the ring periphery describes a three-dimensional path that gradually curves up at the anterior and posterior regions 28 , 30 , and down at the side regions 32 and 33 , as seen in FIGS. 2 and 2 ′. In the illustrated embodiment, the anterior and posterior regions 28 , 30 rise to about the same height, though they may be at different heights as desired.
[0026] As identified by comparing FIG. 3A to FIG. 3B , the width (dimension 34 in FIGS. 3A , 3 B, and 3 C) of the outer band 24 is greater, such as 30% greater, in the posterior region 30 of the ring 10 than at the anterior region 28 . This facilitates the placement of overlapping sutures of the posterior annulus to provide extra security against ring dehiscence. Preferably, the width 34 of the band 24 begins to change at the trigone markings 18 , 20 on the ring 10 , gradually becoming thicker until a maximum at the mid-point of the posterior region 30 . It should also be noted that the width of the outer band 24 at the posterior region 30 is equal to or greater than the width of the band at both the side regions 32 , 33 . For example, as seen by comparing FIGS. 4 A′ and 5 A′, and 4 B′ and 5 B′, the width of the outer band 24 at the posterior region 30 ranges between 1.3 mm (with a titanium core 22 ) to 2.2 mm (with a semi-flexible core), while the width of the outer band 24 at the side regions is a maximum of 1.3 mm (same with all core materials). In contrast, depending on the form and material of the inner core 22 , the width of the outer band 24 at the anterior region 28 is less than, equal to, or greater than the width at the side regions 32 , 33 , as seen by comparing FIGS. 3 A′ and 5 A′, and 3 B′ and 5 B′.
[0027] As discussed above, the core 22 can be provided as being formed of titanium which would tend to make ring 10 rigid. Alternatively, the core 22 may be formed of a more flexible metal, such as Elgiloy or Nitinol, which would make the ring semi-flexible rather than rigid. This semi-flexible alloy allows the ring 10 to flex during the cardiac cycle without losing its shape. Hopefully, the flexibility will minimize local annular stresses likely to produce dehiscence.
[0028] If Elgiloy or Nitinol is used for the core 22 , the core 22 may be shaped somewhat differently than if titanium is used. This change in cross-sectional shape is identified in FIGS. 3A , 3 B, 4 A, 4 B, 3 A′, 3 B′, 4 A′ and 4 B′ using a dotted line 36 . The dotted line 36 represents the outer surface of a titanium core 22 , in contrast to the solid cross-section of a semi-flexible (e.g., Nitinol or Elgiloy) core. In the illustrated embodiment, the solid cross-section includes an axially-oriented surface that defines the outer surface of a semi-flexible core 22 , in contrast to the dotted line 36 which represents the outer surface of a titanium core and has a concave outer profile in radial section as shown.
[0029] If Elgiloy or Nitinol is used for the core 22 , the ring 10 is preferably configured such that it is 20% more rigid in the vertical dimension 14 (the anterior-posterior direction) as compared to the transverse dimension 12 . In other words, it is harder to squeeze the ring 10 between the anterior and posterior regions 28 , 30 in FIG. 1 than it is to squeeze the ring 10 between the side regions 32 , 33 . This difference in rigidity/flexibility derives from a particular cross-sectional shape of the core 22 which overcomes the natural inclination for the ring to be more flexible in the vertical dimension. That is, if the ring 10 were the same cross section all the way around its periphery, the longer moment arm in bending when squeezing the anterior and posterior regions 28 , 30 would naturally permit greater flexing or inward movement than when squeezing the side regions.
[0030] In an exemplary embodiment, the width (dimension 35 in FIGS. 3A-3C and 4 A- 4 C) of the core 22 may be thinner in the anterior and posterior regions ( 28 and 30 ) than in side regions 32 and 33 . More specifically, the width dimension 35 is shown measuring the extent of the core 22 as seen in dotted line 36 , but the width for cores of semi-flexible material such as Elgiloy or Nitinol would only extend to the solid line cross-section. There is thus a difference in the width dimension at the anterior and posterior regions for rings made of a semi-flexible material versus a ring made of a rigid material, such as titanium. However, the core width 35 of both semi-flexible and rigid rings remains the same at the side regions 32 , 33 because it is desirable to maintain in semi-flexible rings the resistance to bending from squeezing the ring 10 in the transverse dimension (vertical in FIG. 1 ).
[0031] Preferably, the width 35 of the core 22 begins to change at the trigone markings 18 , 20 on the ring 10 , and most preferably reduces gradually from the trigones to the mid-point of the anterior and posterior regions 28 , 30 . In particular, the cross-section of the core 22 of semi-flexible rings desirably attains a maximum at the side regions 32 , 33 , as seen in FIGS. 3C and 4C , and gradually reduces toward the anterior and posterior regions 28 , 30 , as seen in solid line in FIGS. 3A-3B and 4 A- 4 B. Alternatively, an abrupt change in cross-section or one which while not abrupt is sharp or non-linear may be utilized. For instance, from a maximum at the side regions 32 , 33 , the width 35 may decrease smoothly but rapidly over an arc of, say, 10° to the lesser width of the anterior and posterior regions 28 , 30 . It is also worth mentioning that the reduced width 35 at the anterior and posterior regions 28 , 30 may be equal or not as desired.
[0032] If Nitinol is used as the core 22 of the ring 10 , the ring 10 could be used in association with a method which is in accordance with an embodiment of the present invention. Specifically, the design would be uniquely well suited for minimally invasive valve cases with working ports too small to accommodate currently available rigid rings. At present, only fully flexible prostheses, such as the Duran ring or the Cosgrove band, can traverse these 20 mm working ports. These fully flexible prostheses do nothing to decrease the vertical dimension, which has been increasingly recognized as important in maintaining a durable valve repair. By immersing the Nitinol core ring in iced saline, the ring would be readily deformable (martensite phase). This would facilitate passage of the ring through 20 mm working ports used in robotic valve repair. As the ring warmed up in the chest, it would resume its saddle shape (austensite phase). The silicon rubber band would facilitate anchoring the band to the annulus with Coalescent Nitinol clips. Until now, these clips could only be used with fully flexible prostheses.
[0033] Regardless of whether the core 22 is made of titanium, Elgiloy or Nitinol, the core 22 can be formed of a round wire, in which case the cross-sectional views taken along lines A-A, B-B and C-C of FIG. 1 would appear as shown FIGS. 3A , 4 A and 5 A, respectively. Alternatively, the core 22 can be a formed metal ring, in which case the cross-sectional views taken along lines A-A, B-B and C-C of FIG. 1 would appear as shown FIGS. 3B , 4 B and 5 B, respectively. A dotted line 36 is also used in FIGS. 3B , 4 B and 5 B to show the situation where the core 22 is an Elgiloy or Nitinol formed metal ring.
[0034] As shown in FIG. 2 , the ring 10 may be provided as being slightly asymmetric, with the portion at the left trigone 20 one mm deeper than the right trigone 18 . In other words, the side regions 32 , 33 drop to different heights, with the left side 32 (as viewed from above with the anterior side 28 up) lying on a reference line seen in FIG. 2 while the right side 33 is slightly spaced therefrom. This more closely reproduces the true natural shape of the healthy mitral annulus. Even if the ring 10 is provided as being slightly asymmetric, the core 22 can be titanium, Elgiloy, or Nitinol, for example.
[0035] FIGS. 1 ′, 2 ′, 3 A′, 4 A′, 3 A′, 3 B′, 4 B′ and 5 B′ correspond to FIGS. 1 , 2 , 3 A, 4 A, 5 A, 3 B, 4 B and 5 B, respectively, but show preferred dimensions, in millimeters. It should be noted that the dimensions shown are only one example, intended to provide the desired properties described herein, and other dimensions may be used while staying fully within the scope of the present invention. For instance, the magnitudes shown may represent dimensionless ratios of the various dimensions. In one example, as seen in FIG. 2 ′, the left side 32 (see FIG. 2 ) has a height of 5 mm from the summit of the anterior side 28 , while the right side 33 has an equivalent height of 4 mm. The downward drop of the left side 32 may be more or less, but desirably is about 20% more than the downward drop of the right side 33 .
[0036] FIG. 6 is a top plan view of a tricuspid ring 40 which is in accordance with an embodiment of the present invention, while FIG. 7 is a side view. The ring 40 is configured to minimize the likelihood of dehiscence while maintaining the shape of a healthy valve annulus. Preferably, the ring 40 comes in different sizes with an internal diameter being between 24-36 mm. Regardless of the size, the ring 40 is not complete in 10% of the circumference around the anteroseptal commissure (i.e., area 42 in FIGS. 6 and 7 ). This prevents suture injury to the conduction system. The ring 40 has a somewhat spiral shape that mimics the shape of the healthy tricuspid annulus. The anterior annulus 44 and anterior half 46 of the posterior annulus 48 are in the same plane (identified with line 50 in FIG. 7 ). The posterior half 52 of the posterior annulus 48 as well as the septal annulus 54 slope down, preferably 4 mm (identified with dimension 56 in FIG. 7 ).
[0037] FIGS. 8A and 9A are cross-sectional views of the ring 40 taken along lines A-A and B-B, respectively, of FIG. 1 . As shown, like the ring 20 described hereinabove, the ring 40 includes a core 58 , an outer band 60 and a cover 62 . Preferably, the core 58 is formed of a semi-flexible material. Specifically, in one embodiment, the core 58 is provided as being formed of Elgiloy. In another embodiment, the core is provided as being formed of Nitinol. Regardless, using a semi-flexible material for the core 58 provides that the ring 40 is semi-flexible rather than rigid, which should decrease the odds of dehiscence. Currently, only rigid rings have been specifically constructed for tricuspid repair. Regardless of what the core 58 is comprised, preferably the outer band 60 is formed of a silastic material, such as silicone, and the cover 62 is comprised of polyester cloth.
[0038] FIG. 8A is a cross-sectional view taken along line A-A of FIG. 6 and provides a cross-sectional view of the anterior region of the ring 40 . This view also applies to the posterior region. In contrast, FIG. 9A provides a cross-sectional view taken along line B-B of FIG. 6 and corresponds to the septal region of the ring. As recognized by comparing FIG. 8A to FIG. 9A , the width (dimension 64 in FIGS. 8A and 9A ) of the outer band 60 is greater (such as 1.3 times greater) in the septal region 54 than either the anterior region 44 or posterior region 48 . This allows overlapping sutures at the septal annulus 54 to allow better anchoring of the ring 40 .
[0039] As discussed above, an embodiment of the present invention provides that the core 58 of the ring 40 is provided as being formed of Nitinol. This allows further flexibility and further minimizes the likelihood of dehiscence. If Nitinol is used as the core 58 of the ring 40 , the ring 40 could be used in association with a method which is in accordance with an embodiment of the present invention. Specifically, cooling the ring 40 in iced saline will facilitate passage of the ring 40 through small working ports for minimal access valve surgery. Additionally, the diameter 64 of the silicone rubber band 60 will facilitate attachment of the ring 40 to the annulus with Coalescent Nitinol clips.
[0040] Regardless of whether the core 58 is made of Elgiloy or Nitinol, the core 58 can be formed of a round wire, in which case the cross-sectional views taken along lines A-A and B-B of FIG. 6 would appear as shown FIGS. 8A and 9A , respectively. Alternatively, the core 58 can be a formed metal ring, in which case the cross-sectional views taken along lines A-A and B-B of FIG. 6 would appear as shown FIGS. 8B and 9B , respectively.
[0041] FIGS. 8 A′, 9 A′, 8 B′ and 9 B′ correspond to FIGS. 8A , 9 A, 8 B and 9 B, respectively, but show preferred dimensions, in millimeters. It should be noted that the dimensions shown are only one example, intended to provide the desired properties described herein, and other dimensions may be used while staying fully within the scope of the present invention. For instance, the magnitudes shown may represent dimensionless ratios of the various dimensions.
[0042] Disclosed herein are several embodiments of mitral and tricuspid rings, each of which is configured to minimize the likelihood of dehiscence while maintaining the shape of a healthy valve annulus. While preferred embodiments of the invention are shown and described, it is envisioned that those skilled in the art may devise various modifications without departing from the spirit and scope of the foregoing description.
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A mitral annuloplasty ring with an inner core and an outer band located therearound is disclosed. The ring has an anterior region, a posterior region opposite the anterior region, and two side regions therebetween. A cross-sectional width dimension of the outer band is greater in the posterior region of the ring than in the anterior region. A cross-sectional width dimension of a semi-flexible core is thinner in the anterior and posterior regions than in the side regions so that the mitral ring is more rigid in the anterior-posterior direction. A tricuspid annuloplasty ring of the invention has an inner core and an outer band located therearound. The inner core has an anterior region separated across a gap from a septal region, and a posterior region. A cross-sectional width dimension of the outer band is greater in the septal region than either the anterior or posterior regions.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a novel process for increasing the rate of hydration of food crop seeds, particularly for the dry instantization of rice.
2. Description of Related Art
The demand by consumers for fast cooking food products has continued to increase in recent years. However, a number of food crop seeds such as brown rice, wild rice and beans require long cooking times, due in large part to their slow rate of hydration. Consequently, the consumption of these food crop seeds has been significantly limited in the United States.
A number of instant or quick-cooking rice and vegetable products have been developed and are currently available. Generally, instant or quick-cooking rice products are prepared by first hydrating and/or precooking raw rice, and subsequently drying the treated rice to a desired moisture content. These methods of instantization require significant amounts of water and energy, adding additional cost to the product and often affecting product quality. Moreover, most of these processes have been developed for production of white rice from which the bran layers have been removed. Relatively few quick-cooking brown or wild rice products have been developed. Because the bran layers contain most of the nutrients in the rice grain, the development of quick-cooking brown and wild rice products acceptable to the consumer would be highly desirable. In one process described by Gorozpe (U.S. Pat. No. 3,157,514), whole grain, brown or white milled rice are first pretreated to create fissures or cracks in the rice grain by heating. The fissured rice is then hydrated, cooked to partially gelatinize the starch, cooled and dried. Other processes for the preparation of quick-cooking brown or wild rice include those described by Carlson et al. (U.S. Pat. No. 4,133,898) and Weibye (U.S. Pat. Nos. 4,677,907 and 4,385,074). However, despite these advances, there remains a need for improved methods for preparing quick-cooking rice and other food crop seed products at less expense.
SUMMARY OF THE INVENTION
I have now discovered a novel process for significantly increasing the rate of hydration of food crop seeds without loss of the nutritious and beneficial portions of the seeds. In this process, the seed of interest is bombarded with an abrasive particulate sufficient to create microperforations in the water resistant outer coat of the seed. Alternatively, the seeds may be propelled toward and impacted against an abrasive surface to create the microperforations in the water resistant outer coat. These microperforations in the treated seed significantly increase the rate of hydration of the seed and hence decrease cooking time accordingly. Moreover, this process effects improved hydration without removing any significant portions of the water resistant outer coat or layers of the seed which lie underneath the coat.
In accordance with this discovery, it is an object of this invention to provide a dry process for significantly increasing the rate of hydration of food crop seeds.
Another object of this invention is to provide a process for increasing the rate of hydration of food crop seeds while leaving nutritious and beneficial portions of the seeds substantially intact.
Yet another object of this invention is to provide a process for the dry instantization of rice without hydration or cooking, while leaving the bran layers substantially intact.
Other objects and advantages of this invention will become readily apparent from the ensuing description.
DETAILED DESCRIPTION OF THE INVENTION
For a number of food crop seeds, the time required to hydrate the seeds, such as prior to or during cooking, may be exceptionally long. The process of the invention described herein significantly increases the rate of hydration of food crop seeds, consequently reducing their associated cooking time. In contrast to previously described processes, the process of this invention may be conducted as a dry process, and does not require hydration, cooking, or heating. While the process is preferably used for the treatment of dehulled (i.e. dehusked) cultivated brown rice or wild rice, particularly strains of Oryza sativa L. and O. glaberrima Steud., it may also be used for the treatment of other food seed crops of interest, including but not limited to beans, soybeans, wheat, oats and corn. As defined herein, dehulled rice refers to a quantity of rice grains which have been dehulled to an extent such that more than or equal to 90% of the grains are dehulled. In the preferred embodiment, more than or equal to about 99% of the rice grains are dehulled. Dehulling may be conducted using conventional techniques.
In a first embodiment, the food crop seed described above is bombarded with a high velocity abrasive particulate which is propelled against the target seed under conditions and for a period of time effective to scarify the seed by creating microperforations (i.e., nicks, holes or cuts) in the water resistant outer layer(s). However, the outer layer(s) are not abraded away, but remain substantially intact on the seed. The second, alternative embodiment is predicated upon the same principle although the roles of the bombarding material and the material impacted are reversed. In this second embodiment, the seeds are propelled at a high velocity and directed against an abrasive surface effective for creating the microperforations in the water resistant layers upon impact therewith.
In either of the first or second embodiments, the bombarding particle (i.e., the abrasive particulate or seed, respectively) are preferably propelled by entrainment in a high velocity gaseous flowstream. However, the bombarding particles may also be propelled mechanically as described in greater detail hereinbelow.
Food crop seeds typically consist of an embryo and endosperm surrounded by one or more relatively tough, water resistant layers, the pericarp and the seed coat or testa. In rice, the embryo and endosperm of the grain are surrounded, in order from the outermost to innermost layers, by the hull, pericarp, seed coat, nucellus and aleurone. Removal of the hull by dehulling exposes the brown rice, also referred to as the caryopsis. The remaining outer four layers of the brown rice, the pericarp, seed coat, nucellus and aleurone, comprise the bran layers of the rice grain and are high in nutrients, with the aleurone layer being particularly high in protein and lipid bodies. However, the pericarp, seed coat and nucellus, which are collectively referred to as the caryopsis coat, each contain a cuticle and are nearly impermeable to water when intact. In accordance with this invention, exposure of dehulled brown rice or wild rice to the abrasive particulates produces microperforations through the pericarp which may also extend through one or more or all of the underlying layers of the caryopsis coat and the aleurone to expose the endosperm. However, this treatment does not remove a substantial portion of the bran layers, but rather the bran layers remain substantially (defined herein as more than 50%, by weight) intact on the rice grains. In the preferred embodiment, more than or equal to approximately 80% by weight of the bran layers remain on the treated rice grains. In other words, the bran layers, and particularly the aleurone layer, remain on the rice grain. Although the pericarp, being the outermost layer, may be partially abraded or eroded away, a substantial portion thereof. (as defined above) remains on the grain. For treatment of other food crop seeds, it is understood that the treatment of this invention may be effective for creating microperforations in the pericarp and/or seed coat to the same extent.
A variety of materials may be used herein as the abrasive particulate. Suitable abrasive particulates should have sharp or angular edges or surfaces and are preferably harder than the seed being treated, although softer particulates may be effective when propelled at higher velocities. The optimal particulate selected will therefore vary with the particular seed being treated and the treatment conditions, particularly the velocity of the particle (including the pressure or velocity of an entraining gas stream), and may be readily selected by the skilled practitioner by routine experimentation. Examples of abrasive particulates which may be used include, but are not limited to, silicas, clays, sand, kaolinite, plastics, metals, diatomaceous earth, extruded or ground plant products such as wild rice chits, rice hulls, corn husks or nut shells, and preferably particulate food grade materials such as parboiled rice flour, spices, salt, sugar and cereal grain flour. The use of such food grade particulate materials is preferred to simplify or even obviate the need for further processing after the scarification to separate the abrasive particulate from the seed. Use of sand or other non-food grade particulates will generally require a subsequent washing or rinsing step to remove the particulate from the treated seed.
The size of the abrasive particulate will also vary with the treatment conditions, particle density, and the type of seed. In general, for any specific particulate, the efficiency of the abrading or scarification is reduced when using very large sizes, particularly those greater than about 200μ, increasing the treatment time necessary to achieve effective microperforation of the seeds. Although particulates greater than 200μ may be used, even up to about 1,000μ, the efficiency of the process decreases significantly. Conversely, very small particulates (i.e., less than 10μ), may lack sufficient mass to be effective under most conditions, requiring exceptionally high velocities to effectively scarify the seeds. Therefore, suitable particulate sizes are typically greater than or equal to about 10μ, and less than or equal to about 1,000μ, and preferably between about 10μ and 200μ. In a preferred embodiment for the treatment of rice, the particulate size will be between about 50 to 150 μ, particularly between about 100 to 150μ, and most preferably between about 120-130μ. The skilled practitioner will recognize that when using volumes of sand, processed food particulates such as flour, or other ground or extruded materials, the size of individual particles within the volume are variable. For these particulates, the sizes are typically expressed as a mesh size, with the particles being capable of passing through an art recognized mesh size opening. Consequently, particles of sizes smaller than those described above as preferred or suitable may be present in the bombarding stream. Nonetheless, the mesh size will typically be selected such that the mesh opening substantially corresponds to or is slightly larger than the suitable or preferred particle sizes described herein.
The apparatus used for the treatment of the seeds in accordance with this invention is not critical, and any device capable of propelling the bombarding particle at a high velocity will be effective. Preferred devices include those capable of producing high pressure or velocity gas streams with a particulate feed such that the particle may be entrained into the stream. Without being limited thereto, the gas streams may be generated using high pressure pumps, blowers or fans. In a particularly preferred embodiment, the treatment is typically effected using a conventional sandblaster directed at the seeds. The treatment conditions, including entraining gas pressure or velocity, and the duration of the treatment will vary with the seed being treated and the desired particulate, and are selected to effectively scarify the seed without removing water resistant outer layers as described above. Optimal conditions and time may be readily determined by the skilled practitioner. When using small, highly abrasive particulates such as fine grain sand for bombarding seeds with relatively soft outer coats, the gas pressure may need only be great enough to pick up and entrain the particulates in the gas stream to be effective. Conversely, the pressure should not be so high that the outer layers of the seeds are substantially or completely removed. The treatment of seeds such as beans which have harder coats, may require higher pressure or velocity gas flowstreams. Without being limited thereto, suitable gas pressures of the sandblaster will therefore vary with the seed and particulate, and may be between about 20 to 10,000 psig. For the treatment of rice and other relatively soft seeds, the gas pressure of the sandblaster is preferably between about 20 to 200 psig, more preferably between about 40 to 120 psig, and particularly between about 60 to 80 psig. Virtually any gas may be used for the entraining gas stream, although air, and particularly low humidity air, are preferred.
Alternatively, rather than entraining the particles in a high velocity or high pressure gas stream, the particles may be mechanically propelled. The particular device selected is not critical and any device capable of propelling the particle (abrasive particulate or seed) as described above may be suitable for use herein. For instance, suitable devices include but are not limited to high speed conveyor belts or wheels positioned to dispense the particles carried thereon toward the target, rotating cylinders with pick-up brushes or impellers effective for propelling the particles upon contact therewith, and pairs of parallel, closely spaced, oppositely rotating cylinders having a particle feed into the space therebetween, which space is selected to contact and promote passage and propulsion of particles at high velocity.
In an optional yet preferred embodiment, the seeds to be treated may be placed upon an inclined, or rocking or vibrating support. Alternatively, an agitator or stirrer may be provided to mechanically move the seeds on the support. In this embodiment, during treatment the seeds will therefore roll or move, exposing different sides thereof to the abrasive particulates and therefore not limiting scarification to only one side of the seeds. Use of screen or mesh supports, having a mesh size sufficient to allow passage of the abrasive particulates but not the seeds, are particularly preferred for ease of separation of the particulate from the seed.
Following treatment, the scarified seeds may be further processed to remove the abrasive particulate therefrom. Suitable methods include but are not limited to washing or rinsing with a liquid such as water, or blowing with a gas stream.
In an alternative embodiment, the seed to be treated is propelled and directed against an abrasive surface under conditions and for a period of time effective for creating the microperforations in the water resistant outer coat of the seed. Like the first embodiment, the outer layer(s) of the seed are not abraded away but remain substantially intact upon the seeds above. The seeds may be propelled using the same techniques as described above, although in the preferred embodiment, the seeds are entrained in a high pressure or velocity gaseous flowstream. Suitable velocities or pressures of the entraining gas flowstream may vary with different seeds, although the minimum pressure or velocity will typically be somewhat higher than described in relation to the first embodiment in view of the greater size and mass of the seeds. However, as described in the first embodiment, optimal conditions, including the pressure or velocity of the entraining gas flowstream and the abrasive surface, may be readily determined by the skilled practitioner by routine experimentation.
The equipment used for generation of the high pressure or velocity gas flowstream and bombarding the seeds upon the abrasive surface is not critical. As described above, the generation of the high pressure or velocity flowstream may be effected, for example, with conventional high pressure pumps, blowers or fans. The seed may be fed into a conduit, duct or channel transporting the flowstream whereupon it may be directed at the abrasive surface. A variety of abrasive surfaces may also be used, and include but are not limited to a surface having any of the above-described abrasive particulates adhered thereon, sandpaper, or the surface itself may be constructed of an abrasive material, such as conventional grinding or cutting blades.
Scarified seeds produced by any of the above-mentioned processes are suitable for use as a fast-hydrating or fast cooking food crop seed product. Optionally, the seeds may be further treated to improve appearance and/or further decrease cooking times. For instance, treated rice grains may be optionally shined by mechanical rubbing or oil treatment to improve appearance. The scarified rice may also be cooked in water and dried, to produce an instant rice capable of cooking in even shorter times. Cooking and drying techniques which are conventionally used to prepare various commercial quick-cooking or instant rices are suitable for use herein. However, the long soaking periods required in those conventional processes may now be omitted.
The following example is intended only to further illustrate the invention and is not intended to limit the scope of the invention, which is defined by the claims.
EXAMPLE 1
Materials and Methods
Long grain, dehulled brown and wild rice was purchased from local stores. Sand (black and white), salt and parboiled rice flour were bought through different sources for use as abrasive particulates in bombarding the rice. Black sand was obtained in a coarse (Starblast®) and fine (Starblast®XL) grade from Dupont. White sand was obtained from Manley Brothers in 70 and 120 average mesh size. Flour salt was obtained from Cargill Salt Co. which had an average particle size of about 120 mesh. This type of salt is cracked between drums and therefore has sharp edges. Parboiled broken rice was obtained from Riviana and passed twice through a pin mill to obtain similar particle size by feel.
120 gram samples of each of the above-mentioned rice types were placed on a U.S. standard 12 mesh screen, and placed below another 8 mesh screen. The screen size was selected so that rice would not fall through the bottom screen. Air at high pressure (approx. 90 psig) carrying sand, salt or parboiled rice flour at high velocity was directed towards the rice in the screen. The screen was held at an angle and agitated, such that the exposure to the particles in the air and the turbulence resulting from the air pressure moved the rice grains in the inclined corner. Thus, all sides of the rice were randomly exposed to the particles.
Results and Discussion
Preliminary experiments were done with black sand. Brown rice was exposed to coarse and fine grade Dupont sand for 5 sec, 10 sec, 20 sec, 30 sec, 1 min, 2 min and 4 min at approximately 90 psig. Use of coarse grade sand required 1 min of exposure to the sandblasting to reduce the cook time of the brown rice to 15 min. In contrast, only 20 sec of exposure to fine sand was necessary to achieve the same effect. Without wishing to be bound by theory, it is believed that the smaller particles of the fine sand can cut, nick, pit or indent the surface more effectively than coarser sand. Unfortunately, use of black sand imparted a greyish color to rice due to the interaction between some of the oil on the rice surface with the mineral in sand.
White sand (120 mesh) obtained from Manley Brothers was used to bombard the brown and wild rice for 15 sec and 30 sec and was found to be extremely effective in maintaining color and also improving rehydration and reducing cook time. Again, less exposure time was required for smaller particle size (120 mesh) and 70 mesh sand was not as effective.
Sandblasting of the brown and the wild rice at 90 psig had noticeable marks on the rice grains and also appeared to remove a significant portion of the outer layer. We then hypothesized that if the air pressure was reduced to a point that it only resulted in nicks, cuts, pits and indentation but did not remove a substantial amount of the bran layers then we should not be able to observe nicks, cuts, pits and indentation to the outside by naked eye. We therefore used the 120 mesh white sand and reduced the air pressure to a point where it would start picking up the sand particle. This produced the desired effect without losing any of the bran layers. The treated product had the appearance of the untreated product to the naked eye. Microperforations in the outer layers of the brown rice grains were only apparent upon microscopic examination, while microperforations in the wild rice could only be seen by the naked eye with great difficulty.
The process described above was repeated with salt and finely ground parboiled flour used as the abrasive. particulates for sandblasting rather than the white sand. Use of these food grade particulates poses no residue problem. When salt and flour were used, wild rice required more exposure time (1-1.5 min) in comparison to brown rice (25 sec) to effect suitable microperforation of the grains.
It is understood that the foregoing detailed description is given merely by way of illustration and that in modifications and deviations may be made therein without departing from the spirit and scope of the invention.
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A process for significantly increasing the rate of hydration of food crop seeds, such as brown and wild rice, without loss of the nutritious and beneficial portions of the seeds, is disclosed. In this process, the seed of interest is bombarded with an abrasive particulate, which is preferably entrained in a pressurized stream of gas, sufficient to create microperforations in the water resistant outer coat of said seed. These microperforations in the treated seed significantly increase the rate of hydration of the seed and hence decrease cooking time accordingly. Moreover, this process effects improved hydration without removing any significant portions of the outer coat or layers of the seed which lie underneath the outer coat.
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FIELD OF INVENTION
[0001] The present invention relates to transistor design, and, in particular, a thermal nitrogen deposition method to improve the uniformity of the nitrided layer of a gate capacitor of a transistor.
BACKGROUND OF THE INVENTION
[0002] The speed requirements for high-performance 0.13 um CMOS devices has driven gate oxide thicknesses to less than 20 Å, with inversion and physical thicknesses trending to less than 20 Å. As the dielectric layers are scaled thinner, the leakage currents through these gates exponentially increase due to more direct tunneling of electrons and holes through the potential barriers of the dielectric. This can affect device properties by causing higher standby power consumption, reliability problems, and degradation of certain chip functions such as timing. Battery powered devices for mobile applications for example, have some of the strictest requirements for leakage current, where lower leakage currents produce longer battery life.
[0003] [0003]FIG. 1 shows a transistor structure with the gate dielectric ( 20 ). Gate leakage current is defined as the current from gate to drain when Vg ( 22 ) is less than the threshold voltage of the device. This current is an exponential function of thickness, with the current increasing by 2-3× for every 1 Å decrease in thickness, in the sub-20 Å thickness range for a gate dielectric layer that is formed using SiO 2 .
[0004] Remote plasma nitridation (RPN) or decoupled plasma nitridation (DPN) are methods used to introduce large concentrations of nitrogen into the gate dielectric layer, thereby forming a silicon oxynitride gate dielectric. With the incorporation of nitrogen, the gate leakage current can by reduced. This is mainly due to increasing the capacitance of the layer which allows for larger physical thicknesses with the same electrical thickness. There is also some reduction in leakage current due to the change in chemical bonding at the dielectric-Si substrate interface. These particular processes are desirable due to their ability to incorporate large concentrations of nitrogen (>4×10 21 at/cm 3 ) and their ability to control the profile of the nitrogen throughout the dielectric layer. These process techniques however, can be inherently non-uniform, thus causing a large non-uniformity of device parameters across the wafer. Non-uniformity of device parameters can cause severe yield degradation in chip performance if certain specifications are out of range. These electrical parameters can include leakage current, electrical thickness, threshold voltage, and device current. This invention addresses this non-uniformity, and demonstrates that the physical thickness and nitrogen concentration is improved by making use of the techniques described in the invention.
SUMMARY OF THE INVENTION
[0005] The present invention relates to a method for improving the uniformity of the nitrided layer that is formed over the base SiO 2 layer of a transistor gate dielectric, thus lowering the leakage current through the base SiO 2 layer.
DESCRIPTION OF THE DRAWINGS
[0006] [0006]FIG. 1 shows a transistor used to define gate leakage current.
[0007] [0007]FIG. 2 shows the cross-sectional profile of a wafer, comprising the base oxide layer and the nitrided layer formed by any nitrogen-deposition process.
[0008] [0008]FIG. 3 shows the cross sectional profile of a wafer, comprising a first base oxide layer, a second nitrided layer formed by any nitrogen-deposition process, and a third NO annealed layer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0009] [0009]FIG. 2 shows the cross sectional profile of a wafer used as a gate dielectric. First a base oxide layer ( 24 ), for example, silicon dioxide (SiO 2 ), of the wafer is formed using known techniques, such as RTO or furnace oxidation. The base oxide layer can be between 5A and 20A thick. The base oxide layer is usually approximately 10A thick. Next, nitrogen is deposited in the base oxide layer using RPN or DPN, resulting in a highly-nitrided second layer ( 26 ) containing a high concentration of nitrogen. This highly-nitrided second layer can be anywhere between 10A-30A thick. However, RPN and DPN result in this highly-nitrided second layer having a non-uniform physical profile. FIG. 2 shows the situation where the height of the second layer is greater in the middle than at the edges of the profile. FIG. 2 shows only this one irregular profile. Other irregular profiles, such as where, for example, the edges of the highly nitrided layer are higher than the middle of the highly nitrided layer are possible as well, are not shown. FIG. 2 defines h max as the highest point of the highly-nitrided second layer above the base oxide layer and h min as the lowest point of the highly-nitrided second layer above the base oxide layer.
[0010] In addition to RPN's and DPN's resulting in the non-uniform physical structure of this highly-nitrided second layer, RPN and DPN also results in a non-uniform deposition of nitrogen within the highly-nitrided second layer. For example, Table 2 shows nitrogen concentrations between the center and the edge of the highly-nitrided second layer differing by 3×10 14 atoms/cm 3 .
[0011] Subjecting this structure shown in FIG. 2 (i.e., a two-layer structure comprising a base oxide layer and a highly-nitrided second layer) to a nitric thermal anneal process reduces the non-uniformity of the profile of the highly-nitrided second layer, resulting in the cross-sectional profile shown in FIG. 3. The resulting structure has a base oxide layer ( 24 ), a highly nitrided second layer ( 26 ), and a NO anneal layer ( 28 ). The NO anneal layer can be between 1A and 30A thick, and is typically between 1A and 5A thick. Subjecting this structure shown in FIG. 2 to a nitric thermal anneal process also reduces the non-uniformity of nitrogen deposition concentration within the highly-nitrided second layer, as shown in Table 2. Two methods can be used to carry out this nitric thermal anneal.
[0012] In a first embodiment of the present invention, a plurality of wafers on which a base oxide layer and a highly-nitrided second layer have been formed are put into an annealing furnace. The time, temperature, and pressure of the annealing process can be varied to achieve the maximum uniformity of the nitric anneal layer. The wafers are exposed to a range of temperatures for times ranging from 5 minutes to 30 minutes. The temperatures to which the wafers are exposed can range between 500-1100 degrees Centigrade. The pressure to which the wafers are exposed during this process can range between 1-760 torr. During the time when the wafers are in the furnace exposed to the annealing temperature and pressure, gas is allowed to flow over the surface of the wafers. This gas can be any gas which under the temperature and pressure conditions under which the anneal is performed dissociates into NO. The gas is heated to a temperature in the range of 800-1100 degrees Centigrade before being admitted into the furnace and allowed to pass over the wafers. Preferably, the gas is heated to 950 degrees Centigrade before being admitted into the furnace and allowed to pass over the wafers.
[0013] In a second embodiment of the present invention, single wafer tools are used to perform the annealing process instead of an annealing furnace. In other words, while using the annealing furnace allows a batch of wafers to undergo thermal annealing at one time, in this embodiment, single wafers are subjected to the annealing process at one time. The time, temperature, and pressure parameters to which the wafers are exposed are the same as in the first embodiment described previously. The wafers are exposed to a range of temperatures for times ranging from 5 seconds to 30 minutes. The temperatures to which the wafers are exposed can range between 500-1100 degrees Centigrade. The pressure to which the wafers are exposed during this process can range between 1-760 torr. During the time when the wafers are exposed to the annealing temperature and pressure, gas is allowed to flow over the surface of the wafers. This gas can be any gas which under the temperature and pressure conditions under which the anneal is performed dissociates into NO. The gas is heated to a temperature in the range of 800-1200 degrees Centigrade before being allowed to pass over the wafers. Preferably, the gas is heated to 950 degrees Centigrade before being allowed to pass over the wafers.
[0014] The advantage of the first embodiment discussed above is that several wafers can be annealed at once. The advantage of the second embodiment is that, in a single wafer process, the required temperature and pressure can be reached in a shorter period of time.
[0015] The following table (Table 1) shows the results obtained for two furnace annealing processes accomplished under the conditions shown. These data are obtained by optical measuring:
Furnace Anneal for 26 Furnace Anneal minutes N 2 O for 13 minutes 800 C (950 C N 2 O 700 C (950 C precombustion precombustion chamber chamber temperature) temperature) Elliptical Std. Elliptical Std. Process/sequence thickness Range Dev. Thickness Range Dev. RPN 21.44 A 2.24 A 0.5 A 21.34 A 1.91 A 0.47 A RPN/Furnace 22.46 A 1.38 A 0.33 A 24.17 A 0.93 A 0.28 A anneal RTO/RPN 20.27 A 1.53 A 0.39 A 20.04 A 1.05 A 0.27 A RTO/RPN/Furnace 23.04 A 0.70 A 0.18 A 26.11 A 0.98 A 0.24 A Anneal
[0016] Where: (a) elliptical thickness represents the thickness of the highly-nitrided layer after the various processes shown; and (b) range shows the difference between the highest and lowest points of the cross-sectional profile of the top of the highly-nitrided layer. All unit measurements shown are in angstroms. As the data above shows, the furnace annealing processes reduces the range; that is, the difference between the highest and lowest points on the cross-sectional profile of the top of the highly nitrided layer.
[0017] The following table (Table 2) shows data obtained from the furnace annealing process measured by secondary ion mass spectrometry.
SIMS N Elliptical TOF-SIMS SIMS N dose concentration Process Wafer site thickness Thickness e14 at/cm 3 (e21 at/cm 3 ) 1. RTO/RPN Center 20.14 A 15.0 A 9 4 (no anneal) Edge 19.02 A 17.0 A 6 3 Mean 19.65 A 2. RTO/RPN Center 23.24 A 20.0 A 9 4 and Furnace 1 anneal Edge 22.29 A 19.0 A 8 4 Mean 22.80 A 3. RTO/RPN Center 26.25 A 23.0 A 8 3.5 and Furnace 2 anneal Edge 25.50 A 23.0 A 7 3.4 Mean 25.79 A
[0018] Where physical elliptical uniformity is defined as 100*(max-min)/(2*mean), where max and min are the maximum height and minimum height, respectively, of the cross sectional profile of the highly nitrided layer, the processes listed above yielded the following data. Process 1 yielded a physical elliptical uniformity of 2.85%. Process 2 yielded a physical elliptical uniformity of 2.08%. Process 3 yielded a physical elliptical uniformity of 1.42%.
[0019] The table also shows the improvement in concentration uniformity gained by the annealing process. Process 1, in which no anneal was performed, yielded a dose uniformity of 67% and a concentration uniformity of 77%. By contrast, process 2 yielded a dose uniformity of 89% and a concentration uniformity of 100%. Process 3 yielded a dose uniformity of 88% and a concentration uniformity of 97%.
[0020] The Furnace 1 process is a furnace annealing process for 13 minutes N 2 O 700 C. (950C precombustion chamber temperature). The Furnace 2 process is a furnace annealing process at 26 minutes N 2 O 800 C. (950C. precombustion chamber temperature).
[0021] The foregoing description encompasses only the preferred embodiments of the present invention. The following claims and their equivalents define the scope of the invention.
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Methods such as Remote Plasma Nitridation (RPN) are used to introduce nitrogen into a gate dielectric layer. However, these methods yield nitrided layers where the layers are not uniform, both in cross-sectional profile and in nitrogen profile. Subjecting the nitrided layer to an additional NO anneal process increases the uniformity of the nitrided layer.
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This is a continuation of U.S. application Ser. No. 07/419,244 filed Oct. 10, 1989, now abandoned, which in turn is a divisional of U.S. application Ser. No. 07/244,274, filed Sep. 14, 1988 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to superconductive photoconductive-substance of the La-Cu-O system defined to be photoconductive, substance correlative with superconductivity whose composition is outside but includes even areas continuously close to that of regular oxide superconductors. Experiments on the optical properties, especially on the photoconduction in response to high-speed pulses, e.g. a pulsed light out of a dye laser, of substance with a chemical formula of La 2 Cu 1 O z have revealed an unexpected correlation between the superconductivity and the photoconductivity of the substance. The invention also relates to a method for producing the above-mentioned substance. When the substance is cooled very quickly, it becomes a photoconductive semiconductor. On the other hand, when the substance is cooled slowly, it becomes a photoconductive superconductor. The substance in the invention is expected to be useful in developing new industrial field of "Superconductive Opto-Electronics".
2. Related Art Statement
There has been no publications on such a system of substance which has superconductive photoconductivity or both superconductivity and inherent photoconductivity.
Conventional superconductors are metals or alloys in the main. Recently, much attention has been paid to high-temperature oxide superconductors, such as superconductors of the Y-Ba-C-O group, and considerable amounts of additives such as barium (Ba) and strontium (Sr) are used to raise the superconductive critical temperature (T c ). Studies and measurements on the optical properties of the superconductors at and in the proximity of visible wavelengths have been limited to the study of reflection and scattering of light therefrom due to a part of the metallic properties of such substance.
It has been believed that light is simply reflected from or scattered by the surface of a superconductor and is not allowed to enter therein. Study of optical properties, except the phenomena of reflection and scattering, has been treated as a completely different field from that of superconductivity in academic institutions, domestic and abroad, and in international conferences.
On the other hand, if any substance having superconductive photoconductivity or both superconductive capability and photoconductive capability is produced, a number of new electronic and optoelectronic devices may be developed; for instance, a superconductive phototransistor, a "superconductive optical computer" with a combined characteristics of the "superconductive computer" based on the currently studied Josephson devices and the "optical computer" proposed in optoelectronics, "superconductive optical fiber", and the like.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide superconductive photoconductive-substance which reveals superconductive photoconductivity or both superconductivity and photoconductivity at a temperature below its critical temperature therefor.
The superconductive photoconductive-substance according to the invention has a general chemical formula of La 2 -Cu 1 -O z , z being 3.84 to 4.00, which substance shows, at a temperature below 20° K., superconductivity and shows, at a temperature below 30° K., photoconductivity in response to incident light of wavelength 420 to 640 nm. The superconductivity may be potential or real.
Another object of the present invention is to provide a method for producing the above-mentioned superconductive photoconductive-substance which reveals superconductive photoconductivity or even both superconductivity and photoconductivity at a temperature below its critical temperature therefor.
With a method according to the invention for producing the superconductive photoconductive-substance with a general chemical formula of La 2 -Cu 1 -O z , z being 3.84 to 4.00, a mixture of starting materials for a composition of said chemical formula is sintered by heating at 900°-1,050° C. for 5-10 hours, so as to cause solid phase reaction in the mixture. The sintered mixture is cooled gradually, and then shaped under pressure. The shaped mixture is sintered again at 700°-1,200° C., and finally cooled either quickly at a rate of 2,000°-900° C./sec or slowly at a rate of 150°-200° C./hour. Whereby, the substance thus produced shows superconductive photoconductivity or both superconductivity and photoconductivity.
The reason for limiting the composition of the substance of the invention to the above-mentioned general chemical formula is in the inventor's finding that the substance of such composition reveals superconductive photoconductivity or both photoconductivity and superconductivity, real or potential, as shown in the embodiments to be described hereinafter, provided that it is treated by the method of the invention; namely, the method comprising steps of heating at 900°-1,050° C. for 5-10 hours so as to cause solid phase reaction, cooling gradually for shaping, re-sintering at 700°-1,200° C., and cooling the sintered substance either quickly at a rate of 2,000°-900° C./sec or slowly at a rate of 150°-200° C./hour.
The inventors have found that even if the substance of the invention appears to be of insulating type, its photoconductivity depends both on temperature and wavelength of excitation light in such manner that a potential correlation with superconductivity of the substance is implied. The present invention is based on systematic studies on the above finding of the inventor.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the invention, reference is made to the accompanying drawings, in which:
FIG. 1A is a simplified block diagram showing principles of a photoconductivity [(a) dotted arrows] and the Hall effect [(b) solid arrows] measuring circuit which uses blocking electrodes and light pulses;
FIG. 1B illustrates time sequence charts showing waveforms of signals in the circuit of FIG. 1A;
FIG. 2A shows sectional views of an essential part of a static susceptibility measuring device using a microwave SQUID (Superconducting Quantum Interference Device);
FIG. 2B is a block diagram of the measuring system with the device of FIG. 2A;
FIG. 2C is a block diagram of the feedback system with the device of FIG. 2A;
FIG. 3A is a graph of light absorption by Cu 2 O as reported by Grosmann;
FIG. 3B is a graph showing the wavelength-dependence of photoconductive response Q(λ,T) of the semiconducting specimen No., P2 La 2 -Cu 1 -O z , z being about 3.88;
FIG. 3C is a graph showing the wavelength-dependence of photoconductive response Q(λ,T) of the superconducting specimen No. S30 La 2 -Cu 1 -O z , z being about 3.92; and
FIG. 4 illustrates the temperature-dependence of superconductive photoconductive-response Q(λ,T) of both the semiconducting specimen No. P2 La 2 -Cu 1 -O z with z=3.88 and the superconducting specimen No. S30 La 2 -Cu 1 -O z with z=3.92 by the curves (a) and (b), respectively, and the temperature-dependence of dark resistance R(T) of the two specimens No. P2 and No. S30 by the curve (c).
DESCRIPTION OF THE PREFERRED EMBODIMENT
Most of conventional oxide compounds such as La-Cu-O, Y-Cu-O or Y-Ba-Cu-O are normally insulators or semiconductors at the ground state, e.g., at low temperatures and in the dark. An elementary excitation can be created by giving the many-body ground state an appreciable amount of energy with relevant magnitude of momentum. Usually, for superconductors, these excitations beyond the energy gap destroy the superconductive ground state in the BCS theory. There is a possibility, however, to create a coherent state of elementary excitations above the ground state of insulating semiconductors such as bipolarons and excitons even in a thermally non-equilibrium state. We have found a new substance as an outcome of studies in fundamental physics and applied physics from the standpoint of the elementary excitation concept, in a sense parallel to, but rather orthogonal to the trend of studies of high-T c (critical temperature) superconductors. Namely, our finding relates to substance whose composition does not result in perfect super conductor, but the substance has a composition close to that of superconductor and reveals superconductive photoconductivity or both superconductivity and photoconductivity. The present invention has been completed based on that finding.
The invention will be described in further detail now by referring to embodiments.
EMBODIMENTS
The composition of the substance found by the inventors can be expressed by a chemical formula of La 2 -Cu 1 -O z . The inventors have tried to seek into details of the complete scheme of a phase diagram of the substance, especially the variation of its properties for different values of z, i.e., the effects of oxygen deficiency. The studies of the inventors covered not only the superconducting phase but also its semiconducting phase and insulating phase.
A large number of specimens of La 2 -Cu 1 -O z system were made from the powders of La 2 O 3 and CuO. The effect of the composition of the starting materials was carefully studied, and it was found that the oxygen content in terms of the value of z was more or less controllable depending on the speed of cooling.
The specimen No. P2 was made by mixing 3.26 g of La 2 O 3 and 0.795 g of CuO, and sintering the mixture so as to produce La 2 -Cu 1 -O z . The specimen No. S30 was made by mixing 3.26 g of La 2 O 3 and 0.795 g of CuO, and sintering the mixture so as to produce La 2 -Cu 1 -O z . Here, z represents the amount of oxygen in the substance, and it varies depending on the sintering conditions so as to produce a variety of physical properties of the final products.
To make the specimens, for instance, the starting materials of the above composition were measured and thoroughly mixed and crushed, and primary sintering of the starting material mixture was effected at 900°-1,050° C. for 4 hours so as to cause solid phase reaction in the mixture. After being cooled gradually, in general, the sintered mixture was shaped, for instance, into pellets under pressure, and secondary sintering was effected at 1,050° C. for 4 to 6 hours. The specimens No. P2 were very quickly cooled to the temperature of liquid nitrogen (77° K.). The other specimens No. S30 were annealed at 900° C. for 3 hours and at 700° C. for 2 hours and then cooled slowly to room temperature in 4 hours. (In general, said primary sintering can be skipped and the secondary sintering may only be applied therefor at the elevated temperature.)
EXPERIMENTAL METHODS
Despite our study efforts to seek into details, the complete scheme of a phase diagram of La 2 -Cu 1 -O z is still under investigation. Particularly important is the control of oxygen deficiency. Irrespective of enormous efforts of scientists, perhaps it will take a while to complete it. Here, we have been interested not only in the superconductive phase but also in semiconducting phases. A large number of specimens of the La-Cu-O system were made from the powders of La 2 O 3 and CuO by using the method already described in numerous references. Composition of starting materials and the annealing or quenching process have been studied in detail and have become more or less controllable.
Since specimens of the La 2 -Cu 1 -O z system within a certain part of the values of z become highly insulating or at least semiconducting at low temperatures, two types of techniques were adopted for resistivity or/and conductivity measurements in our experiments. First, for insulating specimens (ρ≧10 8 Ω·cm at 4.2° K.) such as No. P2, a fast pulse technique with blocking electrodes as shown in FIG. 1A was adopted to overcome the difficulties previously noted, especially such as those associated with the non-ohmic contact electrodes, the build-up of space charge and with the low signal-to-noise ratio due to low carrier density in high-impedance materials.
In this technique we used, for instance, pulse electric fields up to E≃3 kV/cm with a duration of 10 ms and a repetition rate of 13 Hz were used with a synchronized pulse excitation of light of 3 ns, as shown in FIG. 1B. Second, for moderately conducting specimens (ρ≦(10 -2 -10 -1 ) Ω·cm) such as specimen No. S30, resistivity measurements were performed by adopting the usual four-probe method in the dark without using any exciting light.
Static magnetic susceptibility or magnetization M(T,H) was measured in weak fields up to H≃500 Oe by using a microwave SQUID (Superconducting Quantum Interference Device) at 9 GHz as shown in FIG. 2A and FIG. 2B. The system was normally operated in the mode locked to the Q-pattern as shown in FIG. 2C.
In the measurement of photoconductivity, specimens were optically excited by a pulsed dye laser. Spectral responses were also carefully studied. Photocarrier density was of the order of (10 6 to 10 8 )/cm 3 averaged over a specimen. All photosignals were normally detected in the synchronized mode by using the Boxcar integrator.
EXPERIMENTAL RESULTS
A specimen of La 2 -Cu 1 -O z such as No. S30 looks black and usually has resistivity of the order of ρ≦10 -1 Ω·cm. However, we have observed definite signals of photoconductivity in both of the specimens of La 2 -Cu 1 -O z No. S30 and No. P2 at temperature below 30° K. by applying the transient pulse technique described above.
Firstly, the dependence of photoconductivity Q(λ,T,E,H) on E was found to be almost linear up to E≃3 kV/cm at about 4.2° K. No appreciable magnitude of the transverse and longitudinal magneto-resistance in Q(λ,T,E,H) has been observed up to H≃15 kOe at 4.2° K. FIG. 3B and FIG. 3C illustrate typical spectra of pulse-excited transient photoresponse Q(λ,T) over wavelengths 420 to 640 nm of La 2 -Cu 1 -O z specimens No. P2 and No. S30, respectively. FIG. 3A shows the well established reference data of the optical absorption of Cu 2 O reported by Grosmann. The symbols R, Y, G, B and I on the curve of FIG. 3A represent red, yellow, green, blue and indigo regions, respectively.
Secondly, the values of the magnetizations M(T,H) of the superconducting La 2 -Cu 1 -O z specimen No. S30 has been observed to be very small |χ|<3×10 -8 at most at 4.2° K. Similar phenomena have been reported for the La-Cu-O system by Kang et al. They also observed the critical current and critical magnetic field of superconductivity even for such specimens, so as to prove their superconductive properties.
Thirdly, temperature dependence of the pulse-excited transient photoresponse Q(λ,T) in the region between λ≃420-640 nm were studied both for the semiconducting specimen No. P2 and for the superconducting specimen No. S30 as illustrated in the curves (a) and (b) of FIG. 4, respectively. Surprisingly, there definitely exists a remarkable similarity between general features of the transient photoresponse Q(λ,T) for No. P2 and No. S30, regardless or the huge difference in dark resistivity ρ(T) as illustrated in the curve (c) of FIG. 4. One must clearly recognize an onset of "photoconductivity" Q(λ,T) around 30°-40° K. and after a monotonous increase the slight decrease of Q(λ,T) below 5° K. for both semiconducting and superconducting specimens No. P2 and No. S30.
Finally, the resistivity ρ(T) in the dark of the superconducting La 2 -Cu 1 -O z specimen No. S30 and semiconducting La 2 -Cu 1 -O z specimen No. P2 is displayed in the curve (c) of FIG. 4 as a function of temperature. One immediately notices that the specimen No. S30 becomes superconducting below T≃10°-35° K., whereas the specimen No. P2 becomes insulating.
It is by no means easy to interpret these facts in a simple manner. Heating effects of specimens by light excitations have been carefully examined and estimated to be sufficiently small. At 300° K., both La 2 -Cu 1 -O z specimens No. P2 and No. S30 are semiconductive. In the superconducting specimen No. S30, the "photoconductivity" observed with the blocking electrodes is compatible with "superconductivity" probably due to the insulating part of this specimen as illustrated in the curves (b) and (c) of FIG. 4. Surprisingly, there exists an "occurrence of photoconductivity" potentially correlative with superconductivity underlying even in semiconducting specimen No. P2 as displayed in the curve (a) of FIG. 4.
DISCUSSION
It is a widely recognized fact that the specimens La 2 -Cu 1 -O z usually have dark red or black colors. The spectral response of photoconductivity Q(λ,T) in FIGS. 3B and 3C strongly suggests that there exists a region of the Cu 2 O-like state in the specimen of La 2 -Cu 1 -O z , if not atomic layer.
Optical absorption and photoconductivity of Cu 2 O have been thoroughly analyzed in terms of the exciton theory as a typical example of Mott-Wannier exciton. The positions of the fine structures in the Q(λ,T) coincide with those of the fundamental absorption edge in Cu 2 O. We can recognize a few prominent fine structure probably due to the excitons, e.g., in the yellow series n=2 around λ≃580 nm in the photoconductivity spectra of La 2 -Cu 1 -O z similar to those of Cu 2 O. Thus, we may reasonably conceive that there exists at least a finite fraction of the Cu 2 O-like phase which cannot be ignored in the La-Cu-O systems, where the photoexcited electrons and holes are definitely mobile, irrespective of a certain difference of the crystal structures.
A conduction electron or a positive hole in standard types of Cu 2 O crystals has been reported to form a rather "large polaron" with α≃0.14-0.18, α being a coupling constant with the LO-phonon. The sign of the photoresponse in the Dember effect indicates that, among the carriers generated by the photoexcitation whose life is long and whose contribution is significant, the dominant carriers are conduction electrons in the case of Laz-Cu 1 -O z . In both cases of La-Cu-O system and Y-Cu-O and Y-Cu-Ba-O system, however, an onset of "photoconductivity" Q(λ,T) even in the insulating specimens is clearly associated with an onset of "superconductivity" ρ(T) as if the superconductivity potentially underlies at the back of the photoconductive phenomena. Thus, the dynamical effects of a polaron, whether it is a "large polaron" with the LO-phonons, a "small polaron" due to the Jahn-Teller effect or possibly an intermediate one due to both effects, they must be at least substantially important as indicated in FIGS. 3A through 3C and in curves (a) through (c) of FIG. 4, as well as the "electronic polaron effect". They are probably effective in a coherently hybridized form of these elementary excitation. Here, we pay special attention to the electronic polarons, which one may call "an excitonic polaron". No one can fail to recognize close association among polarons and excitons with the experimental data here.
These polarons and excitons had yielded out of the optical interband transition from the hybridized 2p-Oxygen and 3d-Cu valence bands leaving (3d) 9 positive holes to the 4s-Cu conduction band creating a (4s) 1 conduction electron together with the LO-phonon interaction. A polaron can be created either by the optical excitation here or substitution of La by Ba or Sr, especially in the La-Cu-O system. Since the positive holes in the hybrid 2p(O) and 3d(Cu) bands can be created from the many-body ground state by either an intra- or inter-band transition, the electron correlation effect is naturally important. One must pay more attention to the dynamical valence fluctuation between Cu 1+ and Cu 2+ as well as between Cu 2+ and Cu 3+ . Therefore, for the mechanism of high-T c superconductivity, we may reasonably conceive potential roles of an ensemble of polarons, whether large or small, and especially closely associated excitons. The ensemble of united polarons and excitons here are probably a set of bipolarons, polaronic excitons and/or, most probably, "exciton-mediated bipolarons" due to the dynamical electron-phonon and electron correlation effect. As indicated in the curve (a) of FIG. 4, photosignals Q(λ,T) in the La-Cu-O reflect the occurrence of superconductivity in the La-Ba-Cu-O and La-Sr-Cu-O. Consequently, the inventors believe that these studies of elementary excitations here must reveal the nature of the superconducting ground state, irrespective of an enormous difference in carrier density. To the best knowledge of the inventors, this is the first clear experimental indication of the polaron and exciton mechanisms displayed in the high-T c superconductivity with little diamagnetism.
Here, the inventor reports the first observation of expected accordance of the onsets, i.e., the correlation of "spectral photoconductivity" with "superconductivity (zero resistance)" and little diamagnetism (due to certain reasons) at least in superconducting La-Cu-O system and possibly in semiconducting La-Cu-O system at 4.2° K. to 100° K. Thus, we reconfirm the dynamical mechanism due to polarons and excitons, i.e., "the exciton-mediated bipolarons mechanism" in the high-T c superconductivity.
EFFECT OF THE INVENTION
As described in detail in the foregoing, the inventor has succeeded in providing "superconductive photoconductive-substance" of La 2 -Cu 1 -O z (z being 3.84 to 4.00) system and a "method for producing the substance", which substance has little diamagnetism (due to certain reasons) but has such "photoconductivity" that is correlated with "superconductivity (zero resistance)". The invention has been completed by experiments over a wide range of very low temperatures, i.e., 4.2° K. to 100° K., while measuring electric conductivity by using both the d.c. four-probe method and the repetitive optical pulse method and measuring static magnetic susceptibility by using a microwave SQUID.
It should be noted that the invention is an outcome of theoretical and experimental studies on the "dynamical mechanism of polarons and excitons" or "exciton-mediated bipolarons" for "high-temperature superconductivity" as proposed by the inventor. The proposed substance of the invention will open a new scientific and industrial field, to be named as "Superconductive Opto-Electronics", wherein superconductivity is directly controlled by light.
Although the invention has been described with a certain degree of particularity, it must be understood that the present disclosure has been made only by way of the example and that further numerous changes in details, e.g. an extension to La 2-x Ba x -Cu y -O z and La 2-x Sr x -Cu y -O z , may be resorted to without departing from the scope of the invention as hereinafter claimed.
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The disclosed substance has a general chemical formula of La 2 -Cu 1 -O z , z being 3.84 to 4.00. The disclosed substance shows, at a temperature below 20° K., superconductivity, either potential or real, and the substance also shows, at a temperature below 30° K., superconductive photoconductivity in response to incident exciting light in a wavelength range of 420 to 640 nm. The substance is produced by heating a mixture of starting material therefor at 900°-1,050° C. for 5-10 hours to cause solid state reaction, cooling gradually, shaping under pressure, re-sintering at 700°-1,200° C., and cooling either quickly at a rate of 2,000°-900° C./sec or slowly at a rate of 150°-200° C./hour.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of pending application Ser. No. 874,816 filed Feb. 3, 1978 now U.S. Pat. No. 4,153,287 issued May 8, 1979.
FIELD OF THE INVENTION
The invention relates to snow plows and the like which have means associated with the lower cutting edge of the plow blade for scraping the road surface.
BACKGROUND OF THE INVENTION
In the art of snowplows which are used for clearing roadways and the like, considerable effort has been directed toward designing snowplow devices which are aimed at solving a pervasive problem; namely, clearing as much snow and slush as possible from the roadway while at the same time not damaging the road surface and not allowing irregularities in the road surface to damage the snowplow device.
Several different approaches have been tried. In one approach, a motor vehicle is provided with two separate and distinct means for removing snow and slush. Snow is removed by a scraper blade positioned somewhat above the road surface providing a clearance between the blade and the road. Slush is removed by a motor powered rotary brush whose bristles are disposed radially around a central, rotating axis, and which contact the road surface tangentially. This dual approach is complex and expensive requiring a separate scraper and separate motorized rotary brush.
In a second approach to solve the problem, a resilient, relatively soft rubber strip is attached to the lower edge of a plow blade. This strip contacts the road surface, scraping it and resiliently yielding to surface irregularities. Both snow and slush are removed simultaneously. The relatively soft rubber, however, is in constant contact with the road surface, at relatively high speed, and undergoes rapid wear and must be replaced often.
In a third approach, the entire plow blade, not just the leading edge, responds to surface irregularities. The entire plow blade is pivoted so that its leading edge changes from a sharply acute cutting angle to a broader angle allowing the leading edge to ride over an obstruction in the roadway. When the obstruction is passed, a spring action reorients the entire plow blade so that the leading edge returns to the sharply acute cutting angle. This approach requires a complex support structure for the entire plow blade. Furthermore, it requires a heavy duty spring-loaded device to return the blade to normal position.
Finally, another present approach to solve the problem of maintaining the plow blade in close contact with the road surface while simultaneously yielding to and riding over road surface irregularities is found in a hard plastic strip attached to the leading edge of a plow blade. The hard plastic strip is hard enough to maintain an acute cutting angle of the leading edge under normal circumstances, and it is flexible enough to yield to relatively immovable road surface irregularities, such as manhole covers. However, more easily moved surface irregularities, such as uneven borders between the original road surface and potholes, would be susceptible to plow blade damage because of the relatively acute cutting angle of the hard plastic strip. Another disadvantage of the hard plastic strip is evidenced when the hard plastic strip does yield to an immovable surface irregularity in that the strip does not maintain close contact with the sides of the obstruction. For example, a cylindrical obstruction would cause the hard plastic strip to yield in the geometrical outline of a parabola; it must stretch partially horizontally in order to yield to a vertical obstruction. The open space between the vertical wall of the cylinder and the parabolic outline of the hard plastic strip as it yields to the cylindrical obstruction would allow snow and slush to be missed by the plow blade, and pass under the blade.
In view of the above deficiencies and inadequacies of present snow plow devices, one object of the invention is to provide an attachment for a snow plow which solves the problem of close contact with the road surface while at the same time yielding to and riding over road surface irregularities.
A second object of the invention is to provide a brush attachment for a snow plow which does not require a separate motive source for its operation.
A third object of the invention is to provide a road surface brush that has a hardness greater than a typical road surface and will, therefore, be long-lasting.
A fourth object of the invention is to eliminate the need for a complex support structure for a plow blade which causes the entire plow blade to yield to road surface irregularities in order to broaden the cutting angle.
A fifth object of the invention is to provide a snow plow brush attachment whose bristles readily conform to the outline shape of the surface irregularities thereby preventing snow and slush from passing readily under the blade.
A sixth object of the invention is to provide a road surface contacting brush whose bristles have a hardness greater than ice.
A seventh object of the invention is to provide sharp bristles which assist the snow and slush removal process by cutting and pressure melting ice.
An eighth object of the invention is to provide a device for close contact with a road surface while at the same time pressing and brushing down against surface irregularities rather than scraping and shaving them off.
These and other objects are accomplished by the invention as described below.
SUMMARY OF THE INVENTION
The invention is a snow plow attachment comprised of semirigid bristles affixed to a bristle support which is positioned adjacent to the lower edge of the plow blade. The semirigid bristles of the invention serve plural complementary functions. They have enough rigidity to support that portion of the weight of the plow blade which is not supported by the motor vehicle, and they brush and scrape down the road surface which they contact. Also, they have the flexibility to resiliently ride over road surface irregularities and return to their normal orientation when the irregularities are passed. The plow blade itself may serve as the support for the brush attachment. In this case, the bristle support is attached directly to the plow blade. The bristle support may be attached to the plow blade support, in which case the bristle support and plow blade share a common support.
DESCRIPTION OF THE DRAWING
FIG. 1 shows a side view of a bristle support attached directly to a plow blade.
FIG. 2 shows a side view of a bristle support and plow blade sharing a common support.
FIG. 3 shows a side view of a bristle support attached directly to a plow blade and having its bristles positioned forward of the leading edge of the plow blade.
FIG. 4 shows a side view of a bristle support and plow blade sharing a common support and having its bristles positioned forward of the leading edge of the plow blade.
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the invention is shown in FIG. 1. Road surface 1 is contacted by semirigid bristles 2 which are supported by bristle support 3 which is connected to plow blade 4 adjacent to leading edge 5 by bolt 6. The plow blade 4 is attached to the motor vehicle by support 7. Holes may be drilled in the plow blade 4 which would align with holes in the bristle support 3 for insertion of connecting bolts 6. Alternatively, the bristle support 3 could be clamped onto plow blade 4 without the necessity of drilling holes in the plow blade. The snow plow attachment of the invention would generally extend the length of the plow blade and would be installed adjacent to the leading edge 5.
A second embodiment of the invention is illustrated in FIG. 2. Road surface 1 is contacted by semirigid bristles 2 which are supported by bristle support 3. Bristle support 3 is attached to connecting plate 8 which is attached to plow blade support 7 by means of rivets 9.
Plow blade 4 and bristle support 3 are seen to share common support 7 which is attached to the motor vehicle. The bristle support 3 is installed adjacent to leading edge 5 of the plow blade 4.
A third embodiment of the invention is illustrated in FIG. 3. Bristle support 3 is elongated, having a rearward portion 10 and a forward portion 11. Bolts 6 are used to attach the rearward portion 10 of bristle support 3 to plow blade 4. Forward portion 11 of bristle support 3 is adjacent to leading edge 5 of the plow blade and projects forward of the plow blade. With the semirigid bristles 2 in this position, the snow, ice, and slush are directed upward into plow blade 4. The upper surface 12 of forward position 11 is curved with a radius of curvature similar to the plow blade.
A fourth embodiment of the invention is illustrated in FIG. 4. Bristle support 3 is elongated having rearward portion 10 and forward portion 11. The rearward portion 10 of bristle support 3 is attached to connecting plate 8 which is attached to plow blade support 7 by means of rivets 9. Forward portion 11 of bristle support 3 is adjacent to leading edge 5 of plow blade 4 and projects forward of the plow blade. With the semirigid bristles 2 in this position, snow, ice, and slush are directed upward into plow blade 4. The upper surface 12 of forward portion 11 is curved with a radius of curvature similar to the plow blade.
In the operation of the invention, the bristle support also supports that portion of the weight of plow blade which is not supported by the motor vehicle. As the vehicle moves along the road surface, the bristles press down and brush the road surface. The bristles are semirigid; that is, they are rigid enough to carry a portion of the weight of the plow blade, and they are flexible enough to bend when irregularities in the road surface are encountered. The bristles are also resilient so that after a surface irregularity is passed, the bristles return to their normal orientation. A suitable material for the semirigid bristles is flat wire 0.017 in.×0.059 in.×5 in. made of tempered carbon steel. A suitable bristle holder is a hardwood block. The bristles may be attached to the bristle holder by a variety of methods. One suitable method is to staple the bristles into the hardwood block.
The material of which the bristles are comprised should be selected with due consideration given to bristle durability and long life. One factor affecting the durability is the relative hardness between the bristle material and the material comprising the road surface. The above-mentioned example, tempered carbon steel, satisifies this property in that it has a hardness greater than common road surface materials.
The hardness of the semirigid bristles is greater than that of ice and snow. Therefore, the bristles cut through ice and snow facilitating their removal. The cutting into the ice and snow by the semirigid bristles, has an additional benefit. Just as the metal blade of an ice skate melts a thin layer of ice by pressure thereby providing a thin layer of liquid water which serves as a lubricant, the semirigid bristles of the invention pressure melt some ice and snow thereby providing a thin film of liquid water serving as a lubricant, thereby lowering considerably the frictional resistance that the ice and snow impose upon the inertia of the snow plow.
The effectiveness of the brushing action of the bristles can be affected by changing one or more of three variables; namely, bristle material, bristle density, and bristle length. A high bristle density of coarse bristles which are short results in a more rigid character of the semirigid bristles. A low bristle density of the fine bristles which are long results in a more flexible character of the semirigid bristles. An optimum choice depends on the particular set of factors in question. Regarding a snow plow, factors such as the weight of the plow blade which rests on the bristles, the clearance between the leading edge of the plow blade and the road surface, and the ambient temperature at which the plowing is expected to occur are important.
In choosing bristle materials, both ferrous and non-ferrous metals may be used. Hard polymeric material may also be employed.
A heretofore unstated additional advantage of the invention is also realized. Because more snow and slush is removed by the invention than with present devices, less snow and ice is left as a residue on the road surface which will require treatment with salt or abrasives. Therefore, a truckload of salt or abrasives will have a greater area of application than with present devices. Furthermore, by placing less foreign material such as salt or abrasives on the road surface, the road surface, itself, will undergo less deterioration and disintegration than currently occurs. The economic savings in road surface repair would be substantial.
If desired, the bristle support could be adjustably attached to the plow blade or to the plow blade support. Adjustments could be made for lifting the bristles out of contact with the road surface completely, or they could be made to change the angle of attack of the bristles on the road surface. Adjustments could be made manually or by powered means.
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A bristle support, having semirigid long lasting bristles, is attached to a snow plow near the lower cutting edge of the plow blade so that the semirigid bristles project below the blade edge and serve the multiple functions of: rigidly contacting the surface to be cleared thereby providing a cutting action on the undesired material on the surface to be cleared and a brushing of the surface; and at the same time having the flexibility to yield to and ride over small surface irregularities and resiliently return to normal position when the irregularities are passed.
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The present application is the national phase of International Application No. PCT/CN2013/090390, titled “TIME LABEL COMBINATION METHOD AND SYSTEM”, filed on Dec. 25, 2013, which claims the priority Chinese Patent Application No. 201310583127.6, titled “TIME LABEL COMBINATION METHOD AND SYSTEM” and filed with the Chinese State Intellectual Property Office on Nov. 19, 2013, both of which are incorporated herein by reference in entirety.
FIELD
The present disclosure relates to the fields of digital signal processing, photoelectric signal processing and nuclear detection, and particularly to a method and system for combining time labels of arrive of events.
BACKGROUND
In the field of nuclear analysis such as a positron lifetime spectrometer or a positron angle-momentum association analyzer, the field of nuclear detection such as double-coincident high-energy-particle discrimination and the field of medical imaging such as positron emission tomography (abbreviated as PET), a detector has two operating principles. That is, one operating principle is to convert, by a scintillator, a high-energy photon into a visible photon or an ultraviolet photon having low energy, and then convert, by a photoelectric device, the visible photon or the ultraviolet photon into an electrical signal; and the other operating principle is to directly convert a high-energy photon into an electrical signal by a semiconductor material such as Cadmium Zinc Telluride (abbreviated as CZT). The detector outputs the electrical signal in the two operating principles described above.
In a PET system, system performance is improved and an application scope is extended in a case of good time resolution. First, in a case that the time resolution is good enough (for example, less than 800 picoseconds), a location where positron annihilation occurs is deduced based on a time difference of the arrival of two electrical pulses, a value of the location meets the Gaussian distribution, and the full width half maximum of the distribution is less than 12 cm (corresponding to 800 picoseconds). Information on the location has a significant effect on improving a signal-to-noise ratio of an image. Secondly, the good time resolution can facilitate rejecting scattering better, and improving system noise equivalent counting. Thirdly, since the time difference has a positioning ability for a coincident event along a direction of a line of response (abbreviated as LOR), a completeness requirement for a projection data may be reduced by reestablishing a PET image having time information, and thus an image can be reestablished with incomplete data. Again, attenuation data and emission data can be acquired simultaneously in the PET system having the time information, to shorten a scanning time period, and reduce complexity of a hardware system. Also, multiple mice can be imaged respectively at the same time in the system, and aliasing is prevented.
In order to improve the time resolution of the system, there are three normal methods, that is, a method a, a method b and a method c. The method a is to select a crystal having fast attenuation. The method b is to select a photon multiplier tube having small transit time spread and high quantum efficiency. The method c is to optimize a time label method. The method a and the method b are given, the method c is a concerned issue in the art.
A leading edge discrimination (abbreviated as LED) is used as a simplest time label method for acquiring time of arrival of a pulse in a PET data acquiring system. A reference voltage is set, and time when a voltage amplitude of a pulse exceeds the reference voltage represents time of arrival of a signal event. The method is widely used in a case that a rising edge of a processing pulse is steep and a change in the amplitude is small since the method is easy to be implemented and time jitter caused by noise is small. The method has disadvantages that time walk occurs since the method is vulnerable to the amplitude of the pulse and the rise and fall of a slope of the rising edge, thereby reducing accuracy of the time label.
In order to eliminate the time walk due to the amplitude of the pulse, a constant fraction discrimination (abbreviated as CFD below) is set forth, in which, a scintillation pulse includes two signals. One signal is attenuated and reversed at an attenuation terminal of the CFD, and the other signal is delayed for a constant time period at a delay terminal of the CFD. The delayed signal and the attenuated and reversed signal are added to generate a bipolar signal, and a zero-crossing point of the bipolar signal is detected by a zero-crossing discrimination in the CFD. A time instant of the zero-crossing point is time of arrival of a time label event of the CFD. The delay time period and an attenuating proportion in the CFD are preferred, a timing error caused by the amplitude of the pulse and rising time fluctuation is eliminated by the CFD, and therefore good time performance can be obtained for the PET data acquiring system.
Whether the LED method or the CFD method is developed based on an analog circuit in a conventional time acquiring system. Performance parameters of the analog circuit drift with a change in time, a temperature and an operating environment, and it is difficult to maintain the analog circuit in a state of high performance in an actual system. Specifically, it is a huge challenge to correct the performance parameters for a system such as the PET having thousands of detection channels.
With the rapid development of digital technology the digital leading edge discrimination (abbreviated as DLED below) and the digital constant fraction discrimination (abbreviated as DCFD below) have gradually become an important time label method. The two digital time label methods can be flexibly implemented in a digital device such as a field programmable logic array (abbreviated as FPGA below), a digital signal processor (abbreviated as DSP below). However, their performances are limited by a sampling ratio of an analog-to-digital convertor (abbreviated as ADC below) to a great extent, since an existing PET detector is inclined to select a scintillation crystal having a small attenuation time constant and an photon multiplier tube (abbreviated as PML below) having a fast rising time period to acquire good time performance and counting ratio performance. Taking a mainstream scintillation detector such as LSO/PMT as an example, a rising time period of a scintillation pulse signal outputted from the scintillation detector is normally in a range from 1 ns to 20 ns, and duration of the pulse is 200 ns. In order to achieve time performance the same as or similar to that of the CFD method in a case that time of arrival of the pulse is acquired by the DCFD method and no filtering processing is performed on the scintillation pulse, a sampling ratio of the ADC used in the DCFD method is at least up to 1 Giga samples per second (abbreviated as GSPS below). However, it is no doubt that the high sampling ratio of the ADC brings up troubles of high cost, ultra-high data throughout and ultra-high data processing for the PET. Similarly, a digital pulse time extraction method based on the ADC sampling, such as the mean PMT pulse model (abbreviated as MPPM below), the maximum rise interpolation (abbreviated as MRI) and the initial rise interpolation (abbreviated as IRI below) may also get into a conflict between a high sampling ratio requirement and a high time resolution performance.
Therefore, with regard to the technical problems described above, it is necessary to provide a new time label combination method and system for data volume which can be acquired, to overcome the disadvantages described above.
SUMMARY
In view of this, an objective of the present disclosure is to provide a time label combination method and a time label combination system, to effectively combine multiple original time labels or original event shape fluctuation properties, explore a component associated with time information in digital quantity which can be measured, and improve resolution of the time labels.
In order to achieve the objective described above, the present disclosure provides technical solutions below.
A time label combination method is provided, which includes:
S 1 , collecting a digital quantity measurement value of a data acquisition system, and establishing a database for the measurement value;
S 2 , recognizing atomic time label quantities and shape fluctuation statistics;
S 3 , estimating a covariance matrix of the atomic time labels; and
S 4 , giving a time label combination according to the least square criterion.
Preferably, in the time label combination method described above, the time label combination is a combination of multiple atomic time labels and event shape fluctuation properties.
Preferably, in the time label combination method described above, a sum of weighting factors of all atomic time labels in the time label combination is equal to 1.
Preferably, in the time label combination method described above, weighting factors of the event shape fluctuation properties are any real number not equal to 0.
Preferably, in the time label combination method described above, the weighting factors of the atomic time labels and the weighting factors of the event shape fluctuation properties constitute a set of all parameters of the time label combination.
Preferably, in the time label combination method described above, a point source having low activity is used as a standard for establishing the database in step S 1 .
A time label combination system is provided, which includes: a low-dose pre-acquisition data module, a digital quantity recognition module, a digital quantity variance calculation module and a time label combination parameter calculation module, where
the low-dose pre-acquisition data module is configured to store a pre-acquired digital quantity having a low counting ratio;
the digital quantity recognition module is configured to recognize whether the pre-acquired digital quantity outputted from the low-dose preset-acquisition data module is an atomic time label or an event shape fluctuation property;
the digital quantity variance calculation module is configured to calculate a covariance matrix of the atomic time label and determine a parameter of a time label combination; and
the time label combination parameter calculation module is configured to test and operate the acquired parameter of the time label combination.
As can be seen from the technical solutions described above, the time label combination method and the time label combination system according to the present disclosure can effectively improve time resolution of the system, and are particularly suitable for time acquisition of a digital nuclear instrument.
Compared with the conventional technology, the present disclosure has advantageous effects as follows:
(1) good time resolution, that is, the quality of an image outputted in an imaging mode related to the time resolution is raised, and event discrimination accuracy related to the time resolution is raised; and
(2) good adaptability for different scintillation detector systems.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings to be used in the description of the embodiments or the conventional technology are described briefly as follows, so that the technical solutions according to the embodiments of the present disclosure or according to the conventional technology become clearer. It is apparent that the drawings in the following description related to the present disclosure only illustrate some embodiments of the present application. For those skilled in the art, other drawings may be obtained according to these drawings without any creative work.
FIG. 1 is a flow diagram of a time label combination method according to the present disclosure;
FIG. 2 is a structural diagram of a time label combination system according to the present disclosure;
FIG. 3 is a scintillation pulse sample according to the present disclosure;
FIG. 4 is scintillation pulse data after alignment operation in a database according to the present disclosure;
FIG. 5 is a schematic diagram of a multi-leading-edge time label discrimination method according to an embodiment of the present disclosure;
FIG. 6 is a schematic diagram of a multi-convolution/leading-edge time label discrimination method according to an embodiment of the present disclosure;
FIG. 7 is a schematic diagram of a leading-edge and trailing-edge time label discrimination method according to an embodiment of the present disclosure;
FIG. 8 is a time difference spectrum of leading-edge discrimination according to an embodiment of the present disclosure;
FIG. 9 is a time difference spectrum of multi-convolution/leading-edge discrimination according to an embodiment of the present disclosure;
FIG. 10 is a time difference spectrum of leading-edge and trailing-edge discrimination according to an embodiment of the present disclosure;
FIG. 11 is a schematic diagram of a typical system according to the present disclosure; and
FIG. 12 is a schematic diagram of another typical system according to the present disclosure.
DETAILED DESCRIPTION OF THE EMBODIMENTS
A time label combination method and a time label combination system are provided in the present disclosure, which can effectively label time of arrive of an event, and improve time resolution of a module and the system.
Technical solutions according to embodiments of the present disclosure are described in detail hereinafter in conjunction with drawings in the embodiments of the present disclosure. Apparently, the described embodiments are only some of rather than all of the embodiments of the present disclosure. Any other embodiments obtained by those skilled in the art based on the embodiments of the present disclosure without any creative work fall into the scope of protection of the present disclosure.
As shown in FIG. 1 , in a time label combination method disclosed in the present disclosure, a database is established by a digital quantity collected, the established database is used to train and test a combination way of atomic time labels. The method includes:
S 1 , collecting a digital quantity measurement value of a data acquisition system, and establishing a database for the measurement value;
S 2 , recognizing atomic time label quantities and shape fluctuation statistics;
S 3 , estimating a covariance matrix of the atomic time labels;
S 4 , giving a time label combination according to the least square criterion.
In step S 1 , a point source having low activity is used as a standard for establishing the database. A parameterized time label is trained by a system digital quantity generated by the point source having low activity, to output various parameters of the time label via training. A different sample is used in testing or using the time label.
In step S 1 , the data acquisition system may be a readout system including a preamplifier, a pulse shaping circuit and an equidistant analog-digital converter, may also be a system (for example, multi-voltage threshold readout system) in which pre-amplification and shaping is read by multiple comparators.
In step S 1 , for the established database, generally types of the properties of the pulse are greater than or equal to 2, and the number of samples is greater than 1000.
In step S 2 , the atomic time label quantities and the shape fluctuation statistics are recognized by comparing the atomic time label quantities and the shape fluctuation statistics with a true value. In the process of training, the true value of the time label is calculated based on a position of an emission source. The true value is used as a standard for the training.
In step S 2 , in a case that a derivative of an expected value of a property with respect to the position of the emission source is equal to 2/c, the property (or pulse characteristic) is the atomic time label quantity. In a case that a derivative of an expected value of a property with respect to the position of the emission source is equal to zero, the property is the shape fluctuation statistics. In a case that a derivative of an expected value of a property with respect to the position of the emission source is not equal to zero and is not equal to 1, the property is a combination of the shape fluctuation statistics and the atomic time label. Both the shape fluctuation statistics and the atomic time label are provided to S 3 , which are a part of the time label combination, and are also a property of the pulse. The property of the pulse includes an atomic time label property and a shape fluctuation property.
In step S 3 , the covariance matrix includes associations between various properties. In a case that the atomic time label and the shape fluctuation are selected, the associations become prior knowledge for determining weights of the atomic time label and the shape fluctuation in the combination. The covariance matrix is used in the least square criterion in S 4 .
In step S 4 , the time label combination is a combination of multiple atomic time labels and the event shape fluctuation properties.
In step S 4 , a sum of weighting factors of all atomic time labels in the time label combination is equal to 1, which is used as a constraint condition. The lease square is used as an objective in a case that the constraint condition is met, to search a solution. The solution includes all parameters of the time label.
A weighting factor of the event shape fluctuation property is any real number not equal to zero.
The weighting factor of the atomic time label and the weighting factor of the event shape fluctuation property constitute a set of all parameters of the time label combination. Weighting factors of the time label combination are selected according to the least square criterion or other objective functions including a least square item, for example, L1 norm or other norm is added onto L2 norm with an error, which all fall within the protection scope.
As shown in FIG. 2 , a time label combination system is disclosed in the present disclosure, which includes a low-dose pre-acquisition data module 100 , a digital quantity recognition module 200 , a digital quantity variance calculation module 300 and a time label combination parameter calculation module 400 .
The low-dose pre-acquisition data module 100 is configured to store a pre-acquired digital quantity having a low counting ratio. The digital quantity having a low counting ratio may be other digital quantity of the time label combination method disclosed or other digital quantity which affects the time label combination method.
The digital quantity recognition module 200 is configured to recognize whether the pre-acquired digital quantity outputted from the low-dose preset-acquisition data module 100 is an atomic time label or an event shape fluctuation property.
The digital quantity variance calculation module 300 is configured to calculate a covariance matrix of the atomic time label and determine a parameter of a time label combination; and
The time label combination parameter calculation module 400 is configured to test and operate the acquired parameter of the time label combination.
As shown in FIG. 3 to FIG. 10 , the present disclosure is further understood in conjunction with FIG. 3 to FIG. 10 .
FIG. 3 is a scintillation pulse sample according to the present disclosure, a rising time period of the pulse is approximately 0.7 ns, a time constant (a time period during which the pulse is attenuated to 1/e) of a falling edge of the pulse is approximately 22 ns, and the pulse is an electrical pulse outputted from R9800 and is collected by a high-speed oscillograph DPO71604.
FIG. 4 is a scintillation pulse data after alignment operation in a database according to the present disclosure. The pulses are drawn in a timeline after the time of arrival of the pulses is aligned. A main noise type of the scintillation pulse can be deduced from an envelope line of the data.
FIG. 5 is a schematic diagram of a multi-leading-edge time label discrimination method according to an embodiment of the present disclosure. The multi-leading-edge time label discrimination method is an example of multi-threshold time discrimination, for which only the rising edge which changes fast is considered and an influence of the falling edge on the time performance is ignored for an encoding part. The label discrimination method is shown in FIG. 5 , which includes a comparator array, a logic signal acquisition unit and an interpolation or correction module.
FIG. 6 is a schematic diagram of a multi-convolution/leading-edge time label discrimination method according to an embodiment of the present disclosure. The multi-convolution/leading-edge time label discrimination method is achieved by adding an analog convolution module before the leading-edge discrimination, for which only the rising edge which changes fast is considered and an influence of the falling edge on the time performance is ignored for an encoding part. The analog convolution module may be composed of resistance-capacitance circuits, or may be achieved with a differential line and a subtraction circuit. A typical method of the multi-convolution/leading-edge time label discrimination is shown in FIG. 6 , which includes a CFD array, a logic signal acquisition unit and an interpolation or correction module.
FIG. 7 is a schematic diagram of a multiple leading-edge and trailing-edge time label discrimination method according to an embodiment of the present disclosure. The multiple leading-edge and trailing-edge time label discrimination method is an example of the multi-threshold time discrimination, for which not only the rising edge which changes fast is considered, but also an influence of the falling edge on the time performance is considered for an encoding part. The method of the multiple leading-edge and trailing-edge time label discrimination is shown in FIG. 7 , which includes a comparator array, a logic signal acquisition unit and an interpolation or correction module.
FIG. 8 is a time difference spectrum of multi-leading-edge discrimination according to an embodiment of the present disclosure, and the time difference spectrum is given by a method in FIG. 5 .
FIG. 9 is a time difference spectrum of multi-convolution/leading-edge discrimination according to an embodiment of the present disclosure, and the time difference spectrum is given by a method in FIG. 6 .
FIG. 10 is a time difference spectrum of a multiple leading-edge and trailing-edge discrimination according to an embodiment of the present disclosure, and the time difference spectrum is given by a method in FIG. 7 .
As shown in FIG. 3 , FIG. 11 and FIG. 12 , FIG. 11 is a schematic diagram of a typical system in an operating mode according to the present disclosure, FIG. 12 is a schematic diagram of a typical system in another single-channel operating mode according to the present disclosure. Specifically, 500 represents a scintillation crystal, 600 represents an emission source, 700 represents a photomultiplier tube, 800 represents a digital oscilloscope. In conjunction with FIG. 3 , FIG. 11 and FIG. 12 , the time label combination method and the time label combination system according to the disclosure are further described by way of multiple embodiments. In the time label combination method and the time label combination system according to the present disclosure, the related parameters and filter design should be adjusted based on characteristics of acquired data, to achieve good energy resolution performance and short pulse duration. Parameters for processing data in the application embodiments are listed here.
First Embodiment
Parameters for processing data in the first embodiment are listed here.
In an actual system used in step (1), a LaBr crystal and a Hamamassu R9800 PMT are used, and the size of the crystal is 10.0 mm×10.0 mm×10.0 mm. Coupling surfaces between the crystal and the PMT include 100 surfaces, surfaces other than the coupling surfaces are packaged by metal. The data acquisition system has a sampling ratio of 50 Ghz and a bandwidth of 16 Ghz. The emission source is a positron annihilation gamma photon of 511 kev. A coincident time is approximately 2 ns, and an energy window is approximately in a range from 400 keV to 600 keV.
Leading-edge discrimination of multiple voltage threshold parameters is used as an atomic label in step (2).
In step (3), one atomic time label is added every time, the time label added every time increases the time resolution at best. In a case that the increased time resolution is greater than 1 ps, no additional LED leading-edge threshold is increased.
In testing and using in step (4), parameters of the time label combination obtained in step (3) are used.
Second Embodiment
Parameters for processing data in the second embodiment are listed here.
In an actual system used in step (1), a LaBr crystal and a Hamamassu R9800 PMT are used, and the size of the crystal is 10.0 mm×10.0 mm×10.0 mm. Coupling surfaces between the crystal and the PMT include 100 surfaces, surfaces other than the coupling surfaces are packaged by metal. The data acquisition system has a sampling ratio of 50 Ghz and a bandwidth of 16 Ghz. The emission source is a positron annihilation gamma photon of 511 kev. A coincident time is approximately 2 ns, and an energy window is approximately in a range from 400 keV to 600 keV.
Four fixed CFD digital quantities and four fixed EN-LED digital quantities are used in step (2).
In testing and using in step (4), parameters of the time label combination obtained in step (3) are used.
Third Embodiment
Parameters for processing data in the third embodiment are listed here.
In an actual system used in step (1), a LaBr crystal and a Hamamassu R9800 PMT are used, and the size of the crystal is 10.0 mm×10.0 mm×10.0 mm. Coupling surfaces between the crystal and the PMT include 100 surfaces, surfaces other than the coupling surfaces are packaged by metal. The data acquisition system has a sampling ratio of 50 Ghz and a bandwidth of 16 Ghz. The emission source is a positron annihilation gamma photon of 511 kev. A coincident time is approximately 2 ns, and an energy window is approximately in a range from 400 keV to 600 keV.
Four fixed leading-edge over-threshold time digital quantities and four fixed trailing-edge over-threshold time digital quantities are used in step (2).
In testing and using in step (4), parameters of the time label combination obtained in step (3) are used.
The method and the system according to the present disclosure can be applied to nuclear detection, nuclear analysis and a nuclear medicine instrument with a high counting ratio.
In the time label combination method according to the present disclosure, a time label parameter combination of an event pulse is acquired by a point source having low activity. Measurable data quantities are provided from low-dose point source data, and the data quantities are stored into a database. The database of the digital quantities reflects coupling relations between various basic time labels and event shape fluctuation properties. An optimization equation is solved with addition constrain based on an objective function of the least square criterion. A variable to be optimized in the optimization equation is a parameter of the time label combination.
With the time label combination method and the time label combination system disclosed in the present disclosure, the time resolution can be improved, and the image quality is improved by introducing time information in reconstruction, so that detection geometry for incomplete data which can not be achieved in a conventional PET can be reconstructed accurately, and a positron annihilation lifetime spectrometer outputs a lifetime spectroscopy having a wider bandwidth, and can detect some short lifetime physical processes. In an attenuation and correction process, good enough time of flight (abbreviated as TOF) information is introduced, and thus the attenuation coefficient may be taken as a constant. In some detection devices in which double coincidence, anticoincidence and multiple coincidences are used, a particle counting ratio detected can be increased and a spread of likelihood function in list data can be reduced in the same coincident ratio. In addition, multiple new applications such as dynamic PET scanning, attenuation data and the emission data simultaneous acquisition become possible since the time resolution becomes good.
The time label combination method and the time label combination system according to the present disclosure improves the time resolution of the system effectively, and are suitable for time acquisition of a digital nuclear instrument.
Compared with the conventional technology, the present disclosure has advantageous effects as follows:
(1) good time resolution, that is, the quality of an image outputted in an imaging mode related to the time resolution is raised, and event discrimination accuracy related to the time resolution is raised; and
(2) good adaptability for different scintillation detector systems.
It is apparent for those skilled in the art that the present disclosure is not limited to details of the exemplary embodiments described above, and can be implemented in other embodiments without departing from spirit or basic features of the present disclosure. The embodiments are considered in all respects to be exemplary and non-restrictive. The scope of the present disclosure is limited by the appended claims rather than specification described above, all changes within meaning and scope of equivalent elements of the claims are included in the present disclosure. Any reference number in the claims is not considered to limit the claims related to the reference number.
In addition, it should be understood that, although the present disclosure is described based on the embodiments, not every embodiment includes only one separate technical solution, the description way in the specification is just for the sake of clarity those skilled in the art should regard the specification as a whole, the technical solution of each of the embodiments may also be combined to form other embodiments which can be understood by those skilled in the art.
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A time label combination method, comprising the steps: collecting data acquisition system digital measurement values and establishing a database for the measured values; identifying atomic time label quantities and shape fluctuation statistics; estimating a covariance matrix of each atomic time label; according to the least squares criterion, giving the time label combination. Also provided is a time label combination system, comprising a low-dose pre-acquisition data module, a digital identification module, a quantitative variance calculation module, and a time label combination parameter calculation module. By means of using the described time label combination method and system, system and resolution is effective increased, and the invention is particularly suitable for nuclear instrument time acquisition.
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This is a continuation of application Ser. No. 169,035 filed July 15, 1980, and now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to insulation of crawl spaces or other hard to reach spaces of a building and more particularly to a means and method of safely transporting the insulation to the area of interest.
2. Prior Art
It is well known that insulation for buildings may be purchased in rolls or linear batts in which insulation material including rock wool or glass fibers are secured to a backing sheet of paper stock or of an aluminum foil. Typical glass fiber insulation rolls are formed by long strips of insulation rolled about its width or lateral axis and are of the following sizes as purchased from a merchant or manufacturer:
______________________________________INSULA- PACKAGEDTION ROLLVALUE WIDTH LENGTH DIAMETER NOTES______________________________________R11 151/4" 38'6" 26" Plain or Foil FacedR11 23" 70'6" 26" Plain or Foil FacedR19 23" 39'2" 26" Plain or Foil Faced______________________________________
Insulation batts may have the same insulation value, width and facing but is only about 4 feet in length and packaged with several batts in a package.
In order to insulate hard to reach spaces, such as crawl spaces in the attic of a building the insulation rolls are unrolled prior to transportation to the attic and the batts-type is removed from its package. This is especially true for insulating those areas which have a small opening through which the rolls or packages of batts can not be passed when packaged as purchased. Since the insulation rolls are unrolled prior to being carried to the place to be insulated, the backing may become damaged, the insulation may be torn loose from the backing, and glass fibers may come loose and contaminate the air which is breathed. Loose fibers are injurious to the health and torn or damaged insulation may not insulate the area as required.
SUMMARY OF THE INVENTION
A long, narrow heavy plastic or other type of flexible material having a width and length greater than the insulation to be transported is provided with securing means on its edges to enclose the insulation in a longitudinal roll. By enclosing the insulation in a longitudinal roll, the insulation may be passed through a small opening having a diameter, which is considerably less than that of the diameter of a rolled roll of insulation in its regular rolled form and not enclosed within the flexible material.
It is therefore an object of the invention to transport building-type insulation to hard to reach spaces without damage to the insulation while protecting the workman from harmful effects of the insulation.
Another object is to prepare the insulation for passage through small openings without damage to the insulation when passed through the small opening.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 represents a roll of insulation partially unrolled.
FIG. 2 is an enlarged transverse or lateral cross-sectional view of an elongated plastic or fabric material for transporting insulation through a small opening to the space of interest.
FIG. 3 illustrates a plastic or fabric material with two unrolled rolls of insulation thereon.
FIG. 4 is a cross-sectional view illustrating two insulation strips assembled within the plastic or fabric material encircling the insulation.
FIG. 5 illustrates a plastic or fabric material enclosure with insulation therein being passed through a small opening into an area for use.
DETAILED DESCRIPTION
Referring to the drawings wherein like references represent like parts in the different views, there is shown in FIG. 1 a roll of insulation 10, which is partially unrolled to better illustrate the relative structure. For illustrative purposes, the line 12 represents the lateral axis about which the insulation roll is rolled and the arrow 14 represents the longitudinal axis which will be explained later.
FIGS. 2 and 3 illustrate a strip of plastic or fabric material 16 including a male edge 18 and a female edge 20. The male edge has ridges 18a, 18b and 18c which may be pressed into valleys 20a, 20b and 20c in the female edge so that they fit together, such as a plastic zipper in order to form an enclosure when zipped together. The strip of plastic material is wider than the width of a roll of insulation and is longer in length than the roll of insulation in its unrolled state. The male and female edges are shown as separate parts molded to the edges of the plastic sheet. The plastic sheet could be made with thicker edges and the male and female structure formed along the thicker edge portions. Plastic zippers are well known in the art and the zipper structure may be made with well known practices in the art. The important thing is, that the edges of the transport material be connected together along the length of the transport device so that the insulation may be enclosed therein for transport.
FIG. 3 illustrates the insulation transport material laid out flat with two rolls 10 of insulation unrolled along the length of the transport material. The transport material must be of a length which is longer than that of the insulation when unrolled, and of a width which is wider than the width of the insulation, as shown. The insulation transport device in accordance with the teaching of this invention is rolled along its longitudinal axis 14, shown in FIG. 1, and its edges are secured together beginning at one end while enclosing the insulation therein as the transport device is rolled about its longitudinal axis. The edges of the transport device are secured together from one end to the other. The insulation transport device is made of a plastic or fabric, which is flexible so that transport device with the insulation therein will be flexible. Since the insulation is rolled along its longitudinal axis the completed roll within the transport device is much smaller than the roll of insulation as purchased when rolled about its lateral axis. It is obvious from FIG. 4, which illustrates two unrolled rolls of insulation therein, that the insulation enclosed within the transport device will pass through a much smaller opening than it would in its original roll. FIG. 4 further illustrates a means 22 for forcing the edges of the transport device together. The means 22 is also made to separate the edges for removal of the insulation once the insulation has been transported to its desired space in the building.
FIG. 5 illustrates an opening 24 in a building structure 26 through which the insulation transport device with insulation enclosed therein may be passed for transporting the insulation to a desired work area. A longitudinally rolled transport device with insulation therein is shown being passed through the opening.
In carrying out the teaching of the invention, the plastic insulation transport material enclosure of sufficient width and length is spread out in its open form in an open work area such as outside of a building. One roll of insulation is laid upon the open plastic material and unrolled with each end of the insulation within the length of the plastic material. The plastic material transport device is then rolled along the longitudinal axis and zipped along its edges to enclose the length of insulation. More than one layer of insulation may be laid-out on the plastic material, as shown, if the opening through which the plastic material insulation transport means is to be passed is sufficiently large to pass more than one roll of insulation. Of course, if the opening is not large enough to handle more than one bundle of insulation at the same time, only one bundle will be enclosed within the plastic material transport device.
Once the transport device with the insulation enclosed therein has been passed through the opening to the area to be insulated, the transport device is unzipped and the insulation removed. The insulation may be removed by flipping the plastic transport device which will lay the insulation flat. In the event the insulation is to be placed above the ceiling in the spaces between joists of a lower room, the insulation should be laid on the transport device with the foil side up so that when it is flipped-over, the foil side will be down in proper order to be placed in between the joists. Also, if the insulation is to be placed in the rafters, the insulation will be placed on the transport device with the foil up. When flipped, the insulation will be in the proper position for raising the insulation to the rafters.
Once the insulation has been removed from the transport device, the transport device is passed back through the opening to be reloaded with one or more unrolled rolls of insulation.
It will be obvious to one skilled in the art that batts of insulation may be placed upon an opened transport device with the batts laid end to end along the length of the transport device and the transport device rolled along its longitudinal axis and zipped together. In this manner, several batts can be transported to the work area at the same time. More than one layer of batts may be placed on the transport device, provided the opening, through which the loaded transport device is passed, is sufficiently large to pass the transport device with more than one layer of batts therein.
The insulation transport device has been shown with the linear edges zipped together which form an upstanding ridge. It will be obvious that the female slots could be on the other side of the linear edge so that the male linear edge would overlap the female edge and join together to form a more flat enclosure. The particular zipper used does not add or substract from the invention, but relates to one manner of securing the edges of the insulation transport device together so that an enclosure is formed. Other means for closing the device may be used without detracting from the invention. Plastic zippers are well known in the art for various uses. Such zippers may be used in this invention.
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A method and insulation transport device for transporting building-type rolled insulation or batts of insulation through an opening in a building to an area to be insulated, such as a crawl space, in which the opening to the area to be insulated is of less diameter than that of the roll of insulation or package of batts.
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BACKGROUND OF THE INVENTION
(1) Field of the Invention:
The present invention relates to light sensitive compositions, more particularly, to compositions comprising highly sensitized polymethyl isopropenyl ketone which is a photoresist for fine pattern processing.
(2) Prior Art:
Recently, for the development of super LSI, lithography of a precision of up to submicron units attracts public attention. However, according to conventional photolithography, patterns of less than 1 μm cannot be formed due to phenomena such as diffraction and interference of light, since ultraviolet rays having wave lengths of from 350 to 450 nm are used. Under the circumstances as above, techniques of electron beam exposure and soft X-ray exposure are now being developed. However, the electron beam exposure technique has disadvantages in that a large-sized computer is used and a long exposure time is required. Therefore, this technique is impractical for wafer transfer. In the soft X-ray exposure technique, there is no practical light source and mask fitting is very difficult. Further, in both techniques, devices necessitated are very large in size and extremely expensive.
If the ultraviolet rays of wave lengths of 350-450 nm employed in the conventional photolithography can be replaced with ultraviolet rays of shorter wave lengths of 100-350 nm, formation of ultrafine images or patterns of less than 1 μm, is made possible, the conventional lithographic techniques can be used, and light sources such as low pressure mercury lamps, heavy hydrogen lamps and xenon-mercury lamps can be used. Therefore, this is economical and most practical for forming ultrafine images.
After intensive investigation on the techniques of forming ultrafine patterns by irradiation with ultraviolet rays of having wave lengths of from 100 to 350 nm, from this point of view, the inventors found previously that polymethyl isopropenyl ketone has a high sensitivity to ultraviolet rays of wave lengths of 100-350 nm and that a composition comprising the polymethyl isopropenyl ketone combined together with a benzophenone derivative exhibits a higher sensitivity and acts as a resist suitable for the preparation of super LSI (German Patent Application No. P.28 47 764.7 and U.S. application Ser. No. 961,120, filed Oct. 16, 1978.).
FIG. 1 shows spectral sensitivity of polymethyl isopropenyl ketone. The sensitivity range of polymethyl isopropenyl ketone is divided into two parts. Particularly, in a range of wave lengths of 210-260 nm, a high sensitivity is not necessarily shown. Consequently, it is considered that if a sensitizer which increases sensitivity in the wave length range of 210-260 nm and, further, in a wider range is found, an effective spectrum sensitization is possible from the viewpoint of wave length characteristics of xenon-mercury lamp, etc.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a light sensitive composition having a high sensitivity to ultraviolet rays of short wave length of 100-350 nm.
Another object of the present invention is to provide a light sensitive composition with which photolithography can be effected economically by using ultraviolet rays of short wave lengths obtained from a low pressure mercury lamp, heavy hydrogen lamp or xenon-mercury lamp and a pattern of less than 1 μm can be formed.
Still another object of the present invention is to provide a light sensitive composition containing polymethyl isopropenyl ketone have a remarkably increased sensitivity.
The light sensitive composition according to the present invention is characterized by comprising polymethyl isopropenyl ketone of a molecular weight of about 10,000-about 1,000,000 and a compound having the general formula: ##STR1## wherein X 1 , X 2 and X 3 independently represent hydrogen atom, an alkyl group, hydroxyl group, an alkoxyl group or a halogen atom, Y represents hydrogen atom or a group having the formula: --COOR (R being hydrogen atom or an alkyl group), Q represents hydrogen atom, an alkyl group or a lower hydrocarbon chain which may be substituted with hydroxyl group and n represents an integer of at least 1.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows spectral sensitivity of polymethyl isopropenyl ketone (free of sensitizer).
FIGS. 2 through 12 show spectral sensitivities of light sensitive compositions of the present invention.
FIG. 13 is a graph showing the effectiveness of using varios amounts of sensitizer in the light sensitive compositions of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
As described above, the composition of the present invention is a light sensitive composition characterized by comprising polymethyl isopropenyl ketone of a molecular weight of about 10,000--about 1,000,000 and benzoic acid, a substituted benzoic acid or an ester thereof of general formula (I).
Polymethyl isopropenyl ketone which is a sensitive resin (photoresist) and which is a principal component of the composition of the present invention is a polymer of a molecular weight of about 10,000--about 1,000,000 obtained by polymerization of methyl isopropenyl ketone.
The composition is shaped into a film having a thickness of usually about 0.3-1 μm and irradiated with ultraviolet rays having a wave length in the range of 100-350 nm through a mask pattern with a base which transmits ultraviolet rays having a wave length in the range of 100-350 nm such as quartz base. The exposed parts are decomposed and, thereby, become easily soluble in a suitable solvent such as a solvent mixture of cyclohexanone and a cellosolve solvent. Thus, the intended resist image is obtained. If a compound of general formula (I) is incorporated as a sensitizer in the polymethyl isopropenyl ketone, the decomposition is accelerated remarkably without reduction in resolving power as compared with the case of using polymethyl isopropenyl ketone alone. Increased sensitivity of about 30 times as high as usual is observed in the case of using an ultraviolet ray having a wave length of 253.7 nm.
The greatest characteristic feature of the present invention is that the composition contains benzoic acid, a substituted benzoic acid or an ester thereof of general formula (I) as sensitizer. Many of compounds of general formula (I) are accessible on the market as commercial chemicals and, in addition, they are cheap.
Compounds of general formula (I) will be classified into the following groups and examples of them will be given. ##STR2##
Group (a):
Compounds of general formula (I) wherein X 1 represents hydrogen atom or an alkyl group, preferably an alkyl group of 1-8 carbon atoms, X 2 , X 3 , Y and Q represent hydrogen atom, and n represents 1, i.e. compounds of following general formula (II): ##STR3##
As examples of compounds of group (a), there may be mentioned benzoic acid, o-methyl, m-methyl, p-methyl, p-isopropyl, p-n.-butyl, p-tert.-butyl, p-n.amyl and p-n.-octylbenzoic acid.
Group (b):
Compounds of general formula (I) wherein X 1 represents hydroxyl group, X 2 and X 3 independently represent hydrogen atom or hydroxyl group, Q represents hydrogen atom or an alkyl group, preferably an alkyl group of 1-5 carbon atoms, Y represents hydrogen atom and n represents 1, i.e. compounds of following general formula (III): ##STR4##
As examples of compounds of group (b), there may be mentioned p-hydroxybenzoic acid and its methyl and dodecyl esters, 2,4-, 3,4- and 3,5-dihydroxybenzoic acid, ethyl, propyl and isoamyl gallates and protocatechuic acid.
Group (c):
Compounds of general formula (I) wherein X 1 represents an alkoxyl group, preferably an alkoxyl group of 1-5 carbon atoms, X 2 independently represents hydrogen atom or an alkoxyl group, preferably an alkoxyl group of 1-5 carbon atoms, X 3 , Y and Q represent hydrogen atom and n represents 1, i.e. compounds of following general formula (IV): ##STR5##
As examples of compounds of group (c), there may be mentioned o-methoxy-, p-methoxy, 3,4-dimethoxy-, p-ethoxy-, p-n.-amyloxy- and 3,4-di-n.-amyloxybenzoic acids and anisic acids.
Group (d):
Compounds of general formula (I) wherein X 1 represents a halogen atom, preferably chlorine or bromine atom, X 2 independently represents hydrogen atom or a halogen atom, preferably chlorine or bromine atom, X 3 , Y and Q each represent hydrogen atom and n represents 1, i.e. compounds of following general formula (V): ##STR6##
As examples of compounds of group (d), there may be mentioned p-chloro-, 2,4-dichloro-, 3,4-dichloro- and p-bromobenzoic acids.
Group (e):
Compounds of general formula (I) wherein X 1 , X 2 and X 3 each represent hydrogen atom, Y represents --COOR, Q and R independently represent hydrogen atom or an alkyl group, preferably an alkyl group of 1-8 carbon atoms and n represents 1, i.e. compounds of following general formula (VI): ##STR7##
As examples of compounds of group (e), there may be mentioned terephthalic acid, dimethyl terephthalate, dibutyl phthalate and dioctyl phthalate.
Group (f):
Compounds of general formula (I) wherein X 1 represents an alkyl group, preferably an alkyl group of 1-8 carbon atoms, Q represents an alkyl group of 1-12 carbon atoms, preferably a hydrocarbon chain of 2-5 carbon atoms which may be substituted with hydroxyl group and n represents an integer of 2-4, i.e. compounds of general formula (VII): ##STR8##
As examples of compounds of group (f), there may be mentioned dodecyl ester, ethylene glycol diester, propylene glycol diester, 1,4-butanediol diester, glycerol diester, glycerol triester and pentaerythritol di-, tri- and tetraesters of p-tert.-butyl benzoic acid, and methyl ester of p-n.octylbenzoic acid.
Group (g):
Compounds of general formula (I) wherein X 1 and X 2 independently represent an alkoxyl group, preferably an alkoxyl group of 1-5 carbon atoms, X 3 and Y represent hydrogen atom, Q represents an alkyl group of 1-12 carbon atoms, preferably a hydrocarbon chain of 2-5 carbon atoms which may be substituted with hydroxyl group and n represents an integer of 2-4, i.e. compounds of following general formula (VIII): ##STR9##
As examples of compounds of group (g), there may be mentioned dodecyl ester, ethylene glycol diester, propylene glycol diester, 1,4-butanediol diester, glycerol di- and triesters and pentaerythritol di-, tri- and tetraesters of 3,4-dimethoxybenzoic acid and dodecyl ester of 3,4-di-n.-amyloxybenzoic acid.
Sensitizers of general formula (I) contained in the compositions of the present invention have been illustrated above by classifying them into groups. However, the sensitizers in the composition of the present invention are not limited to those given above as examples but include all compounds defined by general formula (I).
In the compounds of general formula (I), substituted benzoic acids having a hydroxyl group, an alkyl group or an alkoxy group on the aromatic nucleus and esters thereof are particularly excellent. The compounds of general formula (I) can be used alone or in combination of two or more of them.
The compounds of general formula (I) are used generally in an amount in the range of from about 0.01 to 50 parts by weight and preferably, from about 1 to 25 parts by weight per 100 parts by weight of polymethyl isopropenyl ketone.
According to a preferred embodiment of the use of the composition of the present invention, a solution of a mixture of polymethyl isopropenyl ketone and a compound having the general formula (I) in a suitable solvent such as cyclohexanone is applied to a base such as a silicon wafer with a spinner or the like, then dried to form a resist layer having a thickness of 0.3-1 μm. The resulting film is subjected to an image forming exposure treatment with a light source which emits rays having wave lengths of from 100 to 350 nm such as low pressure mercury lamps, heavy hydrogen lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, arc lamps, xenon lamps or xenon-mercury lamps through a mask pattern by using a base material which transmits light within said range of wave lengths such as LiF, MgF 2 , CaF 2 , BaF 2 , Al 2 O 3 or SiO 2 . The film is then immersed in a developing solution such as a mixture of cyclohexanone and a cellusolve solvent to effect elution of the parts in which molecular weight has been reduced by the exposure, thereby obtaining a very fine pattern on the surface of the base material.
Now, the description will be made on effects of the compositions of the present invention. As described in the above column of introduction of prior art with reference to FIG. 1, sensitivity range of polymethyl isopropenyl ketone is divided into two parts. Particularly, in a wave length range of 210-260 nm, a high sensitivity is not necessarily shown. By incorporating the compound of general formula (I) of the present invention therein, the composition exhibits a remarkably high sensitivity not only in the ultraviolet ray region of wave length range of 210-260 nm but also in a wider range as shown in FIGS. 2-12 and, in addition, it reproduces a fine pattern faithfully.
Experimental methods of FIGS. 1 and 2 will be illustrated in Example 2. In the figures, the ordinates indicate exposure count numbers and the abscissae indicate wave lengths (unit: nm). A blank part in the histogram indicates a part in which a base was exposed after sensitization followed by decomposition of the photoresist and development. A oblique-lined part indicates a part of half-tone in which sensitization was unsatisfactory. FIG. 9 shows a case in which a combination of two compounds was used.
Spectral sensitivity ranges shown in FIGS. 1-12 vary somewhat depending on the sensitizers employed. Therefore, more effective spectral sensitization is possible by selecting a sensitizer most suitable for the wave length distribution of light emitted by a particular light source.
As will be described in detail in examples given below, the light sensitive composition has an excellent film forming property, a high resolving power, excellent corrosion resistance and other properties desirable as a resist for fine pattern processing. Though wave lengths actually measured were up to 170 nm, the absorption range of the composition comprising polymethyl isopropenyl ketone and the sensitizer extends to a shorter wave lengths. Therefore, the composition is considered to be also sensitive to light having such short wave lengths.
If the composition of the present invention is used, exposure time, which has been a great problem in far ultraviolet lithography (an effective process for ultrafine processing such as super LSI), can be reduced remarkably. Consequently, the treatment can be completed within a period of time substantially equivalent to that required for photoresist processes currently employed in the art, whereby far ultraviolet lithography can be put to practical use.
Although the present invention shall be described in detail by giving the examples as following, it shall not be limited of its scope by these examples.
EXAMPLE 1
100 Parts by weight of polymethyl isopropenyl ketone having a molecular weight of 176,000 were dissolved in cyclohexanone to obtain a solution having a concentration of 10 weight %. 10 Parts by weight of a compound shown in Table 1 were added to the solution and the mixture was subjected to filtration through a filter of 0.2 μm to obtain a sensitizing solution. The sensitizing solution was then applied to a silicon wafer with a spinner. A resist layer having a thickness of about 0.5 μm was thus formed thereon and the resulting wafer was baked at 80° C. for 30 minutes to remove the solvent completely. The photo-sensitive materials thus obtained were exposed stepwise with a commercially available germicidal lamp which radiates ultraviolet rays of 253.7 nm wavelength, from a distance of 5.5 cm.
Then, the silicon wafer was immersed in a developing solution comprising ethyl cellosolve and cyclohexanone for one minute to effect the development, washed with water for one minute and dried. Sensitivity was determined from number of residual steps. The results are shown in Table 1. Relative sensitivity in the table is a relative value based on sensitivity (10) of polymethyl isopropenyl ketone. The remaining rate of the film in the non-exposed parts was more than 90% after the development.
TABLE 1______________________________________ RelativeNo. Sensitizer Group sensitivity______________________________________1 None (PMIPK) -- 102 Benzoic acid a 233 p-Chlorobenzoic acid d 304 2,4-Dichlorobenzoic acid d 305 3,4-Dichlorobenzoic acid d 306 p-Bromobenzoic acid d 407 p-Hydroxybenzoic acid b 808 2,4-Dihydroxybenzoic acid b 239 3,4-Dihydroxybenzoic acid b 17110 3,5-Dihydroxybenzoic acid b 2311 Ethyl gallate b 3012 Propyl gallate b 3013 Isoamyl gallate b 3014 Methyl p-hydroxybenzoate b 21815 Dedecyl p-hydroxybenzoate b 13316 0-Methoxybenzoic acid c 4017 p-Methoxybenzoic acid c 26718 3,4-Dimethoxybenzoic acid c 10019 p-Ethoxybenzoic acid c 13320 p-n-Amyloxybenzoic acid c 24021 o-Methylbenzoic acid a 4022 m-Methylbenzoic acid a 4023 p-Methylbenzoic acid a 8024 p-Isopropyl benzoic acid a 17125 p-tert.-Butylbenzoic acid a 24026 Terephthalic acid d 2327 Dimethyl terephthalate d 4028 p-n-Butylbenzoic acid a 24029 p-n-Amylbenzoic acid a 20030 p-n-Octylbenzoic acid a 18531 Dodecyl p-tert.-butylbenzoate f 23532 Ethylene glycol diester of f 240p-tert.-butylbenzoic acid33 Propylene glycol diester of f 238p-tert.-butylbenzoic acid34 1,4-Butane diol diester of f 235p-tert.-butylbenzoic acid35 Glycerol diester of p-tert.- f 238butylbenzoic acid36 Glycerol triester of p-tert.- f 240butylbenxoic acid37 Pentaerythritol diester of f 235p-tert.-butylbenzoic acid38 Pentaerythritol triester of f 238p-tert.-butylbenzoic acid39 Pentaerythritol tetraester of f 240p-tert.-butylbenzoic acid40 Dodecyl 3,4-dimethoxybenzoate g 9541 Ethylene glycol diester of g 1003,4-dimethoxybenzoic acid42 Propylene glycol diester of g 973,4-dimethoxybenzoic acid43 1,4-Butanediol diester of g 953,4-dimethoxybenzoic acid44 Glycerol diester of 3,4- g 97dimethoxybenzoic acid45 Glycerol triester of 3,4- g 100dimethoxybenzoid acid46 Pentaerythritol diester of g 973,4-dimethoxybenzoic acid47 Pentaerythritol triester of g 953,4-dimethoxybenzoic acid48 Pentaerythritol tetraester of g 1003,4-diemthoxybenzoic acid______________________________________
EXAMPLE 2
A sensitizing solution was prepared in the same manner as in Example 1. The sensitizing solution was applied to a dry glass plate. After the formation of a resist layer having a thickness of about 0.5 μm thereon, it was baked at 80° C. for 30 minutes to remove the solvent completely. In order to obatin data on the spectral sensitivity, the photo-sensitive, the photo-sensitive material was exposed stepwise through a concave diffraction grating of 200 nm blaze with a 5 kW xenen lamp.
Then, it was immersed in a developing solution comprising a solvent mixture of ethyl cellosolve and cyclohexanone for one minute to effect the development. Thereafter, it was washed with water for one minute and dried. The number of steps required for the dissolution was measured. The light energy was measured by using a vacuum thermocouple. Data obtained after conversion so that the irradiated photon number would be constant at every wave length are shown in FIGS. 1-12. In FIGS. 1-12, ordinates indicate exposure count numbers (45×2 n , wherein n is a number of a step, i.e. 0, 1, 2, 3, . . . 8).
Sensitizer indicatied in FIGS. 1 to 12 are shown together in Table 2.
TABLE 2______________________________________Figure Sensitizer______________________________________1 Polymethyl isopropenyl ketone (free of sensitizer)2 Benzoic acid3 p-tert.-Butylbenzoic acid4 p-Hydroxybenzoic acid5 Methyl p-hydroxybenzoate6 Dodecyl p-hydroxybenzoate7 3,4-Dimethoxybenzoic acid8 p-Bromobenzoic acid9 A mixture consists of 5 wt. % of Benzoic acid and 5 wt. % of 3,4-Dimethoxy bonzoic acid.10 Protocatechuic acid11 p-Methoxybenxoic acid12 p-n-Amyloxybenxoic acid______________________________________
EXAMPLE 3
100 Parts by weight of polymethyl isopropenyl ketone of a molecular weight of 176,000 were dissolved in cyclohexanone to obtain a solution of a concentration of 10 weight %. To the solution was then added various amounts of p-methoxybenzoic acid to obtain solutions containing 1-35 parts by weight of p-mehoxybenzoic acid. The solutions were filtrated through a 0.2 μm filter to obtain sensitizing solutions. Each of the sensitizing solutions was applied to a silicon wafer with a spinner. A resist layer having a thickness of about 0.5 μm was thus formed thereon. It was baked at 80° C. for 30 minutes to remove the solvent completely. The photo-sensitive materials thus obtained were exposed stepwise with a commercially available germicidal lamp which radiates ultraviolet rays of 253.7 nm wavelength, from a distance of 5.5 cm. Then, the resulting silicon wafer was immersed in a developing solution comprising a solvent mixture of ethyl cellosolve and cyclohexanone for one minute to effect the development, washed with water for one minute and dried. The sensitivity was determined from number of residual steps. The remaining rate of the film in the nonexposed parts was also measured. The results are shown in FIG. 13. The sensitivity is shown by relative values based on the sensitivity (10) of polymethyl isopropenyl ketone. The remaining rate of the film was hardly changed. The light sensitive composition thus exhibited ideal properties.
EXAMPLE 4
10 Parts by weight of p-methoxybenzoic acid, per 100 parts by weight of polymethyl isopropenylketone, were added to a 10 weight % solution of polymethyl isopropenyl ketone having a molecular weight of 176,000 in cyclohexanone to obtain a sensitizing solution. The sensitizing solution was applied to a silicon wafer with a spinner and baked at 80° C. for 30 minutes to obtain a resist layer having a thickness of about 0.5 μm. Thereafter, a quartz mask pattern was applied closely to the resist layer. After exposure with the same germicidal lamp as employed in Example 1 for two minutes, it was immersed in the same developing solution as employed in Example 1 for one minute to effect the development. After washing with water for one minute followed by drying, a very accurate ultrafine pattern of 0.5 μm was obtained.
The silicon wafer having the thus formed pattern was baked at 130° C. for 20 minutes and then treated with an etching solution containing hydrogen fluoride and ammonium fluoride (weight ratio 1;6) for 11 minutes.
Thus, an etching pattern consistent with the mask pattern could be obtained.
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A sensitive composition comprising polymethyl isopropenyl ketone of limited molecular weight and a compound of a given general formula. The formation of a pattern of less than 1 μm is made possible by employing ultraviolet rays of wave lengths of 100-350 nm in place of those of 350-450 nm utilized in conventional processes. The sensitive composition is highly sensitive to ultraviolet rays in said wave range and reproduces a fine pattern precisely.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a garage door reinforcement system that is interiorly disposed.
[0003] 2. Description of the Related Art
[0004] Several inventions for reinforcements for garage doors have been developed in the past. None of them, however, includes an additional reinforcement member conforming to the structure that extends continuously and transversally across a door panel. The present invention eliminates the U-shaped bars that are externally mounted at present while enhancing its structural integrity.
[0005] Typically, garage doors have multiple panels with multiple widths, with a panel height of 21 inches, preferably, and modular lengths of 8; 9; 12 and 16 feet (2.44; 2.74; 3.66; 4.88 meters, respectively). The most popular designs include four panels that are monolithic throughout the entire length, each having lateral top and bottom edges. These edges have a tongue and groove, shiplap, or equivalent terminations. These terminations are intended to provide structural reinforcement and also act as a barrier to the elements, including water and wind.
[0006] Construction codes in several areas, specifically those that are prone to windstorms and hurricanes, require passing certain wind tests. Thus, the need for reinforcements for garage doors. Typically, garage doors are not prepared to withstand strong winds experienced in many parts of the world. These additional reinforcements are not needed in some areas. There is a need for reinforced garage doors, capable of passing hurricane wind tests for each jurisdiction, on a selective basis. Thus, a system for readily reinforcing the doors, when needed, is quite desirable.
[0007] Applicant believes that the closest reference corresponds to U.S. Pat. No. 6,062,293 issued to Allen Berger, Jr., who is the inventor in the present application, for a garage door reinforcement and method. The present invention improves the wind load resistance of the garage door even more by having reinforcement bars that conform to the shaped of existing structural folded members without detracting from the aesthetics of the door.
[0008] The present invention provides a reinforcement assembly that conforms and follows the lateral edges of a garage door panel. The present invention includes a reinforcement that is compatible with the panels' terminations, namely, tongue and groove, shiplap and others. The reinforcement bar is made with folding manufacturing techniques.
[0009] Other patents describing the closest subject matter provide for a number of more or less complicated features that fail to solve the problem in an efficient and economical way. None of these patents suggest the novel features of the present invention.
SUMMARY OF THE INVENTION
[0010] It is one of the main objects of the present invention to provide an interior garage door reinforcement system that is capable of withstanding high winds and flying objects without adversely affecting the aesthetics of the door.
[0011] It is yet another object to provide a garage reinforcement system that enhances its structural integrity by adding reinforcement members that complement and abuttingly conform to the main structural members of the door.
[0012] It is still another object of this invention to provide a garage door reinforcement system made for standard sized panels, to fit standard sized tracks, in standard sized garages, and yet effective to withstand wind loads of hurricane grade and using roll forming manufacturing processes.
[0013] It is yet another object of this invention to provide such a system that is inexpensive to manufacture and maintain while retaining its effectiveness.
[0014] Further objects of the invention will be brought out in the following part of the specification, wherein detailed description is for the purpose of fully disclosing the invention without placing limitations thereon.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] With the above and other related objects in view, the invention consists in the details of construction and combination of parts as will be more fully understood from the following description, when read in conjunction with the accompanying drawings in which:
[0016] FIG. 1 represents an isometric view the garage door, object of the present application.
[0017] FIG. 2 shows a cross section view of the present invention, taken along line 2 - 2 in FIG. 1 .
[0018] FIG. 3 illustrates an enlarged isometric view of one section of the present invention partially showing two adjacent panels.
[0019] FIG. 4 is an exploded view of the portion represented in FIG. 3 , showing the reinforcing bars of the present invention being mounted.
[0020] FIG. 5 represents an exploded view of an alternate embodiment, showing the shiplap type complementing joint portion and the conforming shiplap type reinforcing bars.
[0021] FIG. 6 is a representation of a front elevational view of an alternate embodiment using shiplap type complementing joint portion and conforming shiplap type reinforcing bars.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0022] Referring now to the drawings, where the present invention is generally referred to with numeral 10 , it can be observed that it basically includes, in the preferred embodiment, several panel sections 20 , reinforcement runner member 50 , reinforcement runner member 60 and hinge assembly 80 .
[0023] As seen in FIG. 1 , panel sections 20 run the entire width of door D and are hingedly mounted to each other with hinge assemblies 80 . As best seen in FIGS. 2 ; 3 and 4 , each panel section 20 includes wall 22 with reversely folded edge portions forming upper longitudinal end 24 and lower longitudinal end 26 , extending therefrom. The reversely folded edge portions form upper longitudinal ends 24 and lower longitudinal ends 26 are articulated to each other in contiguous panels. In the preferred embodiment shown in FIGS. 1 through 4 , ends 24 and 26 are complementing joints of the tongue and groove type. In the preferred embodiment, upper longitudinal end 24 includes longitudinally extending upper wall 25 with longitudinal tongue 32 and longitudinally extending inner wall 29 perpendicularly extending from upper wall 25 , as best seen in FIG. 4 . Lower longitudinal end 26 includes longitudinally extending bottom wall 27 with longitudinally extending groove 42 and longitudinally extending inner wall 28 perpendicularly extending from bottom wall 27 . Longitudinal tongue 32 and longitudinally extending groove 42 are intended to provide reinforcement to ends 24 and 26 , respectively, and protection from the elements. Wall 22 is vertically disposed when door is closed.
[0024] Hinge assembly 80 includes walls 23 with angular walls 82 and 84 at its upper and lower ends, respectively. Angular walls 82 cooperate with angular walls 84 of a contiguous panel section 20 to receive hinge pin 86 through openings 83 and 85 , respectively. Through openings 23 ′ of wall 23 permit fastening members 79 to go through and selectively engage holes cooperatively positioned on walls 28 and 29 and runner members 50 and 60 , respectively.
[0025] In the preferred embodiment for garage door reinforcement system, longitudinal unitary reinforcements as reinforcement runner members 50 and 60 are insertable horizontally and interiorly to the complementing top and bottom joints, namely upper longitudinal end 24 and lower longitudinal end 26 , respectively. Reinforcement runner member 50 includes longitudinally extending walls 52 ; 54 ; 56 ; 58 and 58 ′ and extends along the entire width of door D, as shown in FIGS. 3 and 4 . Wall 54 includes small longitudinal grooves 55 to enhance its strength. Walls 52 and 56 extend perpendicularly from wall 54 and both fold to define walls 58 and 58 ′. These walls extend as a mirror of each other and are separated by longitudinally extending space 53 . Walls 58 and 58 ′ also include, in the preferred embodiment, small reinforcing longitudinal grooves 59 and 59 ′ and complementing longitudinal curved portions 57 and 57 ′ that conform to longitudinal tongue 32 .
[0026] Reinforcement runner member 60 includes longitudinally extending walls 62 ; 64 ; 66 ; 68 and 68 ′ and extends along the entire width of door D, as shown in FIG. 4 . Wall 64 includes small longitudinal grooves 61 to enhance its strength. Walls 62 and 66 extend perpendicularly from wall 64 and both fold to define walls 68 and 68 ′. Walls 68 and 68 ′ extend as a mirror of each other and are separated by longitudinally extending space 63 . Walls 68 and 68 ′ also include, in the preferred embodiment, small reinforcing longitudinal grooves 65 and 65 ′ and complementing longitudinal curved portions 67 and 67 ′ that conform to longitudinal groove 42 .
[0027] The manufacture of reinforcement runner members 50 and 60 is compatible with inexpensive roll forming processes. The function of reinforcement runner members 50 and 60 is to enhance the structural integrity of ends 24 and 26 , respectively, by having complementary longitudinally curved portions 67 and 67 ′ come in longitudinal contact and conforming to the shape of longitudinally extending groove 42 . Similarly, complementary longitudinally curved portions 57 and 57 ′ come in longitudinal contact and conforming to the shape of longitudinally extending tongue 32 . The result is a structure of superior strength. The otherwise vulnerable articulations of the panels are strengthened.
[0028] In the alternate embodiment 100 shown in FIGS. 5 and 6 , each panel section 120 includes wall 122 with upper and lower longitudinal ends 124 and 126 , extending therefrom. Upper and lower longitudinal ends 124 and 126 conform ship lap type complementing joints along the top and bottom edges of panel sections 120 . Upper longitudinal end 124 includes longitudinally extending upper walls 125 and 125 ′ with curved portion 132 and longitudinally extending inner wall 129 in a parallel relationship with respect to panel section 120 . Lower longitudinal end 126 includes longitudinally extending bottom walls 127 and 127 ′ with curved portion 142 and longitudinally extending inner wall 128 in a parallel relationship with respect to panel section 120 . Shiplap type upper and lower longitudinal ends 124 and 126 cooperatively engages as a shiplap type complementing joint, as best seen in FIG. 6 .
[0029] As best seen in FIG. 6 , longitudinal unitary reinforcement runner members 150 and 160 are of the shiplap type and they are insertable horizontally and interiorly to the complementing joints, namely upper longitudinal end 124 and lower longitudinal end 126 . Reinforcement runner member 150 includes longitudinally extending walls 152 ; 154 ; 156 ; 158 and 158 ′ and extends along the entire width of door D. Wall 154 includes small longitudinal grooves 155 . Walls 152 and 156 extend perpendicularly from wall 154 . Walls 158 and 158 ′ define the shiplap type complementing joint. Walls 158 and 158 ′ also include small reinforcing longitudinal grooves 159 and 159 ′, respectively, curved portion 157 with a longitudinally extending space 157 ′ at its central portion.
[0030] Reinforcement runner member 160 includes longitudinally extending walls 162 ; 164 ; 166 ; 168 and 168 ′ and extends along the entire width of door D. Wall 164 includes small longitudinal grooves 165 . Walls 162 and 166 extend perpendicularly from wall 164 . Walls 168 and 168 ′ define the shiplap type complementing joint. Walls 168 and 168 ′ also include small reinforcing longitudinal grooves 169 and 169 ′, respectively, curved portion 167 with a longitudinally extending space 167 ′ at its central portion.
[0031] The foregoing description conveys the best understanding of the objectives and advantages of the present invention. Different embodiments may be made of the inventive concept of this invention. It is to be understood that all matter disclosed herein is to be interpreted merely as illustrative, and not in a limiting sense.
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An improvement for reinforced garage doors that includes using horizontally disposed reinforcement runner members with a longitudinal complementary shape that conform to the longitudinal complementary joints of the panel ends, such as the tongue and groove type or the shiplap type, or equivalent. The reinforcement runner members are made with roll forming processes by creating several longitudinal folds. The reinforcement runner members extends, uninterrupted, the entire width of the panels and enhance the articulation of the panels.
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BACKGROUND OF THE INVENTION
This invention relates to an improved design for seating hard wearing button inserts in interfering sized cavities in percussion drill bits and will be described with particular reference thereto. It is to be appreciated, however, that the invention has broader applications and may be adapted to use in a number of other environments.
Button inserts formed from sintered carbide or other hard materials normally mounted in generally cylindrical cavities in drill bits with one end of the inserts protruding therefrom. The other or inner ends of the inserts are seated against the bottom surface of the associated cavity. During operation, a percussion tool strikes the top of the drill bit. The impact stress waves caused by this percussion travel through the drill bit to the inserts which, in turn, fracture the rock against which the drill is held. As a result of this action, considerable impact forces are generated during the drilling process.
The seating surface between each insert and the associated cavity in a drill bit is the major area for the energy transmission of these impact forces with resultant severe stress concentrations therebetween. These stress concentrations are due to the difference in elasticity between the carbide of the insert (100,000,000 psi) and the bit material (30,000,000 psi). The stress concentrations are also due to the interplay of the manufacturing tolerances for the drill bit and insert, and, eventually, failure results.
In the prior art, great concern has been focused on corner stress concentrations in, and the subsequent fatigue failures of, button insert drills. In some cases some sort of captured shape has been recommended to confine the forces, or a corner clearance has been used to minimize the magnitude of the developed corner forces. These solutions have merit as long as there is no angular manufacturing tolerance deviation between the adjoining contacting surfaces of the insert inner end and the bottom of the cavity, ie., the inner end surface of the insert and the bottom surface of the cavity meet with full planar contact. As soon as there is some sort of angular deviation between these adjoining surfaces, the surfaces will no longer meet in a plane, and the angular stress concentrations will overwhelm the proposed prior art solutions and result in numerous drill failures. Moreover, to limit this angular deviation, the manufacturing tolerances must be tightly controlled in these types of prior art devices.
The present invention overcomes the foregoing problems and others to provide a new and improved insert seat arrangement. The invention successfully compensates for any manufacturing tolerance angular deviation between the adjoining contacting surfaces and minimizes uneven stress concentrations in the drill.
BRIEF SUMMARY OF THE INVENTION
In accordance with the invention an improved design is provided for the seating surface between a button insert and an associated cavity in a drill bit to overcome problems of manufacturing tolerance angular deviations between the mating surface areas thereof.
More particularly in accordance with the invention, compensation for the manufacturing tolerance angular deviations is achieved by rounding one of the inner end surfaces of the insert and the bottom wall of the drill bit receiving cavity. The amount of curvature is such that the instantaneous slope of such rounded surface is slightly greater than the theoretical full manufacturing tolerance slope of the mating surface. With this configuration, the point of contact between the inner end surface of the insert and the bottom surface of the cavity will always occur along the arc of curvature of the rounded surface, and critical edge contact will be avoided for all manufacturing tolerance angular deviations of the mating surfaces.
According to another aspect of the invention where the inner end surface of the insert is rounded, the radius of curvature is substantially greater than the width or diameter of the insert seating surface.
In accordance with a further aspect of the invention, the insert meets the body of the drill bit in a plurality of planes of contact.
In accordance with still another aspect of the invention, the radius of curvature of the rounded surface on one of the insert inner end and cavity bottom wall is mathematically calculated on the basis of predetermined relationships.
It is a primary advantage of the subject invention to confine the contact zone between the inner end of an insert member and the receiving cavity of an associated drill bit within the arc of the seating surface under all manufacturing tolerances.
Another advantage of the invention resides in maintaining sufficient contact area between the inner end of an insert member and the associated cavity in a drill bit during normal drilling operations.
Still another advantage of the invention is found in a reduction of contact stress concentration between the inner end of the insert member and the drill bit.
Yet a further advantage of the present invention is represented by an increase in the useful life of percussion drill bits.
Other advantages and benefits of the invention will become apparent to those skilled in the art upon a reading and understanding of the following detailed specification.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may take form in certain parts and arrangements of parts, preferred and alternate embodiments of which will be described in detail in this specification and illustrated in the accompanying drawings which form a part hereof and wherein:
FIG. 1 is a cross-sectional view showing a portion of a drill bit having a hardened button insert fixedly mounted in an insert receiving cavity in accordance with the concepts of the subject invention;
FIGS. 2-7 are generally schematic views of a series of flat and round bottom carbide button insert seating surfaces showing various manufacturing tolerance conditions;
FIGS. 8-10 are fragmentary cross-sectional views of the inner ends of carbide button inserts showing alternate embodiments of the invention; and,
FIG. 11 is a flow chart of a method for determining the preferred radius of the inner end of a button insert in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings wherein the showings are for purposes of illustrating preferred and alternate embodiments of the invention only and not for limiting same, FIG. 1 shows a small portion of a steel drill bit A having a carbide insert B fixedly secured therein. A drill bit normally contains a plurality of these inserts disposed in a predetermined configuration or pattern. As shown, the drill bit contains a generally cylindrical cavity 10 for receiving the insert, it being appreciated that a plurality of like or similar cavities are disposed in a predetermined pattern to accommodate a plurality of like or similar inserts B. While description will hereafter be made with reference to one insert and associated receiving cavity, it will be appreciated that the arrangements for the other inserts and cavities are identical thereto unless otherwise specifically noted.
Cavity 10 is normally drilled and reamed to conform to the associated insert. A centerline 12 runs axially through the cavity, and a cavity bottom wall 14 is designed to be substantially normal to the centerline. In fact, however, due to normal manufacturing tolerances, bottom wall 14 will vary by ± a certain number of degrees "b" from the desired normal relationship.
Each insert B is substantially cylindrical, and includes an inner end 20 and an outer end 22. Both of inner and outer ends 20, 22 have rounded surfaces, although by different amounts. The insert is located within cavity 10 with insert outer end 22 protruding slightly outwardly from the drill bit surface. Inner end 20 is curved away from the central area of cavity bottom wall 14 in all directions.
The radius 24 of the insert inner end is chosen such that the contact zone 26 between the insert and cavity bottom wall 14 is confined within the arc 28 of the inner end seating surface under all normal manufacturing tolerances. Such relationship avoids critical corner contact while maintaining a sufficient energy dispersal contact area between insert B and drill bit A. The rounded shape efficiently transfers the impact forces between the insert and the drill bit under manufacturing tolerance angular deviations, while avoiding uneven contact of the type that leads to drill failure. The impact deformation of cavity bottom wall 14 occurs more or less centrally and is spread out over a smooth rounded shape. Also, the tensile forces of the insert on the steel of the drill bit are not as quick in producing fatigue cracks which eventually will render the drill unusable, thus significantly increasing the effective life of the drill bit. The rounded shape of insert inner end 20 compensates for tolerance variations from the norrmal which occur in bottom wall 14 as a result of conventional manufacturing procedures.
The foregoing compensation results can readily be appreciated by a comparison of FIGS. 2, 4, and 6 which show typical flat ended prior art inserts under certain bottom angle deviations with FIGS. 3, 5, and 7 which show the subject new rounded end insert under similar deviation conditions. When cavity bottom wall 14 is normal to centerline 12 of the cavity, the typical flat ended insert C has a full surface contact area 34 between the insert inner end 36 and cavity bottom wall 14 (FIG. 2). Under the same conditions, the round ended insert B of the subject invention has central contact zone or area 26 (FIG. 3). When bottom wall 14 of the cavity varies from the normal as by an angle "b" of just a few degrees due to normal manufacturing tolerances, however, flat bottomed insert C will have a very restricted corner type contact area 34 as shown in FIG. 4. As a result, the insert cavity will very quickly suffer terminal fatigue. Under identical conditions, the round ended insert B still has a central contact area 26 (FIG. 5) and restricted contact is not produced by the angular deviation between the insert and cavity contact surfaces. When bottom wall 14 of the cavity varies by the full manufacturing tolerance which equals some predetermined maximum deviation angle "b", the rounded bottom insert still avoids the critical corner contact which is present in the prior art. In this regard, the relative disposition of contact areas 34 and 26 in FIGS. 6 and 7 should be contrasted with each other.
Referring again to FIG. 1, the principal focus of the subject invention is that with ordinary manufacturing tolerances, the actual contact area 26 between inner end surface 20 of the insert and bottom wall 14 of the drill bit cavity occurs within arc 28 of radius 24. The contact area does not occur at the corner of the insert, even if bottom wall 14 deviates from a normal relationship to central axis 12 by the maximum deviation angle "b" permitted under full tolerance conditions.
Note should be taken that it is not necessary for inner end surface 20 of insert B to be shaped with a uniform radius. The shape can vary, e.g., elliptical, stepped, etc., as long as the contact area is along an arc with radius 24, ie., rounded inner end 20 has a greater relative slope than bottom wall 14 of the drill bit cavity.
Since the invention causes contact area 26 to occur near to the center of cavity bottom wall 14 under most manufacturing conditions, deformation of the bottom wall caused by the compressive forces produced by insert B can be dissipated without the localized tensile stress concentrations which are present in the prior art constructions. Specifically, deformation of bottom wall 14 does not occur at the critical corner location. Instead, this deformation occurs primarily over a resilient planar area and significantly increases the operational life of drill bit A.
Radius 24 of insert inner end 20 is normally from about 1 to 100 times the effective width 52 of the seat of insert B, with 5 to 30 times being typical. The actual radius 24 of insert inner end 20 is, however, normally calculated by means of a particular mathematical procedure. Such procedure is schematically shown in FIG. 11. As shown, the procedure is begun at step 80 and encompasses defining the external loading that will be present on insert B. This external loading figure comprises the amount of force that will need to be transferred between the insert and drill bit A to effect the desired drilling results.
The next step is designated by numeral 82 and comprises establishing the preliminary manufacturing tolerances for cavity 10 in the drill bit. To accomplish this, width 52 of the cavity bottom wall and maximum angular deviation angle "b" which will result from manufacturing operations are calculated. The width 52 comprises the distance across the wall with which an ordinary flat shape would be placed in physical contact. Therefore, and with the single flat surface of FIG. 1, width 52 comprises the diameter of cavity 10. Angular tolerances b of the cavity bottom wall comprises the normally expected manufacturing deviations of the bottom wall from a perpendicular relationship to cavity centerline 12.
With more unusual arrangements such as the segmented, angularly displaced surfaces illustrated in FIGS. 9 and 10, the width of the cavity bottom wall comprises the distance across the contact portion thereof and are designated by numerals 54, 56, respectively. With a concave bottom surface on the insert inner end and a concave or convex cavity bottom wall as is shown in FIG. 8, a mathematical approach to determining radius 24 would ordinarily not be used. Instead, a radius 58 of the rounded cavity bottom wall would be calculated. Radius 60 of the insert inner end is then chosen to be slightly less than radius 58, ie., have a greater curvature.
Having established the manufacturing dimensions for width 52, or widths 54 and 56 (FIGS. 9 and 10), along with angular tolerance "b" of bottom wall 14 allowed by the manufacturing tolerances, step 84 in the method comprises calculating radius 24, or radii 62, 64 (FIGS. 9 and 10), of the insert inner end. Radius 24 is mathematically calculated according to the following formula: ##EQU1##
After the radius has been calculated, and with reference again to FIG. 11, step 86 of the method involves calculating the contact stresses between insert B and drill bit A, ie., the effect of external loading on the contact produced by the calculated radius. If these contact stresses will not unduly damage drill bit A and are, therefore, acceptable (step 88), the calculated radius is, in turn, acceptable and can be safely used with drill bit A to obtain a satisfactory drill bit life (step 90).
If the contact stresses will unduly damage the drill bit (step 88), the allowable degree of angular tolerances "b" permitted during manufacture are decreased (step 92), and new tolerances are established (step 94). A new, maximum radius is then calculated in the same manner as previously described (step 84), and the contact stresses are again calculated. This procedure may be repeated until such time that the maximum calculated radius yields acceptable contact stress results.
The actual calculations for width 52 and angular tolerance "b" of bottom wall 14 are to be tempered with an awareness of the statistical mathematical probabilities of a number of variables, ie., the numbers input into the calculation would be compromised based on an awareness of the need for a reasonably priced, marketable product. Specifically, the choice of radius 24 will be a compromise between the desire to compensate for all manufacturing tolerance angular deviations (a smaller radius), and the need to spread the compressive forces of the insert on the cavity bottom wall over as wide an area as possible (a larger radius). Therefore, a radius is selected which optimizes both considerations, recognizing, of course, that wide manufacturing tolerances will lower the costs of manufacture and ease of drill bit construction.
Radius 24 of insert inner end 20 effectively eliminates the critical corner contact while at the same time compensating for any angular deviation of cavity bottom wall 14. The radius insures a sufficient contact area between the insert and the drill bit under normal operating conditions. The above-described features combine to greatly increase the effective, useful life of the bits.
Although the invention has been described with reference to preferred and alternate embodiments, modifications and alterations will occur to others upon a reading and understanding of this specification. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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A percussion drill having a rounded and tapered contact surface conformation between the inner ends of hardened insert members closely received by cavities in a drill bit. Each insert has a radiused inner end in contacting relation with the bottom wall of its associated cavity. The radius is such that it compensates for angular deviations in the cavity bottom wall due to manufacturing tolerances from a normal relation relative to the cavity longitudinal axis. The radius of the insert inner end is calculated on the basis of a mathematical formula. The arrangement provides a structure which prevents corner load and stress, and insures contact away from the corner to thereby increase bit life.
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BACKGROUND OF THE INVENTION
[0001] The present invention concerns a rotary vacuum pump and a structure and a method for balancing thereof.
[0002] In the field of rotary vacuum pumps, it is known that either mechanical bearings, such as ball or roller bearings, or magnetic bearings can be used for supporting the rotating pump shaft.
[0003] The present invention concerns a rotary vacuum pump of the kind equipped with mechanical bearings.
[0004] More particularly, the present invention concerns a turbomolecular rotary vacuum pump of the kind disclosed for instance in U.S. Pat. No. 6,158,986 or U.S. Pat. No. 5,688,106.
[0005] As known, rotary pumps, and especially turbomolecular rotary pumps, are machines equipped with a rotating portion, including a rotating shaft to which a set of parallel rotor discs are secured, and co-operating with a stationary portion, generally a set of stator discs, in order to obtain gas pumping from an inlet port to an outlet port of the pump.
[0006] Depending on the kind of pump, higher or lower vacuum degrees can be obtained. For instance, a turbomolecular pump can generate a vacuum of the order of 10 −7 mbar (10 −5 pa) with a shaft rotation speed in a range 2×10 4 to 9×10 4 rpm.
[0007] A vacuum pump is thus a machine with a mass that is rotated at extremely high speed. In a vacuum pump, such a rotating mass generally includes a rotating shaft, the rotor of the electric motor driving said shaft into rotation, the set of rotor discs and the inner rings of the rolling bearings rotatably supporting the pump shaft.
[0008] When the rotating mass is not arranged with its center of gravity or the rotation axis and thus is not balanced, forces of interior are generated within the pump and are transmitted through the housing to the outside of the pump. Such forces of interior cause unwanted stresses and vibrations, which are sources of noise and lead to an early wear of the rolling bearings.
[0009] Moreover, in some specific applications, for instance where the pump is connected to a precision measuring instrument, such as in mass spectrometry, vibrations are sources of disturbances altering the operation of the measuring instrument and therefore they cannot be tolerated.
[0010] One of the problems encountered in designing a rotary vacuum pump equipped with mechanical bearings is thus how to reduce the vibrations produced by the pump due to unbalance of the rotating masses.
[0011] Generally, it is known that balancing of a rotating mass can be obtained by means of further additional rotating masses, coupled to the main mass so that the center of gravity of the overall mass is brought again on the rotation axis (static balancing) and the rotation axis coincides with a main axis of inertia (dynamic balancing). A dynamically balanced rotor does not transmit stresses to the supports and it is therefore an optimum solution.
[0012] In the field of rotary vacuum pumps, and in particular of turbomolecular ones, the pump rotor is dynamically balanced through an iterative process in which measuring steps of the vibrations transmitted by the pump to an external structure alternate with adjusting steps of the position of one or more additional masses placed on the rotor, until the optimum conditions are attained.
[0013] The main problems related to the rotor balancing step are, on one hand, the definition of the mathematical model used in order to relate the vibrations measured during the balancing step to the rotor unbalance and, consequently, to the arrangement of the correcting masses, and, on the other hand, the choice of the kind of vibration sensors and the arrangement thereof.
[0014] In the field of rotary vacuum pumps, the sensors generally used during the rotor balancing step are accelerometers, that is sensors capable of transforming the acceleration of a moving body to which they are secured into an electric signal, the intensity of which is just a function of the acceleration the sensor is being submitted to.
[0015] According to the prior art, the dynamic balancing of a vacuum pump rotor is performed by placing the pump, without stator discs, inside a bell-shaped casing onto which at least two accelerometers, for instance piezoelectric accelerometers, are located. Once the rotor is rotated at high speed, the accelerometers located onto the stationary bell allow measuring the vibrations induced unbalances, if any, of the rotating masses.
[0016] Yet such a solution has some drawbacks, of which the main is that the point where vibrations are measured, i.e. the area where the accelerometer is located, is relatively far from the source of said vibrations, i.e. the rotor.
[0017] The provision of a set of masses placed between the rotor and the accelerometer, and comprising members that in part are very rigid and in part are resilient and damping, makes it complex to define a reliable mathematical model relating the vibrations to their cause, i.e. the unbalance of the rotor and the other moving masses.
[0018] Consequently, the iterative balancing process may need several pump stopping and starting phases in order to apply the correcting masses, and this results in a considerable increase of the time required to reach the optimum conditions and hence in a considerable slowing down of the production.
SUMMARY OF THE INVENTION
[0019] It is the main object of the present invention to solve the problem of how effectively and quickly to balance the rotating masses of a rotary vacuum pump, more particularly a pump, equipped with mechanical bearings such as a turbomolecular vacuum pump.
[0020] The above and other objects are achieved by means of a vacuum pump and a balancing method as claimed in the appended claims.
[0021] Due to the positioning of displacement sensors close to the rotating masses of the pump, it is possible to obtain a more direct measurement of the rotor vibrations and hence to make the proper balancing thereof simpler and quicker.
[0022] According to the invention, the vibration measurement is not affected by the presence of other pump components, which allows for a considerable simplification of the mathematical model relating the measured displacements to the rotor unbalance inducing them.
[0023] Advantageously, the provision of displacement sensors permanently located inside the pump allows for measuring the rotating mass unbalance also during steady state operation of the same pump, that is when the pump has been completed with the stator part, assembled and delivered to the customer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Two embodiments of the invention, given by way of non-limiting example, will be described hereinbelow with reference to the accompanying drawings, in which:
[0025] FIG. 1 is a diagrammatic view of the displacement sensor;
[0026] FIG. 2 is a diagram of the electronic circuitry of the displacement sensor;
[0027] FIG. 3 a is a cross-sectional view of a first embodiment of a vacuum pump according to the present invention;
[0028] FIG. 3 b is a cross-sectional view of a second embodiment of a vacuum pump according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] Referring to FIG. 3 a , a first turbomolecular rotary pump 101 is schematically shown.
[0030] Pump 101 comprises a stationary portion and a rotating portion. The stationary portion comprises a basement 103 on which the rotating portion is mounted. The latter comprises a rotating shaft 105 supported by rolling bearings 107 , for instance ball bearings. Rotor 109 of electric motor 111 (the stator of which has not been shown for sake of simplicity) used to rotate shaft 105 , and pump rotor 113 , equipped with smooth or finned discs 115 , are mounted on the rotating shaft 105 .
[0031] As clearly shown in FIG. 3 a , according to the construction design of pump 101 , the pump rotor 113 has a bell-shaped cavity 117 housing rotating shaft 105 of the pump and electric motor 111 , in order to make the pump axially more compact. Such an arrangement is generally used for big turbomolecular pumps (rotor diameter of about 250 mm).
[0032] In FIG. 3 a the pump is shown during the balancing phase and hence rotor 113 is not located inside the pump housing, which is equipped with stator discs, but inside a vacuum-tight stationary bell 119 specifically intended for the balancing of said rotor 113 . Vacuum in the bell is achieved by means of an ancillary pumping system, not shown.
[0033] According to the present invention, a plurality of displacement sensors (four in the disclosed embodiment) 121 A- 121 D are directly mounted in basement 103 of pump 101 , close to rotor 113 and to rotating shaft 105 thereof. Each sensor faces the shaft 105 or the rotor 113 so that changes, if any, in the distance between the rotor and the sensor during rotation of the rotor can be detected.
[0034] More particularly, in the case depicted in FIG. 3 a , a first pair of sensors 121 A, 121 B face rotating shaft 105 and are turned towards it, whereas a second pair of sensors 121 C, 121 D face internal wall 113 a of rotor 113 and are turned towards such wall.
[0035] According to present invention, eddy current displacement sensors are advantageously employed.
[0036] Referring to FIG. 1 , there is schematically shown a generic displacement sensor 51 comprising a coil 53 , which is wound on a core 55 and in which a high frequency AC current generating a main magnetic field flows. The variation of distance “a” between coil 53 and an electrically conducting body R, for instance the pump rotor or the shaft thereof, causes a corresponding variation of the magnetic field induced and consequently of impedance Z measured in the coil of sensor 51 .
[0037] By using an impedance-to-voltage converter, such as that shown in FIG. 2 , a voltage signal D, the value of which depends on impedance Z and hence on the distance of the metal body from the sensor, can be obtained at the output from sensor 51 .
[0038] More precisely, the circuit shown in FIG. 2 comprises a high frequency oscillator 65 , an impedance 67 in series and a demodulator 63 . Impedance 67 must be sufficiently high to obtain a high sensitivity. Demodulation of voltage signal u outgoing from the sensor allows obtaining a voltage signal D that is a function of distance “a”.
[0039] Eddy current displacement sensors are capable of measuring distance variations of the order of 1 nm and are perfectly suitable for use in balancing turbomolecular pump rotors.
[0040] More particularly, in the described embodiment, a variation of the distance of internal wall 113 a of rotor 113 from facing sensors 121 C, 121 D, caused by an unbalance in rotor 113 , will cause a measurable impedance variation in the sensors. By measuring such an impedance variation, it is possible to obtain the distance variation, and hence the unbalance having generated it, and to correct such unbalance.
[0041] The process in case of a distance variation between rotating shaft. 105 and sensors 121 A, 121 B is similar.
[0042] To correct the unbalance of rotor 113 , cylindrical threaded bores 123 are provided in rotor 113 and are arranged with their axes lying in a plane orthogonal to the rotation axis of the rotor and tangentially relative to the same rotor. Additional masses consisting of threaded dowels can be located and displaced in said bores.
[0043] As an alternative, other balancing methods comprise the insertion of masses consisting of threaded dowels to be screwed into bores with axes radially arranged relative to the rotor.
[0044] Further in accordance with the invention, and still referring to FIG. 3 a , a third pair of displacement sensors 121 E, 121 F is provided, which sensors are arranged close to external wall 113 b of rotor 113 , between a pair of said rotor discs, and are turned towards the wall. The sensors 121 E, 121 F are cantilevered on a vertical support 120 adjacent to a wall of outer bell 119 .
[0045] It is clear that, at the end of the balancing phase, bell 119 and support 120 , if provided, will be removed and replaced by pump housing 121 with the stator integral thereto, so that the pump will be ready for being sent to the customer and used. Consequently, at the end of the balancing phase, displacement sensors 121 E, 121 F integral with bell 119 will be removed. On the contrary, sensors 121 A- 121 D mounted in basement 103 of pump 101 will remain inside the pump even during operation thereof, and they could be advantageously used to carry out measurements on the rotor balance conditions during normal pump operation.
[0046] Turning now to FIG. 3 b , a second embodiment of the invention is partially depicted.
[0047] A turbomolecular pump 201 differs from that previously disclosed with reference to FIG. 3 a in that rotor 213 has no bell-shaped cavity receiving rotating shaft 205 and electric motor 211 . Shaft 205 is instead supported by a pair of rolling bearings 207 , for instance ball bearings, and is driven by an electric motor 211 , the bearings and the motor are located in a pump region that is axially separated from the pumping region where rotor 213 is located.
[0048] Such arrangement is generally used for small and medium size turbomolecular pumps (rotor diameter smaller than about 160 mm).
[0049] Similarly to what is described above, according to the present invention a pair of displacement sensors 221 A, 221 B is provided in basement 203 of pump 201 , opposite rotating shaft 205 and at opposite sides of rotor 209 of electric motor 211 .
[0050] Also in that second embodiment, said displacement sensors are preferably eddy current sensors.
[0051] Like in the previous embodiment, further displacement sensors 221 C, 221 D and 221 E, 221 F are provided, which are integral with outer bell 219 and face rotor 213 .
[0052] More particularly, in the embodiment shown, a second pair of sensors 221 C, 221 D is provided close to internal wall 213 a of rotor 213 , whereas a third pair of sensors 221 E, 221 F is provided close to external wall 213 b of rotor 213 . These sensors are turned towards the rotor so that any variation in the distance between the rotor and the sensor during rotation of the same rotor can be detected.
[0053] In order to properly locate the second pair of sensors 221 C, 221 D, bell 219 is advantageously equipped with a central cylindrical projection 219 a penetrating into central bore 213 c of rotor 213 .
[0054] A removable vertical support 220 is provided adjacent to one of the walls of external bell 219 for the cantilevering of the third pair of displacement sensors 221 E, 221 F.
[0055] Similar to previous embodiment, pump 201 also has multiple threaded bores 223 with axes lying in planes orthogonal to the rotation axis of rotor 213 to allow locating and displacing additional masses.
[0056] Also in this case, threaded dowels located in radial bores instead of tangentially oriented bores can be used.
[0057] When, at the end of the balancing phase, bell 219 and support 220 , if present, will be removed, displacement sensors 221 C, 221 D and 221 E, 221 F will be removed as well, whereas sensors 221 A, 221 B mounted in basement 203 of pump 201 will remain inside said pump even during operation thereof, and they could be advantageously used to carry out field measurements.
[0058] It is clear that the turbomolecular pump according to the invention attains the intended aims, since using displacement sensors directly mounted inside the pump, close to the rotor or the rotating shaft thereof, allows using simpler and more precise mathematical models to determine the rotor unbalance. Consequently, the balancing phase might be carried out in quicker manner and with better results.
[0059] It is also clear that the above description has been given only by way of non-limiting example and that several modifications are possible without departing from the scope of the invention.
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A rotary vacuum pump ( 101; 201 ) comprising displacement sensors ( 121 A- 121 F; 221 A- 221 F), variously coupled to the pump basement ( 103; 203 ) and arranged close to the pump rotor ( 113; 213 ) and/or to the rotating shaft ( 105; 205 ) thereof, the sensors being turned towards it (them) and being perpendicular thereto, in order to detect non-homogeneous distributions, if any, of masses of said rotor ( 113; 213 ) with respect to its rotation axis. The invention also relates to a structure for and a method of balancing a rotary pump.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel varnish composition. During manufacturing a glass fiber laminate, a glass fiber cloth is dipped within a novel varnish composition, solvent removal by oven, and then dried to obtain a glass fiber prepreg. The obtained prepreg is laminated onto a copper foil to obtain a novel glass fiber laminate which has high glass transition temperature, good flame retardance, good heat resistance, and low coefficient of thermal expansion, and therefore is suitable for high-performance printed circuit boards.
2. Description of Related Art
A commercially available dual-functional is a brominated epoxy resin which is a mature product and has been used for long time. The long-term modified physical properties of the brominated epoxy resin grant a glass fiber laminate made of the brominated epoxy resin good mechanical properties, electrical properties, physical properties and dimensional stability. Such a modified brominated epoxy resin has great adhesion to glass fiber or copper foil. Therefore, glass fiber laminates made of brominated epoxy resin can be widely used in electronics and aviation industry. However, halogen in high temperature breaks down harmful substances which are harmful to our living environment and human health. Halide-containing substrates have been gradually inhibited for use. European Unit announced to implement related protection regulations such as Directive on the Waste Electronics and Electrical Equipment (referred to as WEEE), and Directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment (referred to as RoHS) in 2006. Another aspect in the lead-free manufacturing process, a welding process for lead-free packaging and assembly needs a higher temperature (an increase from 220° C. to 260° C.). The glass fiber laminates made of the existing dual-functional brominated epoxy resin cannot meet the requirements. Currently, multi-functional phenolic epoxy or phenolic novolac resin is used to achieve the required glass transition temperature and heat resistance for the lead-free manufacturing process. In a halogen-free substrate, a significant proportion of a polymer of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (referred to as DOPO) and phenol phenolic epoxy resin, or a polymer of DOPO and o-cresol phenolic epoxy resin is used along with dicyandiamide (referred to as Dicy) resin curing agent or multi-functional phenolic resin curing agent such as phenol novolac resin in order to increase the glass transition temperature (referred to as Tg) and heat resistance.
Physical properties of a printed circuit board are mainly determined by three major materials of the glass laminate combination: (1) epoxy (2) filling material and (3) reinforcing material. The development of the substrate continuously requires increasing the glass transition temperature (Tg), the temperature of heat resistance, while decreasing coefficient of thermal expansion (referred to as CTE). For the properties of epoxy resin systems, multi-functional phenolic epoxy resins are commonly used to modify the substrate properties. The multi-functional phenolic epoxy resin is, for example, tetraphenyl ethane phenolic epoxy resin made by Nan Ya Plastics company (trade name NPPN-431). The FR-4 substrate composed by NPPN-431, a phenol curing agent and a glass fiber cloth (grade E glass), the glass transition temperature is 180° C. (according to thermal mechanical analysis) and the heat resistance is above 10 minutes (solder oven at 288° C.). The physical properties of the multi-functional phenolic epoxy resin based laminates are gradually unable to meet the requirements of higher-performance boards.
Therefore, there is a need of a novel varnish composition which overcomes the above disadvantages.
SUMMARY OF THE INVENTION
The application of printed circuit board follows the development trend of light, thin, short, small characteristics. In order to comply with this trend, a glass fiber laminate must have higher glass transition temperature, low coefficient of thermal expansion and good heat resistance. In some specific fields, integrated circuit substrates of new generation need higher requirements such as higher glass transition temperature (Tg), lower coefficient of thermal expansion and better heat resistance. Unfortunately, most of commercially available multi-functional phenolic epoxy resins cannot be applicable. Moreover, major impact of environmental regulations on the printed circuit board industry is the inhibition to the use of lead and halogen. Conversion of lead-free processes forces the temperature for assembly to rise. Increase in temperature brings a harsh challenge to material reliability. The halogen-free conversion results in the decrease in glass transition temperature (Tg) while increase in water absorption rate for the glass substrates, both challenging the material reliability as well. The increase in water absorption rate definitely deteriorates the heat resistance of the substrates. Therefore how to increase the glass transition temperature and decrease the water absorption rate for the halogen-free substrate becomes a critical issue to overcome for those skilled in the art.
In order to achieve the aforementioned objects, according to an embodiment of the present invention, a resin varnish composition with high glass transition temperature includes (1) a benzoxazine resin having highly symmetric molecular structure; (2) at least one of naphthol novolac resins, aniline novolac resins and phenolic novolac resins; (3) fillers; and suitable flame retardant agents, curing accelerators, and solvents. The benzoxazine resin is a novel benzoxazine resin having a highly symmetric molecular structure and high proportion of tri-functional resin monomer or tetra-functional resin monomer.
The used of the novel resin varnish composition containing the benzoxazine resin in producing the glass fiber laminate effectively reduces the coefficient of thermal expansion while increase the glass transition temperature for the glass fiber laminate, which meets the requirement of light, thin, short, small characteristics for high-end products. Without changing procedures of the impregnating and laminating processes, the manufacturing conditions for the glass fiber laminate and downstream process of producing circuit boards, the glass fiber laminates can be made efficiently in mass using the current processing equipment and current manufacturing conditions.
In order to further the understanding regarding the present invention, the following embodiments are provided along with illustrations to facilitate the disclosure of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The aforementioned illustrations and following detailed descriptions are exemplary for the purpose of further explaining the scope of the present invention. Other objectives and advantages related to the present invention will be illustrated in the subsequent descriptions and appended tables.
According to the invention, a varnish composition with high glass transition temperature which can be applied to a glass fiber laminate includes (1) benzoxazine resin having a highly symmetric molecular structure; and (2) curing agent such as at least one of naphthol novolac resins (for example, tetra-functional naphthol novolac resin, tri-functional naphthol novolac resin, or di-functional naphthol), aniline novolac resins and phenolic novolac resins. (3) Fillers can be included as well. Some suitable flame retardant agents, curing accelerators, and solvents can be included as needed. The amount of (1) benzoxazine resin based on the total amount of (1) benzoxazine resin and (2) curing agent is in the range of 60-95 wt %. The amount of (2) curing agent based on the total amount of (1) benzoxazine resin and (2) curing agent is in the range of 5-40 wt %.
The benzoxazine resin is characterized in that it has high proportion of tri-functional resin monomer or high proportion of tetra-functional resin monomer, a small molecular structure and a highly structural symmetry. Therefore, the glass fiber laminate made of benzoxazine resin has advantageous properties which suit the application for integrated circuit substrates, such as high glass transition temperature (Tg), low coefficient of thermal expansion (CTE), and good heat resistance and stability.
The benzoxazine resin can be obtained by the following steps.
Step 1. A phenolic hydroxyl aromatic aldehyde compound (A), such as para-hydroxybenzaldehyde, 2,6-Dimethyl-4-hydroxybenzaldehyde or salicylaldehyde, reacts with a phenol compound (B) such as phenol or m-cresol to obtain a phenolic novolac resin (C) having highly structural symmetry and high proportion of tri-functional resin monomer.
Step 2. A aldehyde compound (A) such as glyoxal or terephthalaldehyde reacts with a phenol compound (B) such as phenol or m-cresol to obtain a phenolic novolac resin (D) having highly structural symmetry and high proportion of tetra-functional resin monomer.
Step 3. The phenolic novolac resin (C) having high proportion of tri-functional resin monomer, formaldehyde and a primary amine compound (E) such as aniline, p-toluidine, 3,5-dimethyl aniline are subject to dehydration and heterocyclic ring formation to obtain a benzoxazine resin (F1) as a specific example of the (1) benzoxazine recited in the invention.
Step. 4. The phenolic novolac resin (D) having high proportion of tetra-functional resin monomer, formaldehyde and a primary amine compound (E) such as aniline, p-toluidine or 3,5-dimethylaniline are subject to dehydration and heterocyclic ring formation to obtain benzoxazine resin (F2) as another specific example of the (1) benzoxazine recited in the invention.
The formation of phenolic novolac resin (C) having high proportion of tri-functional resin monomer includes the following steps.
8 to 20 weight percent (wt %) of aldehyde compounds such as para-hydroxybenzaldehyde, and 80 to 95 weight percent (wt %) of phenolic compounds such as phenol, with phenol/para-hydroxybenzaldehyde mole ratio being 10 to 20, are mixed and dissolved at 60˜100° C., and then subject to condensation reaction in the presence of an acidic catalyst (such as methyl sulfonic acid, p-toluenesulfonic acid, boron trifluoride or aluminum chloride) for 3 to 4 hours to obtain having a phenolic resin having high proportion of tri-functional resin monomer. By means of analytic patterns of gel permeation chromatography (referred to as GPC), the proportion of the tri-functional resin monomer is greater than 70 area percent (Area %), the remaining 30 area percent (Area %) being phenolic resins having 1˜4 resin repeating units. Tri-functional resin monomer structure is as follows
Wherein R1 can be H or CH3.
The formation of the phenolic novolac resin (D) having high proportion of tetra-functional resin monomer includes the following steps.
5 to 20 weight percent (wt %) of aldehyde compounds such as glyoxal, and 80 to 95 weight percent (wt %) of phenolic compounds such as phenol, with phenol/glyoxal mole ratio being 10 to 30, are mixed and dissolved at 60˜100° C., and then subject to condensation reaction in the presence of an acidic catalyst (such as methyl sulfonic acid, p-toluenesulfonic acid, boron trifluoride or aluminum chloride) for 3 to 5 hours to obtain having a phenolic resin having high proportion of tetra-functional resin monomer. By means of analytic patterns of gel permeation chromatography (referred to as GPC), the proportion of the tetra-functional resin monomer is greater than 70 area percent (Area %), the remaining 30 area percent (Area %) being phenolic resins having 1˜4 resin repeating units. Tetra-functional resin monomer structure is as follows
Wherein R2 can be H or CH3;
X can be
The formation of the benzoxazine resin (F1) having high proportion of tri-functional resin monomer includes the following steps.
The phenolic resin (C) having high proportion of tri-functional resin monomer, formaldehyde, aniline compounds such as aniline, and a solvent such as propylene glycol monomethyl ether (referred to as PM), with mole ratio of 1:2.1:1 are subject to heterocyclic condensation at 70 to 100° C. to obtain benzoxazine resin (F1). According to analytic patterns of gel permeation chromatography (GPC), the proportion of tri-functional resin monomer in the obtained product is more than 60 area percent (Area %).
The tri-functional resin monomer of the phenolic resin (C) have the following structure:
R1 can be H or CH3;
R3 can be
The formation of the benzoxazine resin (F2) having high proportion of tetra-functional resin monomer includes the following steps.
The phenolic novolac resin (D) having high proportion of tetra-functional resin monomer, formaldehyde, aniline compounds such as aniline, and a solvent such as propylene glycol monomethyl ether, with mole ratio of 1:2.1:1 are subject to heterocyclic condensation at 70 to 100° C. to obtain a benzoxazine resin (F2). According to analytic patterns of the gel permeation chromatography (GPC), the proportion of tetra-functional resin monomer in the obtained product is more than 60 area percent (Area %).
The tetra-functional resin monomer of the phenolic novolac resin (D) have the following structure.
R2 can be H or CH3;
R3 can be
and
X can be
The formation of the phenolic resin (C) having high proportion of tri-functional resin monomer is achieved by the following steps.
The steps include: in a 2 L four-necked glass reactor equipped with a heating mantle, a temperature controller, an electric mixer and a condenser are poured 274.5 g of para-hydroxybenzaldehyde and 3172.5 g of phenol, and then mixed and dissolved at 60° C.; after adding 43.2 g methyl sulfonic acid catalyst, the temperature is raised up to 70° C. for further 3-hour reaction; after sodium hydroxide (referred to as NaOH) is added to neutralize for phenol removal in vacuum, a solvent methyl isobutyl ketone (referred to as MIBK) and water are added to wash off; and then, the solvent methyl isobutyl ketone (MIBK) is removed in vacuum to obtain a phenolic resin (C) having high proportion of tri-functional resin monomer.
In the formation of the above resin (C), the aldehyde compounds are generally para-hydroxybenzaldehyde, 2,6-dimethyl-4-hydroxy benzaldehyde or salicylaldehyde etc. Para-hydroxybenzaldehyde is preferably used.
The phenolic compounds, generally, are phenol or m-cresol, etc. Phenol is preferably used.
The formation of the phenolic novolac resin (D) having high proportion of tetra-functional resin monomer is achieved by the following steps.
The steps include: in a 2 L four-necked glass reactor equipped with a heating mantle, a temperature controller, an electric mixer and a condenser are poured 135 g of glyoxal (40 wt % aqueous solution) and 2188 g of phenol, and then mixed and dissolved at 70° C.; after adding 3 g methyl sulfonic acid catalyst, the temperature is raised up to 98° C. for further 3.5-hour reaction; after sodium hydroxide (NaOH) is added to neutralize for phenol removal in vacuum, a solvent methyl isobutyl ketone (MIBK) and water are added to wash off; and then, the solvent methyl isobutyl ketone (MIBK) is removed in vacuum to obtain a phenolic novolac resin (D) having high proportion of tetra-functional resin monomer.
In the formation of the above resin (D), the aldehyde compounds are generally glyoxal or terephthalaldehyde. Glyoxal is preferably used.
The phenolic compounds, generally, are phenol or m-cresol, etc. Phenol is preferably used.
The formation of the benzoxazine resin (F1) having high proportion of tri-functional resin monomer is achieved by the following steps.
The steps include: in a 2 L four-necked glass reactor equipped with a heating mantle, a temperature controller, an electric mixer and a condenser, 350 g of phenolic resin (C) having high proportion of tri-functional resin monomer and 246 g of paraformaldehyde are dissolved thoroughly in the presence of 816 g of a solvent propylene glycol monomethyl ether at 85° C., 334.4 g of aniline is dropped in the course of 3 hours into the reactor at constant speed by a quantitative pump to proceed the reaction at 85° C. After finishing the dropping addition of aniline, the temperature is kept at 85° C. for aging for 2 hours, then the temperature is raised to 105° C. After water and part of the solvent are removed, a benzoxazine resin solution with 56 wt % solid is obtained. According to gel permeation chromatography (GPC) analysis, the proportion of the tri-functional resin monomer in this benzoxazine resin is up to 60 area percent (Area %) or more.
The formation of the benzoxazine resin (F2) having high proportion of tetra-functional resin monomer is achieved by the following steps.
The steps include: in a 2 L four-necked glass reactor equipped with a heating mantle, a temperature controller, an electric mixer and a condenser, 200 g of phenolic novolac resin (D) having high proportion of tetra-functional resin monomer and 124.5 g of paraformaldehyde are dissolved thoroughly in the presence of 816 g of a solvent propylene glycol monomethyl ether at 85° C., 169 g of aniline is dropped in the course of 3 hours into the reactor at constant speed by a quantitative pump to proceed the reaction at 85° C. After finishing the dropping addition of aniline, the temperature is kept at 85° C. for aging for 2 hours, then the temperature is raised to 105° C. After water and part of the solvent are removed, a benzoxazine resin solution with 56 wt % solid is obtained. According to gel permeation chromatography (GPC) analysis, the proportion of the tetra-functional resin monomer in this benzoxazine resin is up to 60 area percent (Area %) or more.
In the formation of the benzoxazine resins F1 and F2, the aldehyde compounds used in the preparation of symmetrical benzozazine, paraformaldehyde is preferred. For amine compounds, primary amines are commonly used, and aniline is preferred.
In the resin varnish composition of the invention, the second component (2) is a curing agent, including (a) naphthol novolac resin, such as tetra-functional naphthol novolac resin by synthesis of 2,7-dihydroxynaphthalene and formaldehyde, tri-functional naphthol novolac resin by synthesis of 2,7-dihydroxynaphthalene, β-naphthol and formaldehyde, and di-functional naphthol; (b) aniline novolac resin (referred to as AN), such as aniline novolac resin by the synthesis of aniline and formaldehyde, or 4,4-diamino diphenyl methane (referred to as DDM), etc.; and (c) phenol novolac resin, such as phenolic novolac resin (referred to as PN) by the synthesis of phenol and formaldehyde, amino triazine novolac resin (referred to as ATN), bisphenol-A novolac resin (referred to as BN) and tetraphenyl ethane novolac resin (referred to as TPE).
When the above second component is used as the curing agent, the dry weight ratio of the curing agent and benzoxazine resin is in the range of 0.05 to 0.5, and the most preferred ratio is 0.1 to 0.3.
In the resin varnish composition of the present invention the third component is a filler, including silica, quartz powder, barium sulfate, and alumina, etc. Silica is preferred. The filler can be used alone or in mixture of two or more selected from above. The amount of the filler based on the total weight of the resin (benzoxazine resin (1)+curing agent (2)) is in the range of 80 to 200 phr, preferred ratio is 100 to 120 phr.
The resin varnish composition of the invention can further contain flame retardants including phosphorus-containing organic flame retardants, phosphorus resins. The phosphorus resins are DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), DOPO-hydroxyquinone (DOPO-HQ), etc.
The resin varnish composition of the invention can further contain a curing accelerator including tertiary phosphines, tertiary amines, quaternary phosphonium salts, quaternary ammoniums, imidazole compounds. The tertiary phosphines include triphenylphosphine, etc.; tertiary amines include trimethyl aniline, triethyl amine, tributyl amine, etc.; quaternary phosphonium salts include halide-containing quaternary phosphonium, such as tetrabutyl phosphonium bromide, tetraphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, etc.; quaternary ammoniums include halide-containing quaternary ammoniums, such as tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrabutyl ammonium bromide; imidazole compounds include 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-ethyl-4-hydroxymethyl imidazole, etc. Among those recited above, 2-methyl-imidazole or 2-ethyl-4-methyl imidazole is preferred. The curing accelerator can be used alone or mixed with two or more simultaneously.
The resin varnish composition of the invention can further contain organic solvents including organic aromatic solvents, aprotic solvents, ketone solvents, ether solvents and ester solvents. Examples of appropriate solvent include N,N-dimethyl formamide, acetone, methyl ethyl ketone, propylene glycol monomethyl ether (PM) and so on. Main function of the organic solvent is to dissolve the benzoxazine resin and curing agent to achieve uniform mixing and adjust the viscosity of the resin varnish composition for easy production of glass fiber laminates.
Specific procedures of making glass fiber laminates by using the above composition of this invention include the following steps.
Step 1: Preparation of benzoxazine resin varnish composition. The component (1) is benzoxazine having novel, highly symmetrically structural characteristics. The amount of component (1), the benzoxazine resin, relative to the sum of the component (1) and the component (2) is between 60 and 95 wt %. The amount of the component (2), the curing agent, relative to the sum of the component (1) and the component (2) is 5 to 40 wt %. The amount of the component (3), the filler, relative to the sum of the component (1) and the component (2) is 80 to 200 phr; the amount of the flame retardant relative to the sum of the component (1) and the component (2) is 0 to 30 phr; the curing accelerator relative to the component (1) is 0.01 to 1 phr; and the organic solvent relative to the sum of the component (1) and the component (2) is 30 to 60 phr. The components (1), (2), (3), the fire resistant agent, the curing accelerator and the organic solvent are then mixed thoroughly to complete the preparation of varnish composition.
Step 2: Preparation of a prepreg. A glass fiber cloth is impregnated in the resin varnish composition obtained at step (1) for 1 to 3 minutes. Then the resin-impregnated glass fiber cloth is placed into a heat oven at 170° C. for 2 to 5 minutes. After removal of the organic solvent, the glass fiber cloth is taken out of the oven, stays aside for cooling to obtain a prepreg.
Step 3: Hot press of glass laminates. A plurality of prepregs are stacked in layers in a manner that on one or both surfaces of the stack is placed a copper foil and then put into a thermal press to apply pressure and heat over the stack for curing so as to obtain the glass fiber laminate having excellent properties.
The resin varnish composition of the invention can be cured at 100 to 300° C., preferably 150 to 210° C. If the curing temperature is too low, then the curing rate is too slow and therefore it needs to prolong the curing time, which do not meet the requirement of production efficiency. However, excessively high curing temperature tends to make resin cracking, disadvantageously deteriorating physical properties of the glass fiber laminate.
EXAMPLE
The following specific embodiments of the present invention describe the invention in details. Codes and its components used in Examples and Comparative Examples are as follows:
Resin F1: Benzoxazine having high proportion of tri-functional resin monomer according to this invention.
Resin F2: Benzoxazine having high proportion of tetra-functional resin monomer according to this invention.
Resin 1: Tetraphenyl ethane phenolic novolac epoxy resin manufactured by Nan Ya Plastics Corporation, trade name NPPN-431A70, epoxy equivalent of 200˜220 g/eq; solid content of 69 to 71 weight percent.
Resin 2: Tetra-functional naphthalene epoxy resin manufactured by Dainippon ink company, trade name EXA-4700, epoxy equivalent of 150 to 170 g/eq.
Resin 3: Bisphenol-A typo benzoxazine resin made by Nan Ya Plastics Corporation, trade name NPEX-230.
Curing agent 1: Tetraphenyl ethane phenolic novolac resin manufactured by Nan Ya Plastics Corporation; trade name TPN.
Curing agent 2: Tri-functional naphthol resin made by Nan Ya Plastics Corporation, from 2,7-dihydroxynaphthalene, β-naphthol and aldehydes.
Curing agent 3: 4,4-diamino diphenyl methane (referred to as DDM), containing 14.1 wt % nitrogen.
Curing agent 4: amino triazine novolac resin, softening point of 80˜85° C.; 5˜20 wt % nitrogen.
Flame retardant 1: phosphorus-containing flame retardant manufactured by Otsuka Chemical Company, Japan; 13.4 wt % of phosphorus, trade name SPB-100.
Curing accelerator 1: 2-methyl imidazole (referred to as 2-MI) solution of 14.2 g of 2-methylimidazole (2MI) dissolved in 85.8 g N,N-dimethyl formamide (DMF).
Filler 1: silica (SiO 2 )
Fiberglass cloth: glass fiber cloth 7628 (Level E glass) manufactured by Nan Ya Plastics Corporation.
Example 1
45.5 dry weight parts of benzoxazine resin F1 having symmetric structure and high proportion of tri-functional resin monomer, 4.5 dry weight parts of curing agent 1, 60 dry weight parts of filler 1 are formulated with an appropriate solvent by a well-known method of preparing glass fiber laminate to obtain a resin varnish composition having 50 wt % solids. The formula is detailed in Table (1). In the preparation method, one 7628 glass fiber cloth is impregnated with the above resin varnish composition, and then dried at 170° C. (oven temperature) for few minutes. By means of adjusting drying time, a prepreg having melt viscosity of 8000 to 12000 poises is obtained. Four prepregs are stacked in layers between two copper foils each of which has a thickness of 35 μm, and subject to thermal pressing under pressure of 30 kg/cm 2 to obtain the glass fiber laminate.
The temperature control procedures are as follows.
Example 2
45.5 dry weight parts of benzoxazine resin F1 having a symmetric structure and high proportion of tri-functional resin monomer, 4.5 dry weight parts of curing agent 2, 60 dry weight parts of filler 1 are used. The formula is detailed in Table 1. The procedures are same as in Example 1.
Example 3
45.5 dry weight parts of benzoxazine resin F1 having a symmetric structure and high proportion of tri-functional resin monomer, 4.5 dry weight parts of curing agent 3, 60 dry weight parts of filler 1 are used. The formula is detailed in Table 1. The procedures are same as in Example 1.
Example 4
45.5 dry weight parts of benzoxazine resin F1 having a symmetric structure and high proportion of tri-functional resin monomer, 4.5 dry weight parts of curing agent 4, 50 dry weight parts of filler 1 are used. The formula is detailed in Table 1. The procedures are same as in Example 1.
Example 5
45.5 dry weight parts of benzoxazine resin F2 having a symmetric structure and high proportion of tetra-functional resin monomer, 4.5 dry weight parts of curing agent 1, 60 dry weight parts of filler 1 are used. An appropriate solvent is used to obtain the resin varnish composition having 50 wt % solids. The formula is detailed in Table 1. In the preparation method, one 7628 glass fiber cloth is impregnated with the above resin varnish composition, and then dried at 170° C. (oven temperature) for few minutes. By means of adjusting drying time, a prepreg having melt viscosity of 8000 to 12000 poises is obtained. Four prepregs are stacked in layers between two copper foils each of which has a thickness of 35 μm, and subject to thermal pressing under pressure of 30 kg/cm 2 to obtain the glass fiber laminate.
The temperature control procedures are as follows
Example 6
45.5 dry weight parts of benzoxazine resin F2 having a symmetric structure and high proportion of tetra-functional resin monomer, 4.5 dry weight parts of curing agent 2, 60 dry weight parts of filler 1 are used. The formula is detailed in Table 1. The procedures are same as in Example 5.
Example 7
45.5 dry weight parts of benzoxazine resin F2 having a symmetric structure and high proportion of tetra-functional resin monomer, 4.5 dry weight parts of curing agent 3, 60 dry weight parts of filler 1 are used. The formula is detailed in Table 1. The procedures are same as in Example 5.
Example 8
45.5 dry weight parts of benzoxazine resin F2 having a symmetric structure and high proportion of tetra-functional resin monomer, 4.5 dry weight parts of curing agent 4, 50 dry weight parts of filler 1 are used. The formula is detailed in Table 1. The procedures are same as in Example 5.
Comparative Examples 1˜3
The formula of the resin 1, the resin 2, the resin 3, the curing agent 1 and the curing agent 4 is detailed in Table 2. Acetone is used to adjust solids content to 65 wt % of the resin varnish composition. Glass fiber laminates are prepared in the same way with the implementation of Example 1.
Measurement
1. The glass transition temperature:
Using Thermal Mechanical Analyzer (referred to as TMA), heating rate=20° C./min, 30° C. to 300° C.
2. Coefficient of Thermal Expansion (Referred to as CTE)
Using Thermal Mechanical Analyzer (referred to as TMA), heating rate=20° C./min, 30° C. to 300° C.
3. Water Absorption Test:
A water absorption test method includes taking a glass fiber laminate having a copper foil thereon, removing the copper foil on the glass fiber laminate by using a ferric chloride solution; and then cutting into 5 cm×5 cm square specimens. The specimens are dried in an oven at 105° C. for 2 hr. Then, the specimens are placed inside a steam pressure cooker. The pressure cooker tester (referred to as PCT) conditions are 2 atm×120° C. After placed in the pressure cooker for 120 min, the weight differences of the specimens before and after placed in the pressure cooker are divided by the initial weights of the specimens to obtain the water absorption rate.
4. Heat Resistance Test:
After the 5 cm×5 cm square specimens of the glass laminates whose copper foils have been removed laminate are tested by the water absorption test, those specimens are placed in a solder furnace at 288° C. until the glass laminates delaminate.
5. Flame Resistance Test:
The Specimens are cut into 5 rectangular pieces of 0.5 in×4.7 in. 2 cm-high blue flames is used to burn for 10 seconds for each specimen and then removed. This flame burning repeats twice. Flame self-extinguishing time after removal of the flame for each burning is recorded. The total flame self-extinguishing time for each specimen is no more than 10 seconds. The sum of flame self-extinguishing time for all specimens is no more than 50 seconds, and at this moment it reaches 94V0.
TABLE 1
Formula of the resin varnish composition and physical
properties of the glass fiber laminates (Examples).
Example 1
Example 2
Example 3
Example 4
Example 5
Example 6
Example 7
Example 8
Components of resin
1. resinF1 (parts)
45.5
45.5
45.5
45.5
varnish composition
2. resinF2 (parts)
45.5
45.5
45.5
45.5
3. curing agent1 (parts)
4.5
4.5
4. curing agent2 (parts)
4.5
4.5
5. curing agent3 (parts)
4.5
4.5
6. curing agent4 (parts)
4.5
4.5
7. filler1 (parts)
60
60
60
50
60
60
60
50
8. flame retardant1
0.5
0.5
0.5
0
0.5
0.5
0.5
0
(parts)
9. curing
0
0
0
0
0
0
0
0
accelerator1(parts)
Physical [properties
1. glass transition tempera-
215
209
214
232
222
217
213
242
of glass fiber laminates
ture (° C.) (TMA)
2. heat resistance (288° C.)
10 min ↑
10 min ↑
10 min ↑
10 min ↑
10 min ↑
10 min ↑
10 min ↑
10 min ↑
3. Water Absorption
0.23
0.21
0.3
0.18
0.286
0.29
0.26
0.26
Rate (wt %)
(PCT: 2 hr * 120 min)
4. coefficient of thermal
25/110
21/130
16/135
33/139
25/118
22/136
24/122
28/121
expansion (α1/α2)
(μm/(m° C.))
5. Flame Resistance
94V0
94V0
94V0
94V0
94V0
94V0
94V0
94V0
pass
pass
pass
pass
pass
pass
pass
pass
Note:
the “parts” of Table 1 means “dry weight parts” which do not include solvent.
TABLE 2
Formula of the resin varnish composition and physical properties
of the fiber laminates (Comparative Examples).
Comparative
Comparative
Comparative
Example1
Example2
Example3
Components
1.
resin1 (parts)
36
of resin
2.
resin2 (parts)
36
of
3.
resin3 (parts)
36
composition
4.
curing agent1 (parts)
4
4
5.
curing agent4 (parts)
4
6.
filler1 (parts)
60
60
60
7.
flame retardant1 (parts)
1.2
1.2
0.5
8.
curing accelerator1 (parts)
0.01
0.04
0
Physical
1.
glass transition temperature
187
200
178.4
properties
(° C.) (TMA)
of lass
2.
heat resistance (288° C.)
8 min ↑
8 min ↑
8 min ↑
fiber
laminate
3.
Water Absorption Rate (wt %)
0.56
0.49
0.21
(PCT: 2 hr*120 min)
4.
coefficient of thermal
30/112
30/90
20/116
expansion(α1/α2)
(μm)(m ° C. ))
5.
Flame Resistance
94V0 pass
94V0 pass
94V0 pass
Note:
the “parts” of Table 2 means “dry weight parts” which do not include solvent.
Comparing with the glass fiber laminates made of tetra-functional Tetraphenyl ethane phenolic novolac epoxy resin or tetra-functional naphthalene epoxy resin, the glass fiber laminates made of Benzoxazine having high proportion of tri-functional resin monomer and Benzoxazine having high proportion of tetra-functional resin monomer has better physical properties, for example, the glass transition temperature increases from 187-200° C. to above 213° C., the water absorption rate decreases from about 0.5 wt % to lower than 0.3 wt %, and the heat resistance and coefficient of thermal expansion are improved. Thus, the manufactured glass fiber laminates are suitable for substrates of high performance integral circuit.
The descriptions illustrated supra set forth simply the preferred embodiments of the present invention; however, the characteristics of the present invention are by no means restricted thereto. All changes, alternations, or modifications conveniently considered by those skilled in the art are deemed to be encompassed within the scope of the present invention delineated by the following claims.
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A varnish composition includes (1) a benzoxazine resin having highly symmetric molecular structure; (2) at least one of naphthol novolac resins, aniline novolac resins and phenolic novolac resins; (3) fillers. The benzoxazine resin having highly symmetric molecular structure, and the at least one of naphthol novolac resins, aniline novolac resins and phenolic novolac resins contribute to increase the glass transition temperature of the varnish composition, while decrease the coefficient of thermal expansion and moisture absorbability due to their small and highly symmetric molecular structures. A copper substrate can meet the requirement of high glass transition temperature (TMA≧200° C.) and low coefficient of thermal expansion (α1/α≦30/135 (μm/m° C.). Therefore, the composition of the invention can be widely used as high-performance electronic material.
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1. PRIORITY CLAIM
[0001] This application is a continuation of and claims priority under 35 U.S.C. §120 and/or 35 U.S.C. §365 to co-pending PCT Application No. PCT/GB2009/050543 having an international filing date of May 20, 2009, which claims priority to Great Britain Application No. 0809235.5 filed on May 21, 2008.
2. FIELD OF THE INVENTION
[0002] The present invention relates to a Supervisory System Controller (SSC) for controlling and monitoring the generation of electrical energy from renewable sources, managing the storage of energy so generated and interconnecting the energy generating elements, storage and load.
3. RELATED ART
[0003] One type of radio communications system is a cellular communications system. In a cellular communications system, the area over which service is provided is divided into a number of smaller areas called cells. Typically each cell is served from a base transceiver station (BTS) which has a corresponding antenna or antennas for transmission to and reception from a user station, normally a mobile station and a backhaul connection for routing of communications to a fixed switching centre for onward transmission to fixed user terminals or other communications networks. Presently established cellular radio communications systems include Global System for Mobile communications (GSM), Code Division Multiple Access (CDMA), Worldwide Interoperability for Microwave Access (WiMAX), and also the Universal Mobile Telecommunication System (UMTS).
[0004] Such base transceiver stations and their associated equipment require electrical power to operate. Typically this power has been provided by connection to an electrical grid, or in cases where this is not available connection to a standalone diesel generator. More recently power generated from renewable means such as wind turbines or to photovoltaic (PV) arrays has been used as an alternative to diesel generators for sites without a grid connection.
[0005] While this offers considerably advantages in operational costs over a diesel generator their performance is very dependant on the prevailing weather conditions and significant energy storage is required to provide a reserve for periods of low renewable energy generation. The disadvantage with these systems is that in order to provide the high level of power availability required for reliable operation of a radio communications system the size of both the generation equipment and the storage capacity has to be considerably increased over that of a system that is not required to provide continuous power.
[0006] Renewable energy generators such as wind turbines and PV arrays require electronic control systems to regulate their performance and to ensure that batteries used for energy storage are charged according to the correct profile for the size, type of cell technology employed in the battery, and environmental factors such as temperature. Whilst PV controllers exist that perform this function, when a wind turbine and PV system are combined together the usual mode of operation is for the turbine controller to err on the side of under charging the batteries as its control is based on fixed voltage level thresholds that do not take account of battery condition or temperature. When these thresholds are exceeded, dump loads are switched in to dissipate excess energy and to prevent damage occurring to the battery by charging it with too high a current. The use of fixed thresholds for controlling dump loads is wasteful of energy and can lead to the over sizing of both turbines and battery systems to compensate.
[0007] In a system described above it is normal to provide a means of preventing the batteries from becoming deeply discharged or to prevent discharge below a certain defined state of charge to extend the batteries operating life. This is provided by a low voltage disconnect device that will remove all loads from the batteries when the batteries terminal voltage drops below a preset voltage threshold. Hysteresis is provided in the detection circuitry to prevent the loads reconnecting again until the battery is being recharged. This hysteresis is also of a preset, fixed value. The use of fixed thresholds for the control and switching of loads offers none of the flexibility required to permit the most efficient implementation of a renewable energy powered telecommunications system.
[0008] Present control systems do not permit the automatic, selective operation of disconnect devices to remove loads of a specific type for the purpose of prolonging the operation of a higher priority load, thereby permitting the use smaller batteries. Neither do existing systems permit an operator to remotely command a disconnect device to remain connected, to override a low voltage disconnect, and provide additional reserves of power under exceptional circumstances should it be required.
[0009] Existing systems have no means of receiving predicted weather data or correlating such weather data with the local micro climate to predict the availability and quantity of renewable energy at the site. Neither do they accurately determine the state of charge of batteries and use this data together with the energy prediction data to control the loads to within the system, either by variable power control or by means of selective disconnection and reconnection. Existing systems do not permit communications between the telecommunications equipment and the system controller for the purpose of power control or the passing of data, monitoring and alarm information.
[0010] Due to the failings mentioned above it is also not possible to obtain the most efficient use of a fossil fuelled backup generator, both in fuel usage and service maintenance intervals.
[0011] Existing systems do not offer dual or N+1 redundancy of critical components in the renewable energy components, for example splitting individual PV panels between multiple PV controllers for the purpose of failure tolerance. Neither are critical components that ensure reliability of supply to the telecommunications equipment duplicated to ensure the highest levels of reliability. Although multiple strings of batteries are occasionally used in such systems they are not configured to permit the automatic removal and testing of an individual battery string or the automatic removal of a battery string that has developed a fault.
SUMMARY
[0012] The present invention addresses some or all of the above disadvantages.
[0013] According to one aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources, managing the storage of energy so generated and interconnecting the energy generating elements, storage and load.
[0014] According to another aspect of the present invention, there is provided a method of receiving weather forecast data and using said data to predict renewable energy availability at a site for the purpose of connecting, disconnecting or controlling the power consumption of loads connected to a battery.
[0015] According to another aspect of the present invention, there is provided a method of more efficiently controlling a fossil fuelled backup generator by overriding or delaying the operation of said fossil fuelled generator to recharge a battery if predicted weather data indicates that renewable energy will become available within an acceptable timeframe.
[0016] According to another aspect of the present invention, there is provided a method to conserve generator fuel and extend generator servicing intervals by delaying a scheduled generator maintenance running period, that may be required to preserve generator condition and starting capability, such that it occurs when weather data is predicting low renewable energy availability and a battery is in a reduced state of charge.
[0017] According to another aspect of the present invention, there is provided a plurality of independent disconnection devices that are controlled by an algorithm that uses voltage levels, battery charge status, a real time clock, predicted renewable energy availability and operator remote commands to control said devices.
[0018] According to another aspect of the present invention, there is provided a control system that can dynamically vary the disconnection thresholds of one or more disconnect devices to remove power load from a DC bus to make available a greater proportion of energy to one or more specific loads that may remain connected. This may specifically include the disconnection of a base station to make available a greater proportion of battery energy to backhaul communications equipment.
[0019] Further aspects of the invention are as claimed in the dependent claims. Additional specific advantages are apparent from the following description and figures which relate to a merely exemplary embodiment of the present invention.
[0020] The present invention is applicable to, but not limited to, radio communication systems such as the Global System for Mobile communications (GSM), Code Division Multiple Access (CDMA), Worldwide Interoperability for Microwave Access (WiMAX), and also the Universal Mobile Telecommunication System (UMTS).
[0021] According to another aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources, which operates to maximise the power transfer from a wind turbine to a battery by automatically varying the threshold levels at which turbine dump loads are switched based upon system inputs and measurements.
[0022] According to another aspect of the present invention, there is provided an apparatus which varies the threshold levels at which turbine dump loads are switched according to the precise state of charge of the battery and the usage pattern of the battery preceding the charge period.
[0023] According to another aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources that can communicate with a remote device to obtain weather forecast data for the purpose of predicting future renewable energy generation capability.
[0024] According to another aspect of the present invention, there is provided an apparatus which correlates local micro climate conditions with forecasted weather data for the purpose of predicting future energy availability.
[0025] According to another aspect of the present invention, there is provided an apparatus that uses predicted renewable energy availability for the purpose of connecting, disconnecting or controlling the power consumption of loads connected to a battery.
[0026] According to another aspect of the present invention, there is provided an apparatus that can override or delay the operation of a fossil fuelled generator to recharge a battery if predicted energy data indicates that renewable energy will become available within an acceptable timeframe.
[0027] According to another aspect of the present invention, there is provided a method to conserve generator fuel and extend generator servicing intervals by delaying a scheduled generator maintenance running period, that may be required to preserve generator condition and starting capability, such that it occurs when renewable energy availability is predicted to be low and a battery is in a reduced state of charge.
[0028] According to another aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources that has plurality of disconnect devices to allow independent disconnection of individual loads from a DC bus according to an algorithm that uses voltage levels, battery state of charge, time and override command.
[0029] According to another aspect of the present invention, there is provided an apparatus that uses the measure of battery state of charge for the purpose of connecting, disconnecting or controlling the power consumption of loads connected to a battery.
[0030] According to another aspect of the present invention, there is provided an apparatus wherein one or more said disconnect devices can have their operating thresholds adjusted to remove power load from a DC bus to make available a greater proportion of energy to one or more specific loads that may remain connected.
[0031] According to another aspect of the present invention, there is provided an apparatus that that may dynamically vary the disconnection threshold of a disconnect device controlling a base station to make available a greater proportion of battery energy to backhaul communications equipment.
[0032] According to another aspect of the present invention, there is provided an apparatus that can be commanded to override the normal operation of battery protection disconnect devices to provide additional operational power under an emergency condition.
[0033] According to another aspect of the present invention, there is provided an apparatus that can communicate with telecommunications equipment to command said equipment to reduce its power consumption.
[0034] According to another aspect of the present invention, there is provided an apparatus whereby a communications system comprises two BTSs, one providing BCCH carriers and a second with additional capacity, that can exercise power control by disconnecting the second BTS.
[0035] According to another aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources that has a plurality of PV arrays and individually switched and controlled PV controllers to offer redundancy of power supply in the event of a PV array or PV controller failure by disconnecting the failed device from the remainder of the functioning system and communicating the failure to the system controller.
[0036] According to another aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources that has a plurality of contactor devices to offer redundancy of power connection in the event of a contactor or central controller failure.
[0037] According to another aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources that has a plurality of batteries to offer redundancy of battery power in the event of a fault within an individual battery string.
[0038] According to another aspect of the present invention, there is provided an apparatus that has a plurality of batteries to permit automatic, periodic removal and capacity measurement of an individual battery string without interruption of normal operation.
[0039] According to another aspect of the present invention, there is provided an to apparatus that has a plurality of batteries to permit battery replacement at the batteries end of life without affecting the normal operation of the communications equipment.
[0040] According to another aspect of the present invention, there is provided An apparatus for controlling and monitoring the generation of electrical energy from renewable sources that has redundant contactors to improve reliability for the switching of safety devices such as mast warning lights to assist in aircraft collision avoidance.
[0041] According to another aspect of the present invention, there is provided an apparatus that controls redundant contactors for the switching of safety devices, such as mast warning lights used to assist in aircraft collision avoidance, continue to receive power when other system loads have been disconnected.
[0042] According to another aspect of the present invention, there is provided an apparatus for controlling and monitoring the generation of electrical energy from renewable sources that has a plurality of individually switched and controlled wind turbines to offer redundancy of power supply in the event of a turbine failure by disconnecting the failed device from the remainder of the functioning system and communicating the failure to the system controller.
[0043] Other systems, methods, features and advantages of the invention will be or will become apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the invention, and be protected by the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. In the figures, like reference numerals designate corresponding parts throughout the different views.
[0045] FIG. 1 is an exemplary illustration of a radio communications site powered by renewable energy generated by a wind turbine and photovoltaic array, containing a supervisory system controller for monitoring and controlling the system according to an embodiment of the present invention.
DETAILED DESCRIPTION
[0046] The embodiment hereinafter described relates to a renewable energy powered storage system for powering radio communications systems.
[0047] In FIG. 1 , the components contained in the dotted box represent a Supervisory System Controller 100 . A software enabled system controller 101 has a control interface 115 for the control of interconnect and switching of externally housed batteries 105 and turbine dump loads 106 . Control is also provided to switch mast warning light contactors 120 for the supply of power to aircraft warning lights 125 mounted on the radio mast 119 , backhaul equipment contactors 121 for the supply of power to backhaul equipment 124 , and Base Station contactors 122 for the supply of power to the Base Station 118 from a DC bus 114 .
[0048] The system controller 101 also possesses a generator control interface 109 to permit the start and stop control of an optional generator 102 and also to receive status information from the generator if one is present. A maintenance interface 110 is provided to permit the connection of a local maintenance terminal 112 for the purpose of software upgrades, changing site control parameters and the monitoring of system performance data. A security interface 111 is provided for the connection of site security monitoring devices 113 . The SSC management interface 116 provides connection to a remote maintenance terminal 117 for the provision of remote access to the controller for software upgrades, changing site control parameters and the monitoring of system performance data.
[0049] A BTS signaling interface 123 is provided to permit two-way signalling between the SSC and the base station 118 for the purpose of base station power control and the reporting of status and alarms.
[0050] The SSC 100 has provision for the connection of a PV array 103 via one or more PV controllers 108 and for the connection of a wind turbine 104 to the DC bus 114 via interconnect and switching 107 .
[0051] Under normal operation the SSC 100 will manage the renewable energy power from the PV array 103 and wind turbine 104 to maintain power to the system loads of the base station 118 , backhaul equipment 123 , mast warning lights 119 , and to charge the batteries 105 . The PV controllers 108 control all aspects of battery charging from the PV array 103 to prevent over charge when surplus power is available from this source. When surplus power is available from the wind turbine 104 one or more of the dump loads 106 are switched on to dissipate the excess energy and prevent overcharge of the batteries 105 for the duration of the excess power being available. The voltage thresholds at which these loads are switched on and off are dynamically controlled based on the state of charge of the battery 105 to improve the capture of turbine power.
[0052] When insufficient power is available from renewable sources the system loads take their power from the batteries 105 which are sized to maintain normal operation for a specified period of time. When renewable power becomes available again the system will revert to normal operation as described above.
[0053] The system controller 101 can receive weather forecast data from the remote maintenance terminal 117 which it uses to efficiently manage the power system. In a system that does not have a generator 102 , if renewable energy is not available and the forecast is not predicting renewable energy becoming available in the required timescale, the SSC can implement a number of power saving options to maximise the system's operating time. The SSC 100 can command the base station 118 to implement any power reduction features that it may possess such as turning off non-BCCH transceivers. The SSC 100 can also disconnect the base station 118 via the contactors 122 during off-peak times, such as at night, to conserve battery power for the periods of maximum demand. For remote sites carrying little or no night time traffic, a controlled nightly shut down can give considerable savings in required energy generation elements and battery capacity.
[0054] Another option available to conserve power is to configure two, lower power base stations onto one site in place of one larger capacity base station and configured so one base station provides the BCCH carriers and the second one peak hour capacity. The SSC 100 can then exercise power control by disconnecting the second base station from the battery at off-peak times or as remotely commanded by the operator.
[0055] Ultimately, if no renewable power becomes available, the system controller 101 will perform a low voltage disconnect, where it commands the contactors 120 , 121 and 122 to disconnect their respective loads from the DC bus 114 to prevent the battery 105 from discharging to a level where it will sustain damage.
[0056] In a system that does have a generator 102 , if renewable energy is not available and the forecast is not predicting energy becoming available in the required timescale, the SSC 100 can start the generator 102 and this will provide power to the system loads and also to charge the battery 105 . Once the battery is charged, or renewable energy is forecast to become available in the required timescale, the SSC 100 will stop the generator 102 to conserve fuel. Similarly, if generator usage is low and a generator maintenance run is required to preserve generator condition and starting capability, the SSC 100 can automatically schedule this to occur at a time when the battery capacity is reduced and weather data is predicting low renewable energy availability. This ensures the energy produced during the generator maintenance run will be absorbed by the battery and is not wasted.
[0057] The SSC can also inhibit a low voltage disconnect and postpone a generator start for a short period of time if renewable energy is predicted to become available but after the normal low voltage disconnect point for the load. This offsets a generator start against occasionally running the battery to a slightly lower state of charge but conserves fuel and extends generator service intervals.
[0058] In some situations the backhaul equipment 124 links on to provide connection for routing of communications for other base station sites to a fixed switching centre for onward transmission to fixed user terminals or other communications networks (daisy chaining) In the event of the system controller 101 determining there insufficient power being available to operate the radio site continuously, it is desirable to provide a longer period of battery operation to this backhaul equipment than to the site base station 118 . The SSC 100 can independently control how long each load will remain connected to the dc bus 114 . By disconnecting the base station 118 after a predetermined time period the SSC 100 will reduce the power load on the battery and so extend the time backhaul equipment 124 can operate before the battery 105 becomes discharged to the point where a low voltage disconnect will occur. The SSC has the ability to vary the operating time of the base station 118 to increase or decrease the operating time of the backhaul equipment 124 .
[0059] In the event of the energy sources sustaining damage, and power generation becoming limited or unavailable, an operator can remotely command the SSC 100 to disconnect base station 118 power immediately in the interest of maintaining communications in the remainder of his network for a much longer period. The SSC 100 also has the option to override one or more of the low voltage disconnects to power the base station and/or the backhaul equipment to provide additional operating time at the expense of potentially damaging the batteries by deep discharge. This feature would only be exercised in extreme conditions where the potential cost of replacement batteries is considered acceptable to meet the operational need, for example, in the event of a natural disaster where life may depend upon working communications.
[0060] High levels of reliability and availability are achieved by configuring the PV array 103 to be split between multiple PV controllers 108 , such that a failure in one PV controller 108 will not remove all of the available solar power to the SSC 100 . The SSC also employs dual redundant low voltage disconnect components, 121 , 122 , to ensure that a contactor failure will not remove a load from the battery. The battery 105 , may also be configured as two or more strings of cells to permit automatic, periodic removal and capacity measurement of one battery string whilst the system continues to operate from the remaining battery string(s). The use of multiple battery strings also permits the removal of an individual battery string in the event of a fault within an individual cell whilst maintaining operation from the remaining battery string(s). Additionally it facilitates the replacement of the batteries at end of life without the need to take the site off air.
[0061] While various embodiments of the invention have been described, it will be apparent to those of ordinary skill in the art that many more embodiments and implementations are possible that are within the scope of this invention. In addition, the various features, elements, and embodiments described herein may be claimed or combined in any combination or arrangement.
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A supervisory system controller for controlling and monitoring the generation of electrical energy from renewable sources and management methods for the storage of energy so generated and interconnecting the energy-generating elements, storage and load. The supervisory system controller operates to maximum the power transfer from a wind turbine to a battery by automatically varying the threshold levels at which turbine dump loads are switched based on system inputs and measurements. The method conserves generator fuel by delaying a scheduled generator maintenance running period such that it to occurs when renewable energy availability is predicted to be low and battery is in a reduced state of charge. Further modifications and management methods are also provided.
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FIELD AND BACKGROUND OF THE INVENTION
The present invention relates to a device to be mounted in sewing units and intended for adjusting plies of material, which are to be sewn together by means of a sewing machine and which register with each other at their leading edges, to mutually equal lengths and/or for holding them in such adjusted equal length position.
While sewing together plies of material, for example, cut pieces such as used in the manufacture of trousers, to obtain a faultless working result, it is necessary to sew the plies together so as to bring not only their outlines but also their lengths into registration. Differences in length may occur so that, in spite of an exactly uniform operation of the feed tools, the plies of material are fed at unequal advance velocities due to unequal friction conditions, with the result of a mutual displacement of the plies during the sewing operation. However, it may happen that already the initial lengths of the plies are different, because of an inaccurate cutting.
In a known sewing unit, prior to the sewing operation, the leading edges of the plies of material are clamped in registry with each other between the feed tools of the sewing machine, and the trailing edges are clamped, also in registry with each other, into a horizontally movable, weight loaded, trailing clamp. Due to the stretching of the two plies caused by the trailing clamp, a small displacement of the plies can be compensated while, during the sewing operation, the ply advanced at a lower speed contracts again, without forming wrinkles. Further, by means of the trailing clamp, if the pieces of material are cut inaccurately, to unequal lengths, the plies can be adjusted in length before starting the sewing operation or their lengths can be maintained during the sewing operation. The trailing edges may, in this case, be brought into registration, or mutually adjusted, so that either the shorter ply is manually stretched to the measure of the longer one or the longer ply is adjusted by upsetting or creasing to the shorter ply with, in the latter case, the stretching of the plies being produced by the trailing clamp. While, for stretching the shorter ply of material, a pull must be exerted thereon by the operator, in the second case, the operator has to exert a pull on the trailing clamp in order to displace it from the initial position thereof to the trailing edges of the two plies. Thus, the alignment and clamping of the plies in the trailing clamp requires, in any case, a more or less considerable exertion of force on the part of the operator and a certain amount of attention so that, particularly if pieces are involved having unequal lengths already prior to the sewing operation, the quality of the resulting work still depends on the reliability and skill of the operator, in spite of a partial mechanization of the operations.
SUMMARY OF THE INVENTION
The present invention is directed to automation of the mutual adjustment in length of plies of material which, in unsewn state, have unequal lengths, in order to provide permanently constant conditions, independent of outside influences, for an optimum working result.
To this end, the present invention is directed to a device which, in the course of a relative motion taking place between the device and the plies of material, engages the plies automatically at a permanently constant distance from their trailing edges and, in order to produce an adjustment to equal lengths exerts a pull on the trailing edges, depending on the respective differential length.
For this purpose, in accordance with the invention, an intermediate plate is provided separating the two plies of material and, at each side of the plate, a sensing mechanism is mounted which is operationally controllable by the respective ply of material for controllably engaging a clasp which is movable in the feed direction of the plies of material. The clasps are connected to each other through a structural part exerting a pull in a direction opposite to the feed direction of the plies of material.
During a relative motion between the material plies, on the one hand, and the mechanisms and clasps, on the other hand, during which either the material plies move in the sewing direction and/or the mechanisms and clasps move in the opposite direction, if the material plies are of unequal lengths, the trailing edge of the shorter material ply comes first into the sensing range of the respective associated sensing device constituted, for example, by a reflex light barrier, whereupon, the corresponding clasp is actuated and engages the respective ply of material. The structural part connecting the clasps to each other then exerts a pull on the shorter ply, which may be produced, for example, by gravity or by friction between the structural part and a backing. The pull leads to a stretching of the shorter ply and must be provided at least in a magnitude such that the shorter ply continues to be stretched at least until also the trailing edge of the initially longer ply of material comes into the sensing range of the sensing device associated therewith, whereupon this ply is engaged by the respective clasp. Then, both plies of material are adjusted to the same length.
In order to obtain a secure adjustment in length also under unfavorable conditions, the pull exerted by the structural part connecting the clasps to each other is advantageously chosen to have a magnitude such that the initially longer ply of material, after being engaged by the associated clasp, is first also stretched to a small extent and that, thereupon, only the tensile forces issuing from the material plies in stretched state become stronger than the oppositely directed pull exerted by the structural part and it is only from that instant that the clasps and the structural part are pulled along by the two plies of material. As soon as the two plies of material are stretched or elongated, a displacement of the material plies occurring during the sewing operation and due to unequal friction conditions can also be compensated by the inventive device.
The relative motion between the plies of material, on the one hand, and the mechanisms and clasps, on the other hand, is advantageously produced so that, after clamping the plies between the feed tools of the sewing machine and introducing them into the zone of action of the mechanisms and clasps, the sewing operation is started, whereupon the plies move relatively to the mechanisms and clasps which are at rest in their initial positions. In this manner, the detection of the trailing edges, the connection of the plies to the clasps and the mutual adjustment in length take place during the sewing operation, so that no additional time extending the total duration of a sewing cycle is required for the mentioned operational steps. Thus, since the operator has only to bring the plies of material in position and the subsequent operations take place automatically, working results are obtained which are uniform to the largest extent and, in practice, independent of any lack of attention or skill of the operator.
In accordance with a development of the invention, the intermediate plate extends in a substantially vertical plane and the clasps are secured to a support which is movable in a substantially vertical direction. Due to the vertical disposition of the intermediate plate, the plies of material can be placed in the range of action of the mechanisms and clasps in a freely suspended and, thereby, unobstructed position, so that this operation may be effected by means of an air blast acting on the plies of material, which again relieves the operator of working effort. As compared to a horizontal arrangement, the vertical orientation of the plies of material has the further advantage that, during a positioning of long plies, there is no need for the operator to shuttle between the clamping point of the sewing machine and the clasps, nor to contort his or her body.
Although the clasps are able to produce a certain pull on the plies already due to their own weight, the pull necessary for the complete adjustment in length is mainly produced by the support, so that the support performs the function of the above mentioned structural part intended for producing the pull. Besides, the vertical direction of motion of the clasps permits a direct connection to the mentioned structural part so that additional connecting elements, such as traction ropes and return pulleys, which would be needed with horizontally moved clasps, become superfluous.
In order to ensure a timely and rapid engagement of the plies by the clasps at a permanently constant distance from the trailing edges thereof even with ready-made pieces of unequal size, a motor-driven lifting carriage is provided below and within the range of motion of the support, which carriage is also movable vertically and comprises at least one mechanism for stopping the lifting carriage, operationally controllable by one of the plies of material. In this case, the mechanisms for engaging the clasps are movable, at least up to the instant of engagement, in synchronism with the clasps. For this purpose, these mechanisms may be secured to the support for the lifting carriage.
The lifting carriage elevates the clasping station, comprising the clasps and the support, as well as the mechanisms associated with the clasps, up to a level at which the shortest possible plies of material, for example, cut pieces of childrens' shorts, are just still engageable. Thereupon, the lifting carriage with the clasping station and the mentioned mechanisms resting thereon moves downwardly again until, by means of the mechanism serving to stop the lifting carriage, the trailing edge of one of the plies of material is detected and, in consequence, the lifting carriage is stopped. Since two plies of material to be sewn together fit each other in size and, therefore, differences in length are limited to a few centimeters, it is sufficient to sense only one of the two plies of material, as long as the vertical distance between the mechanism associated with the lifting carriage and the mechanisms associated with the clasps is sufficiently large. The up and down motion of the lifting carriage can be superposed in time to other operations within a sewing cycle so that the total time of a sewing cycle is not extended by the operation of the lifting carriage.
Since, in the presence of guide elements, for example, guide rollers, the clasping station could be too heavy for some kinds of material, a pulling means is provided, in accordance with a further development of the invention, and this is passed around return pulleys, is attached to the support, and is loadable by a counterbalance weight reducing the pull exerted on the plies of material by the clasping station. At the same time, the effective weight of the clasping station is reduced to an extent such that the highest pull admissible for thin and delicate materials is not exceeded. To be able to exert a pull which is sufficiently strong also for thicker and firmer materials, it is further provided to connect one of the return pulleys to a braking mechanism which is capable of transferring frictional or braking forces to the pulling means. These frictional or braking forces are transmitted to the clasping station, whereby the pull exerted on the plies is increased, more or less, depending on the adjustment of the braking mechanism. In addition, the braking mechanism is designed so as to perform still another function. That is, as soon as, toward the end of the sewing operation, the clasps are disengaged and, thereupon, the clasping station falls back from its lifted position, the clasping station is braked down, by means of the braking mechanism, before impinging upon the lifting carriage.
In a particularly advantageous embodiment of the clasps, each clasp comprises a plurality of retaining needles which are arranged one after the other in the feed direction of the plies of material, extend perpendicularly to the intermediate plate, and are adapted to project into a groove provided in the intermediate plate and extending parallel to the feed direction of the plies. Due to the particular arrangement of the retaining needles, the pull produced by the clasping station is transferred to the plies in the form of a plurality of smaller, individual, forces whereby the risk that the plies could tear up in the area of their trailing edges is eliminated. The grooves of the intermediate plate opposing the retaining needles ensure a secure engagement of the needles into the plies and, in addition, enable the stationary intermediate plate to cooperate with the respective clasp as a second half of a clamp, which makes it possible, because of a saving of such a second half of a clamp movable along with the support, to design the clasps in a particularly simple manner.
In accordance with a second, modified, embodiment of the invention, the support supporting the clasps, and also the mechanisms for engaging the clasps, are secured to a pulling means which is connected, through an engageable and disengageable clutch, to a drive mechanism. This second embodiment differs from the first one in a simpler design using a conventional clutch instead of a lifting carriage and an expensive braking mechanism.
An object of the invention is to automate the mutal adjustment in length of plies of material which, in the unsewn state, have unequal lengths.
Another object of the invention is to provide a device for effecting automation of such mutual adjustment in length of plies of material which, in the unsewn state, have unequal lengths.
A further object of the invention is to provide such a device which, in the course of a relative motion between the device and the plies of material, engages the plies automatically at a permanently constant distance from their trailing edges and exerts a pull on the trailing edges depending on the respective differential length.
For an understanding of the principles of the invention, reference is made to the following description of typical embodiments thereof as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a sectional view of the sewing unit incorporating one embodiment of the inventive device;
FIG. 2 is a detail of FIG. 1 in which the position of the clasping station and the lifting carriage is shown in a later phase of the sewing cycle;
FIG. 3 is a sectional view of the part of the sewing unit comprising the clasping station and the lifting carriage, taken along the line III--III of FIG. 4;
FIG. 4 is a sectional view of the part of the sewing unit comprising the clasping station and the lifting carriage, taken along the line IV--IV of FIG. 3;
FIG. 5 is an elevation view of the braking mechanism, partly in section;
FIG. 6 is an elevation view of a sewing unit, partly in section, showing a second embodiment of the inventive device;
FIG. 7 is a view, partly in section at a right angle to FIG. 6, of the second embodiment of the inventive device; and
FIG. 8 is a sectional view of the inventive device taken along the line VIII--VIII of FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The sewing unit comprises a casing 1 of which a bottom plate 2, a cover plate 3 and two side walls 4, 5 are shown in FIG. 1 and two further side walls 6 and 7 are shown in FIG. 4. Cover plate 3 supports a sewing machine 8 which is equipped for upper and lower feeds and of which the bed plate 9, the column 10 and the head 11 are indicated. Head 11 supports the needle bar 12 carrying the needle 13. Also shown are the presser foot 14, the top feed dog 15 and its drive mechanism 16, as well as the bottom feed dog 17.
In casing 1, an intermediate plate 18 is mounted extending in a vertical plane from bottom plate 2 up to cover plate 3 and projecting laterally from an opening of side wall 6. Intermediate plate 18 is formed with a vertically extending slot 21 (FIG. 4) and, on each of its larger plane surfaces, with a respective vertically extending groove 19, 20. On each plane surface of intermediate plate 18, a spacer plate 22, 23 is provided and a respective guide plate 24, 25 is applied against each spacer plate. Guide plates 24, 25 extend, within casing 1, parallel to intermediate plate 18 and from bottom plate 2 up to cover plate 3 and, in the same manner as intermediate plate 18, project laterally from the mentioned opening of side wall 6. The portions of guide plates 24, 25 which are located within casing 1 form, along with intermediate plate 18, two parallel guide slots 26, 27 extending across cover plate 3 and intended for receiving the plies of material A, B to be sewn together, while the portions of guide plates 24, 25 located outside casing 1 are angled away from each other, whereby inlet flares 28, 29 are formed. Each guide plate 24, 25 is provided with a respective slot 30, 31 located opposite the respective groove 19, 20 and also extending vertically.
In the first embodiment shown in FIGS. 1-5, guide rails 32, 33 are secured to guide plates 24, 25, and also extend from bottom plate 2 up to cover plate 3. Aside from the fixed plates, the device serving for adjusting plies of material to equal lengths and/or holding them in that position further comprises a clasping station 34 and a lifting carriage 35. Clasping station 34 includes a substantially U-shaped support 36 (FIG. 4) which, in the zone of intermediate plate 18, extends through slot 21 and which is vertically movable and secured against lateral tilting or torsion by means of eight guide rollers 37 running on guide rails 33, 32. Support 36 is provided with lugs 38, 39 which are angled outwardly and support respective clasps 40, 41. Clasp 40 comprises an electromagnet 42 with a pull rod or armature 43, a needle bar 44 secured to the end of pull rod 43 and carrying three needles 45, and a compression spring 46 surrounding pull rod 43. Clasp 41 is of identical design and, consequently, comprises an electromagnet 47 with a pull rod or armature 48, a needle bar 49, three needles 50 and a compression spring 51. As shown in FIG. 4, clasps 40, 41 are mounted so that, in working position, needles 45, 50 extend through slots 30, 31 into grooves 19, 20. Support 36 is further provided with a stop angle 52 cooperating with a limit switch 53 which is secured at the upper end of guide rail 33. A stop plate 54, cooperating with a limit switch mentioned hereinafter, is also carried by support 36.
Lifting carriage 35 comprises a frame 55 which has a shape similar to support 36 and which also extends, in the zone of intermediate plate 18, through slot 21 and is vertically movable and secured against lateral tilting or torsion by means of eight guide rollers 56 running on guide rails 32, 33. Lifting carriage 35 is driven by means of a chain drive comprising a motor 57 secured to bottom plate 2, a sprocket wheel 59 secured to the motor shaft 58, a sprocket wheel 61 mounted for free rotation on a support 60, and a chain 62. Chain 62 is firmly attached to frame 55 of lifting carriage 35. On frame 55, in front of slots 30, 31, two reflex light barriers 63, 64 are mounted, each comprising a light source and a photoconductive cell (not shown in detail). The base surface of each of grooves 19, 20 serves as the reflecting surface. Along with respective signal amplifiers (not shown), reflex light barriers 63, 64 form two sensing devices 65, 66 for controlled engagement of clasps 40, 41, which are operationally controllable by the plies of material A, B to be sewn together.
As may be seen in FIG. 1, in the zone of cover plate 3, ply B advances along a path having a greater radius of deflection than ply A, wherefore ply B has to cover a longer distance to the stitch forming area of sewing machine 8, given by the difference between the two deflection radii. Taking this fact into account, reflex light barrier 64 is mounted higher than reflex light barrier 63, by a distance corresponding to the mentioned difference between the radii of deflection. Beneath reflex light barrier 63, facing slot 30, a further reflex light barrier 67 is mounted on frame 55 which, along with a corresponding signal amplifier (not shown), forms a sensing device 68 for controlled stopping of lifting carriage 35, and which is operationally controllable by ply A. Frame 55 further carries a limit switch 69 cooperating with stop plate 54. A stop plate 70, provided on frame 55, cooperates with a limit switch 72 which is mounted on an angle plate 71. Angle plate 71 is displaceable along a slot 73 provided in side wall 7 and can be fixed by means of a screw 74 which is actuable from outside casing 1.
A bearing bracket 75 supporting a freely rotatable pulley 76 is secured to bottom plate 2. To the underside of cover plate 3, a support 77 is secured with a partly threaded bolt 78 non-rotatably mounted thereon. A pulley 79 is mounted for free rotation on bolt 78. A rope 80, attached to support 36 and carrying a counterbalance weight 81, is passed around pulleys 76, 79. There are also mounted on bolt 78, as shown in FIG. 5, a brake disc 82, a compression spring 83 and, on the threaded portion of the bolt, a hand wheel 84 also provided with a thread. Brake disc 82 comprises two flats 85 which are provided at mutually opposite locations of the disc. A brake lever 87, pivoted in a slot 86 of support 77 and having a forked end, is engaged, by the fork, over the two flats 85 thereby preventing brake disc 82 from rotating. Brake lever 87 is hinged to a pull rod or armature 88 of an electromagnet 89 which is secured to support 77. Component parts 82 through 89 constitute a braking mechanism, generally designated 90. Before the stitch forming area of sewing machine 8, a well-known guide mechanism 91 is provided on cover plate 3, serving for an automatic congruent alignment of the side contours of plies A, B.
The second embodiment of the inventive device, shown in FIGS. 6, 7 and 8, also comprises an intermediate plate 18 and two guide plates 24, 25 which, in connection with two spacer plates 22, 23, form two guide gaps 26, 27 for the plies of material C, D. A bearing block 100 is supported on bottom plate 2 and a bearing support 101 is secured to the underside of cover plate 3. Instead of guide rails 32, 33 used in the first embodiment, in this case, there is provided a guide bar 102 extending vertically between block 100 and support 101 and provided with guide grooves 103. A clasp carriage 104 is mounted on guide bar 102 and comprises a support 105 and two ball retainers 106, 107 with a plurality of balls 108. Balls 108 run in guide grooves 103 whereby clasp carriage 104 is vertically movable and secured against lateral tilting or torsion.
By means of two clamping strips 111, 112, support 105 is secured to the ends of a gear belt 113 which is run over two gears 114, 115. Gear 114 is mounted for free rotation on a shaft 116 which is secured to bearing support 101. Also mounted on shaft 116 is a pulley 117 which is non-rotatably connected to gear 114. A rope 118 is attached to pulley 117, trained around a corner pulley 120 which is mounted on a supporting bracket 119, and loaded, at its other end, with a counterbalance weight 121. Counterbalance weight 121 reduces the effective weight of clasp carriage 104 to approximately 300 g.
Shaft 116 also supports a braking mechanism 122 comprising an axially shiftable brake disc 123, a compression spring 124, and a hand wheel 125 which is provided with a thread and is screwed on a threaded portion of shaft 116. Brake disc 123 carries a pin 126 which engages into a slot 127 provided in shaft 116 and thereby prevents brake disc 123 from rotating.
Gear 115 is mounted for free rotation on a shaft 128 which, in turn, is mounted on bearing block 100. Shaft 128 carries an electromagnetically actuable clutch 129 of which one part 130 is mounted for free rotation on shaft 128 but, at the same time, non-rotatably connected to gear 115. The other part 131 of the clutch is secured to shaft 128 and firmly connected to a pulley 132. The drive mechanism comprises a conventional brake motor 133, a pulley 135 secured to the motor shaft 134 and a drive belt 136 passed around pulleys 132 and 135.
Two mounting brackets 109, 110 are provided on support 105, each carrying a respective clasp 40, 41. Clasps 40, 41 are identical with the corresponding clasps 40, 41 of the first embodiment, so that their description need not be repeated. Support 105 is further provided with a stop angle 52 cooperating with a limit switch 53 which is secured to bearing support 101.
Two angle pieces 137, 138 are secured to support 105, each carrying a respective reflex light barrier 63, 64 facing a respective slot 30, 31. Reflex light barriers 63, 64 comprise a light source and a photoconductive cell (not shown) and the base surface of each of the grooves 19, 20 serve as the reflecting surface. Along with corresponding signal amplifiers (not shown), reflex light barriers 63, 64 form respective devices 65, 66 for a controlled engagement of respective clasps 40, 41, which are operationally controllable by the plies of material C, D to be sewn together. Since the top outlet of guide gap 26, receiving ply C, is located nearer to the stitch forming area of sewing machine 8 than is the top outlet of guide gap 27, receiving ply D, ply D must cover a longer distance to the stitch forming area than ply C. For taking into account this difference, reflex light barrier 64 is mounted at a correspondingly higher location relative to reflex light barrier 63. A further reflex light barrier 67 facing slot 30 is mounted below reflex light barrier 63 on an angle piece 139 which is secured to support 105 and this barrier 67, along with a corresponding singal amplifier (not shown), forms a device 68 for controlled stopping of clasp carriage 104, which is operationally controllable by the ply C.
Before the stitch forming area of sewing machine 8, another well known guide mechanism 91 is provided on cover plate 3, and serves for an automatic, congruent, alignment of the side contours of plies C and D.
The device in accordance with the invention operates as follows:
The plies of material A, B shown in FIG. 1, are cut pieces of mens' or boys' trousers having side pockets. The side seams are sewn from the waistband to the hem and, during each sewing cycle, first, the approximately 10 to 15 cm long seam portion located in the pocket zone is formed.
At the beginning of a sewing cycle, comprising the operations of positioning the material, sewing, and removing the material, with needles 45, 50 retracted, the plies of material A, B are introduced into guide gaps 26, 27 and are brought into contact with spacer plates 22, 23. Then, with guide mechanism 91 swung back, the leading edges of plies A, B, lying in the waistband zone, after being brought into registry with each other, are tightly clamped between presser foot 14 and the needle plate of sewing machine 8 (not shown). Following this, sewing machine 8 is put into operation and, thereby, the sewing operation is started. Since, during the sewing in the pocket zone, plies A, B must be guided with particular care to obtain a flawless working result, this portion of the seam is formed with the guide mechanism 91 still swung back and at a relatively low speed, while feeding the material into the sewing machine manually.
During the above-described operations of positioning the material and sewing in the pocket zone, lifting carriage 35 brings clasping station 34 into an initial position corresponding to the respective length of the pair of plies. For this purpose, simultaneously with the positioning of plies A, B, motor 57 is started so as to move, through chain 62, the lifting carriage 35 and the clasping station supported thereon upwardly. As soon as stop plate 70 of lifting carriage 35 actuates limit switch 72, the direction of rotation of motor 57 is reversed whereupon lifting carriage 35 along with clasping station 34 supported thereon is moved downwardly again. During this motion, the beam emitted by reflex light barrier 67 senses the ply of material A. Depending on whether the treated pieces are parts of boys' or mens' trousers, or are of large or small size, the trailing edge of ply A will run out of the beam of reflex light barrier 67 sooner or later and then the light beam will be reflected by the base surface of groove 19. In response thereto, motor 57 is stopped and lifting carriage 35 along with clasping station 34 remains in this position.
The stopping of lifting carriage 35 takes place approximately at the same time at which the sewing in the pocket zone is terminated. With the seam portion located in the pocket zone completed, sewing machine 8 is stopped, guide mechanism 91 is swung forwardly into its working position and then sewing machine 8 is started again, however, now at a higher speed, in order to sew the remaining, larger, portion of the seam more rapidly. During this phase, top feed dog 15 and bottom feed dog 17 produce a relative motion between the two plies A, B on the one hand, and the stopped reflex light barriers 63, 64, on the other hand. As soon as the trailing edge of the shorter ply B runs out of the light beam of reflex light barrier 64, the beam is reflected by the base surface of groove 20, whereupon device 66 actuates clasp 41 by de-energizing electromagnet 47. Compression spring 51, thereby released, pushes needles 50 through ply B, which is backed by intermediate plate 18, into groove 20 whereby the trailing end of ply B becomes firmly attached to clasping station 34. In the course of further feed of plies A, B, clasping station 34 which, as before, is supported on lifting carriage 35, holds the trailing end of ply B back, which results in a stretching of ply B. At the instant at which the initially shorter ply B is stretched to exactly the length of the initially longer ply A, the trailing edge of the hitherto still freely suspended ply A also runs out of the light beam of its associated reflex light barrier 63 whereby clasp 40 is also actuated and needles 45 are pushed through ply A into groove 19.
To securely obtain an exact adjustment in length of the initially unequally long plies of material A, B, it must be ensured that the pull in the upward direction, which is exerted on clasping station 34 by ply B and constantly increases during the stretching operation, is adjusted so that only after ply A is also engaged by the clasp, the upward pull becomes stronger than the downwardly directed pull exerted on ply B by the clasping station, which could also be designated as a braking or retaining force. The pull produced by clasping station 34 depends on the difference between the weight of clasping station 34 and the weight of the counterbalance 81 as well as on the braking force exerted by braking mechanism 90 on rope 80. The total pull exerted by clasping station 34 can be varied by turning hand wheel 84 which produces a variation of the contact pressure of brake disc 82. It would also be possible, in extreme cases, to replace counterbalance weight 81 by another weight. In order to enable the operator to actuate hand wheel 84 rapidly and without particular complications, it is advantageous to provide a sufficiently large opening in side wall 6 of casing 1, which modification is not shown in the drawings.
After ply A is also engaged by its associated clasp and, thereby, firmly connected to clasping station 34, in addition to the stretching of ply B, ply A is also stretched to a small extent until the pulls presently exerted on clasping station 34 by both of the plies A and B exceed the braking or retaining force exerted by the clasping station. As from this instant, the two plies A and B pull the clasping station along and, during this upwardly directed motion, clasping station 34 retains the two plies A, B in their previously established longitudinally correctly aligned position, thereby ensuring that the plies A, B are sewn together in longitudinal registration with each other. The upwardly directed motion of clasping station 34 is stopped as soon as limit switch 53 is actuated by stop angle 52 since, then, electromagnets 42 and 47 are energized, needles 45 and 50 are retracted from grooves 19, 20 and guide gaps 26, 27 and, consequently, plies A and B become disengaged from the clasps. While the now still remaining portion of the seam to be produced is sewn to the end, clasping station 34 moves downwardly again, automatically. As soon as stop plate 54 actuates limit switch 69, whose switching element 69a, in unloaded state, projects beyond the upper edge of frame 55, electromagnet 89 is energized for a short time whereby brake disc 82, through pull rod 88 and brake lever 87, is pressed against pulley 79 so strongly that the downward movement of clasping station 34 is decelerated just shortly prior to touching down on lifting carriage 35. In this manner, a hard impact of clasping station 34 on lifting carriage 35 is prevented.
In the second embodiment of the invention, the plies of material C, D (FIG. 7) are assumed to be cut pieces of women's or girls' slacks having no side pockets.
At the beginning of a sewing cycle, the two plies of material C, D are positioned in the sewing unit or introduced into gaps 26, 27 in the manner as in the example of the first embodiment and are also clamped, with their leading edges in registry with each other, between the presser foot 14 and the needle plate (not shown) of sewing machine 8. Since slacks have no side pockets, there is no need for a manual sewing in the pocket zone as with men's trousers. In consequence, immediately after the clamping of the leading edges of plies C, D, guide mechanism 91 can be swung into its working position. Thereupon, sewing machine 8 is started to produce the side seam, first, at a reduced sewing speed.
During the introduction of plies C, D into guide gaps 26, 27, the brake of brake motor 133 is released and the motor is started. Since, at that time, electromagnetically actuable clutch 129 is engaged, gear belt 113 is driven counterclockwise, as viewed in FIG. 6, the clasp carriage 104 is moved downwardly from its upper standstill position. During this motion, the beam emitted by reflex light barrier 67 senses the ply of material C. Depending on whether the treated piece is a part of women's or girls' slacks, or of large or small size, the trailing edge of ply C will run out of the beam of reflex light barrier 67 sooner or later, whereupon the light beam is reflected by the base surface of groove 19. In consequence, brake motor 133 is switched off whereby clasp carriage 104 is stopped in this position which is an initial position for the subsequent engagement of clasps 40, 41.
As soon as clasp carriage 104 has reached the mentioned initial position, the sewing operation is continued at a higher speed. The adjusted vertical distance between reflex light barriers 63, 64, on the one hand, and reflex light barrier 67, on the other hand, is so small that the trailing edge of the shorter ply D runs out of the beam of reflex light barrier 64 only a short time after the stopping of clasp carriage 104, whereupon the light beam is reflected by the base surface of groove 20. In response thereto, device 66 actuates clasp 41 by de-energizing electromagnet 47. Due to the following release of compression spring 51, needles 50 are pushed, through ply D backed by intermediate plate 18, into groove 20 whereby the trailing end of ply D becomes firmly connected to clasp carriage 104. Simultaneously with engagement of clasp 41, electromagnetically actuable clutch 129 is disengaged so that, from this instant and for the duration of the following sewing operation, clasp carriage 104 is no longer connected to brake motor 133. Due to the disengagement of clutch 129, clasped ply D becomes loaded with the effective weight of clasp carriage 104 and, depending on the resistance of the material, is more or less stretched, whereby the distance between the trailing edge of clasped shorter ply D and the trailing edge of the not yet clasped longer ply C is reduced. In the course of the continuing sewing operation, the not yet clasped ply C is advanced somewhat faster than ply D by which clasp carriage 104 is pulled along because, due to the pull produced by clasp carriage 104 and opposed to the direction of advance, a slip occurs at each individual feed step produced by the feed tools. Thus, the trailing edge of ply C gradually draws closer to reflex light barrier 63 which is moved in the upward direction more slowly, at the advance speed of ply D. At the moment at which the initially shorter ply D is exactly as long as the initially longer ply C, the trailing edge of ply C runs out of the beam of reflex light barrier 63, whereupon clasp 40 is also actuated and needles 45 are pushed through ply C into groove 19. Since the initially longer ply C is also clasped to clasp carriage 104, during the subsequent, remaining, sewing operation, clasp carriage 104 holds the two plies C, D in a position of mutually equal length which results in a longitudinally correctly aligned sewing together of plies C and D.
The upward movement of clasp carriage 104 is terminated as soon as stop angle 52 actuates limit switch 53 whereby electromagnets 42, 47 are energized, needles 45, 50 are retracted from grooves 19, 20 and guide gaps 26, 27 and, consequently, plies of material C and D are released. Simultaneously with the disengagement of clasps 40, 41, clutch 129 is engaged whereby clasp carriage 104 is coupled to the switched-off brake motor 133. In this manner, clasp carriage 104 is arrested in its upper position wherefrom it is moved downwardly only after a new positioning to two further plies of material and switching on of brake motor 133.
Due to counterbalance weight 121, the effective weight of clasp carriage 104 is reduced to an extent such that the strongest pull admissible for thin and delicate materials is not exceeded. In order to be able to exert a sufficiently strong pull on the respective shorter ply of thicker and more resistant materials, brake disc 123 can be pressed against gear 114 by turning hand wheel 125. Thereby, a braking force is produced impeding the motion of clasp carriage 104 so that a stronger pull is exerted on the clasped shorter ply of material.
Only a very short period of time elapses between the detection of the trailing edges of the plies of material by reflex light barriers 63 or 64 and the engagement of clasps 40, 41. This ensures that, with small differences in length, even an only slightly longer ply is properly clasped. That is, with a difference in length which is smaller than the distance through which clasp carriage 104, after the clasping of the shorter ply and the disengagement of clutch 129, is lowered relative to the non-clasped ply, a risk would be run, due to the slow reaction velocity of devices 65, 66 and clasps 40, 41, that only a part of needles 45 or 50 would engage the ply while the other part would be pushed into empty space, beneath and past the trailing edge of the ply.
The device disclosed as the second embodiment of the invention is particularly suited for the manufacture of girls' or women's slacks since clasp 104 reaches the initial position for the engagement of clasps 40, 41 sooner than clasping station 34 of the first embodiment. Consequently, a higher sewing speed can be used from an earlier point of time, which shortens the sewing cycle.
With the exception of the operations of positioning the plies of material, clamping beneath the presser foot 14, as well as, with boys' or men's trousers, manually guiding the material during formation of the seam in the pocket zone, all of the following operations, namely, the adjustment to equal length of the unequally long plies of material, the congruent alignment of the lateral edges, and the sewing together of the registering plies, take place automatically. Since the last-mentioned operations represent the majority of the entire sewing cycle and the adjustment to equal lengths requires an exactly dimensioned pull on the shorter of the two plies of material, which remains constant for the duration of the sewing operation, the operator is quite considerably relieved of physical effort by the automation of these operations. As a further, very substantial advantage due to the automation of the mentioned operations, a constantly flawless output is obtained, since a possible lack of attention or skill of the operator has no influence whatsoever on the result.
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.
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The device is for use in a sewing unit including a sewing machine and includes a vertically oriented relatively elongated intermediate plate separating two plies of material in advance of the sewing machine. Guide elements adjacent the intermediate plate support a clasping station for movement longitudinally of the intermediate plate. The clasping station includes a support mounting two clasps each selectively engageable with a respective ply of material. Photoelectric sensing devices are movable with the clasping station, and include respective sensing devices operatively associated with each ply of material and each operable to control engagement of a respective clasp with the associated ply of material responsive to sensing of the trailing edge of the associated ply of material. A counterweight arrangement exerts an adjustable pull on the clasping station in a direction opposite to the feed direction of the plies of material. In one embodiment, a lifting carriage supports the sensing devices and effects lifting of the clasping station. In a second embodiment, the sensing devices are mounted on the same support which mounts the clasps.
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This application is a Divisional Patent Application of U.S. patent application Ser. No. 10/230,827, filed Aug. 29, 2002.
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a method for adjusting the saturation levels of the pixels of a time varying image being represented using RGB signals in an RGB color system. The method does not require the RGB signals to be converted into YUV signals in order to subsequently perform saturation adjustment. Hence, the associated H/W complexity required to perform the inventive method is low when compared to that required to perform the typical saturation level adjusting method.
The luminance and chromatic component Y, U, V color system, also known as the luminance and color difference color system (Y, R−Y,B−Y) is the color system that is most widely used in video systems. For example, in a digital TV system, the Y, U, and V signals of a video are compressed and transmitted. In such a system, since the color information is embedded in the chroma signals U and V, the color saturation level is simply adjusted by multiplying the chroma signals U and V by a color saturation adjusting gain a as expressed by the following equations:
U o =α·U and V o =α·V.
U o and V o now represent color adjusted chroma signals. FIG. 1 is a block diagram of a prior art color saturation adjusting circuit 10 that can be used to multiply the sample values of the chroma signals U and V by the color saturation adjusting gain α. Note that if the color saturation adjusting gain α=0, the resulting sample value will have no color. If the color saturation adjusting gain α>1, then the color of the resulting sample value will be enriched.
In a prior art RGB color system, color saturation adjustment is performed using the color saturation adjustment circuit 12 shown in FIG. 2 . Each RGB input sample vector is converted to a YUV sample value, and the color saturation adjusting method shown in FIG. 1 is performed on each YUV sample value. The output color saturation adjusted RGB sample vectors are then obtained by converting the Y 0 , U 0 , V color sample values to RGB color sample vectors. As can be seen, considerable computation is required for the conversions.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide a method for color saturation adjustment in an RGB color system which does not require the RGB color sample vectors to be converted into luminance and chroma samples in order to adjust the saturation levels of the RGB color sample vectors.
With the foregoing and other objects in view there is provided, in accordance with the invention, a method for adjusting a color saturation level of at least one color pixel of an input image obtained from a time varying RGB video signal. The method includes steps of: obtaining an RGB color sample vector {right arrow over (C)} representing the color pixel of the input image obtained from the time varying RGB video signal; decomposing the RGB color sample vector {right arrow over (C)} into a white vector {right arrow over (w)} and a color tone vector {right arrow over (C)} T ; obtaining a saturation adjusted color tone vector {right arrow over (C T o )} by multiplying the color tone vector {right arrow over (C)} T by a saturation adjustment parameter; obtaining a saturation adjusted RGB color sample vector {right arrow over (C)} o by adding the white vector {right arrow over (w)} and the saturation adjusted color tone vector {right arrow over (C T o )}; and using the saturation adjusted RGB color sample vector {right arrow over (C)} o to represent a color pixel of an output image.
In accordance with an added feature of the invention, the saturation adjustment parameter is constructed such that the saturation level of the saturation adjusted color tone vector {right arrow over (C T o )} will not exceed a predetermined limit value.
In accordance with an additional feature of the invention, the saturation adjustment parameter is constructed as a color saturation adjusting gain α, and it is ensured that when the color saturation adjusting gain α equals zero, the saturation adjusted RGB color sample vector {right arrow over (C)} o becomes a gray value. This is accomplished by performing the following additional steps: a luminance vector {right arrow over (Y)} is defined where each component of the luminance vector {right arrow over (Y)} is a luminance value obtained from the RGB color sample vector {right arrow over (C)}; the saturation adjustment parameter is configured to include at least a color saturation adjusting gain α; a gray mixing ratio α g is obtained by selecting a minimum value from the group consisting of one and the color saturation adjusting gain α; and a gray level adjusted vector is obtained by multiplying the luminance vector {right arrow over (Y)} by a quantity obtained by subtracting the gray mixing ratio α g from one. In addition, the step of obtaining the saturation adjusted RGB color sample vector {right arrow over (C)} o is performed by: before adding the white vector {right arrow over (w)} and the saturation adjusted color tone vector {right arrow over (C T o )}, multiplying the white vector {right arrow over (w)} by the gray mixing ratio α g ; and when adding the white vector {right arrow over (w)}, which has been multiplied by the gray mixing ratio α g , and the saturation adjusted color tone vector {right arrow over (C T o )}, also adding thereto, the gray level adjusted vector to obtain the saturation adjusted RGB color sample vector {right arrow over (C)} o . The color saturation adjusting gain a can be manually obtained from an adjustment by a user of the color system, or can be automatically set by an appropriate circuit.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a prior art color saturation adjusting circuit;
FIG. 2 is a block diagram of a prior art color saturation adjusting circuit that is used in an RGB color system;
FIG. 3 shows a graphical representation of the decomposition of an RGB color sample vector into a white vector and a color tone vector;
FIG. 4 is a block diagram of a circuit for performing an example of a first embodiment of the method for color saturation adjustment;
FIG. 5 is a block diagram of a circuit for performing another example of the first embodiment of the method for color saturation adjustment;
FIG. 6 is a block diagram of a circuit for performing an example of a second embodiment of the method for color saturation adjustment;
FIG. 7 is a block diagram of a circuit for performing another example of the second embodiment of the method for color saturation adjustment;
FIG. 8 is a block diagram of two multipliers;
FIG. 9 is a block diagram of a circuit for performing a first embodiment of a method of calculating a saturation adjusted color tone vector {right arrow over (C T o )};
FIG. 10 is a block diagram of a circuit for performing a second embodiment of the method of calculating the saturation adjusted color tone vector {right arrow over (C T o )};
FIGS. 11-13 are graphs of mathematical functions;
FIG. 14 is a block diagram of a circuit for performing a third embodiment of the method of calculating the saturation adjusted color tone vector {right arrow over (C T o )}; and
FIG. 15 is a flowchart showing the steps performed in a fourth embodiment of the method of calculating the saturation adjusted color tone vector {right arrow over (C T o )}.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following text uses a single digital RGB color sample vector {right arrow over (C)}=(R,G,B) to explain the invention. It should be readily apparent, however, that in a practical application, the inventive method will be applied to a plurality of digital RGB color sample vectors {right arrow over (C)} representing the images obtained from the time varying RGB video signals of an RGB color system.
The invention begins with decomposing a given digital RGB color input sample vector {right arrow over (C)}=(R,G,B) into two components according to the following equation:
{right arrow over (C)}={right arrow over (w)}+{right arrow over (C)} T . (1)
Here, {right arrow over (w)} represents a white vector and {right arrow over (C)} T =(R T ,G T ,B T ) represents a color tone vector associated with the color input sample vector. The white vector {right arrow over (w)} presumably contains the lightness quantity and the color tone vector {right arrow over (C)} T =(R T ,G T ,B T ) contains the color information. FIG. 3 shows a graphical representation of this decomposition. The range of the color samples is assumed to be 0≦R,G,B≦255, however, the invention can be used with color samples having any range. Note that the direction of the color tone vector {right arrow over (C)} T is associated with the “hue”, while the magnitude of the color tone vector {right arrow over (C)} T is associated with the “saturation”.
A first embodiment of the method for color saturation adjustment is based on applying the following equation:
{right arrow over (C)} o ={right arrow over (w)}+P·{right arrow over (C)} T ={right arrow over (w)}+ {right arrow over ( C T o )}. (2a)
Here, P is a saturation adjustment parameter, which when multiplied against the color tone vector {right arrow over (C)} T , works to adjust the saturation of the color tone vector {right arrow over (C)} T . The vector P·{right arrow over (C)} T represents a saturation adjusted color tone vector {right arrow over (C T o )}. The vector {right arrow over (C)} o is a saturation adjusted RGB color sample vector, which can be output to represent a pixel of an output image.
Subsequently, in this text, four specific examples of methods are provided that can be used to obtain the saturation adjusted color tone vector {right arrow over (C T o )}. These methods differ in the specific form of the saturation adjustment parameter P that is used. The saturation adjustment parameter P can take the form of a color saturation adjusting gain α. This color saturation adjusting gain a can be obtained from the actions of a user of the system or from a circuit constructed to set the color saturation adjusting gain α. The saturation adjustment parameter P can alternatively include two factors, namely a color saturation adjusting gain a and a saturation limiting parameter β, which are multiplied together. In an additional alternative, the saturation adjustment parameter P can be a variable denoted by r. The saturation adjustment parameter P can also take the form of a real color adjusting gain x. The specific forms of the saturation adjustment parameter P will become clear with regard to further explanations provided later on in this text.
An example of the first embodiment of the method for color saturation adjustment will be further explained in a version in which the saturation adjustment parameter P takes the form of a color saturation adjusting gain α, where (α≧0). This example of the first embodiment of the method for color saturation adjustment will then be based on applying the following equation:
{right arrow over (C)} o ={right arrow over (w)}+α·{right arrow over (C)} T ={right arrow over (w)}+ {right arrow over ( C T o )}. (2b)
In equation (2b), it can be seen that the saturation adjusted color tone vector {right arrow over (C T o )} equals α·{right arrow over (C)} T . Note that {right arrow over (C)} o ={right arrow over (w)} if α=0 (no color), {right arrow over (C)} o ={right arrow over (C)} when α=1, and the color saturation level is increased if α>1.
FIG. 4 shows a block diagram of a circuit 20 for performing the example of the first embodiment of the method for color saturation adjustment in which the saturation adjustment parameter P takes the form of a color saturation adjusting gain α. The white and color tone separator 22 decomposes the input color vector {right arrow over (C)}=(R,G,B) into a white vector {right arrow over (w)} and a color tone vector {right arrow over (C)} T =(R T ,G T ,B T ) as described by equation (1). The saturation adjusted color tone vector {right arrow over (C)} T o is obtained using the multiplier 24 , which performs the operation {right arrow over (C)} T o =α·{right arrow over (C)} T . The saturation adjusted RGB color sample vector {right arrow over (C)} o is obtained from the vector summer 26 , which adds the white vector {right arrow over (w)} and the saturation adjusted color tone vector {right arrow over (C T o )}.
The input color vector {right arrow over (C)}=(R,G,B) can be decomposed into a white vector {right arrow over (w)} and a color tone vector {right arrow over (C)} T =(R T ,G T ,B T ) using any of a number of different decompositions. Although, the invention is not meant to be limited to any specific decomposition, the decomposition can be performed, for example, by using any of the following decompositions:
{right arrow over (C)} T =( R−Y,G−Y,B−Y ) and {right arrow over (w)} =( Y,Y,Y ), where Y is a luminance value; (3)
C → T = ( R - X , G - X , B - X ) and w → = ( X , X , X ) ,
where X = R + G + B 3 ; and ( 4 ) C → T = ( R - G + B 2 , G - R + B 2 , B - R + G 2 ) and
w → = ( G + B 2 , R + B 2 , R + G 2 ) . ( 5 ) FIG. 5 shows a block diagram of a circuit 30 for performing the first embodiment of the method in which the decomposition described in equation (3) is performed. The white vector calculation circuit 32 calculates a luminance value Y from the RGB color sample vector {right arrow over (C)} and constructs a white vector {right arrow over (w)}. Each component of the white vector {right arrow over (w)} is equal to the luminance value Y. The vector summer 34 subtracts the white vector {right arrow over (w)} from the RGB color sample vector {right arrow over (C)} to obtain the color tone vector {right arrow over (C T )}. The multiplier 36 multiplies the color tone vector {right arrow over (C T )} by the color saturation adjusting gain a to obtain the saturation adjusted color tone vector {right arrow over (C T o )}. The vector summer 38 adds the saturation adjusted color tone vector {right arrow over (C T o )} and the white vector {right arrow over (w)} to obtain the saturation adjusted RGB color sample vector {right arrow over (C)} o . It is assumed that the color saturation adjusting gain α is equal to or greater than zero.
Turning our attention to the case when the color saturation adjusting gain α=0 in equation (2b), note that the saturation adjusted RGB color sample vector {right arrow over (C)} o may not be a gray value depending on the choice of the color tone vector {right arrow over (C T )} or equivalently on the choice of the white vector {right arrow over (w)}. For instance, if we choose to use equation (3) for the decomposition, the saturation adjusted RGB color sample vector {right arrow over (C)} o will be (Y,Y,Y) when the color saturation adjusting gain α=0. This implies that the saturation adjusted RGB color sample vector {right arrow over (C)} o is a gray value. However, if we choose to use equation (4) for the decomposition, the saturation adjusted RGB color sample vector {right arrow over (C)} o will be (X,X,X) when α=0. In this case, the saturation adjusted RGB color sample vector {right arrow over (C)} o becomes a gray value, but it is somewhat different from the typical gray value denoted as Y. Furthermore, if we choose to use equation (4) for the decomposition, the saturation adjusted RGB color sample vector {right arrow over (C)} o will be
( G + B 2 , R + B 2 , R + G 2 )
when α=0, which is not a gray value, in general. In most cases, it is desirable to ensure that the saturation adjusted RGB color sample vector {right arrow over (C)} o becomes a gray value whose gradation level is associated with the luminance value of the input signal {right arrow over (C)}=(R,G,B) when α=0. For this purpose, a gray mixing ratio is defined as:
α g =min(1.0,α).
A second embodiment of the method for color saturation adjustment is based on applying the following equation:
{right arrow over (C)} o ={right arrow over (Y)} ·(1−α g )+ {right arrow over (w)}·α g +P·{right arrow over (C)} T ; or
{right arrow over ( C )} o ={right arrow over ( Y )}·(1−α g )+{right arrow over ( w )}·α g +{right arrow over ( C T o )}; where {right arrow over (Y)} =( Y,Y,Y ). (6a)
As with the first embodiment, P is the saturation adjustment parameter and {right arrow over (C T o )} is a saturation adjusted color tone vector. It should be clear that the second embodiment of the method for color saturation adjustment is equivalent to the first embodiment except for the fact that additional steps are performed. In particular, the gray mixing ratio α g is multiplied with the white vector {right arrow over (w)} before the summation is performed, and the term {right arrow over (Y)}·(1−α g ) is included in the summation. The term {right arrow over (Y)}·(1−α g ) is defined as a gray level adjusted vector.
An example of the second embodiment of the method for color saturation adjustment will be further explained in a version in which the saturation adjustment parameter P takes the form of a color saturation adjusting gain α, where (α≧0). This example of the second embodiment of the method for color saturation adjustment will then be based on applying the following equation:
{right arrow over (C)} o ={right arrow over (Y)} ·(1−α g )+ {right arrow over (w)}·α g +α·{right arrow over (C)} T ; where {right arrow over (Y)} =( Y,Y,Y ). (6b)
The saturation adjusted RGB color sample vector {right arrow over (C)} o approaches (Y,Y,Y) as a approaches 0. Therefore, the saturation adjusted RGB color sample vector {right arrow over (C)} o becomes a gray value whose gradation level is Y. Note that the saturation adjusted RGB color sample vector {right arrow over (C)} o in equation (6b) is equivalent to that in equation (2b) when α≧1.
FIG. 6 shows a block diagram of a circuit 40 for performing this example of the second embodiment of the method for color saturation adjustment. The white and color tone separator 42 decomposes the input color vector {right arrow over (C)}=(R,G,B) into a white vector {right arrow over (w)} and a color tone vector {right arrow over (C)} T =(R T ,G T ,B T ) as described by equation (1). The saturation adjusted color tone vector {right arrow over (C T o )} is obtained using the multiplier 44 , which performs the operation {right arrow over (C)} T o =α·{right arrow over (C)} T . The minimum value selection circuit 46 obtains the minimum value selected from one and the color saturation adjusting gain α, and provides the result as the gray mixing ratio α g . The output signal of the mixer 48 is {right arrow over (Y)}·(1−α g )+{right arrow over (w)}·α g . The saturation adjusted RGB color sample vector {right arrow over (C)} o is obtained from the adder 50 , which adds the saturation adjusted color tone vector {right arrow over (C T o )} and the term {right arrow over (Y)}·(1−α g )+{right arrow over (w)}·α g obtained from the mixer 48 .
FIG. 7 shows a block diagram of a particular implementation of the circuit 50 for performing the second embodiment of the method for color saturation adjustment. The circuit 50 implements equation (3) to perform the decomposition. The white vector calculation circuit 52 calculates a luminance value Y from the RGB color sample vector {right arrow over (C)} and constructs a white vector {right arrow over (w)}. Each component of the white vector {right arrow over (w)} is equal to the luminance value Y. The vector summer 54 subtracts the white vector {right arrow over (w)} from the RGB color sample vector {right arrow over (C)} to obtain the color tone vector {right arrow over (C T )}. The multiplier 56 multiplies the color tone vector {right arrow over (C T )} by the color saturation adjusting gain α to obtain the saturation adjusted color tone vector {right arrow over (C T o )}. The minimum value selection circuit 58 chooses a minimum value from one and the color saturation adjusting gain α, and provides the result as the gray mixing ratio α g . The output signal of the mixer 60 is {right arrow over (Y)}·(1−α g )+{right arrow over (w)}·α g . The saturation adjusted RGB color sample vector {right arrow over (C)} o is obtained from the adder 62 , which adds the saturation adjusted color tone vector {right arrow over (C T o )} and the term {right arrow over (Y)}·(1−α g )+{right arrow over (w)}·α g that is obtained from the mixer 60 .
One common drawback of the first and second embodiments of the method for color saturation adjustment is that a color can be saturated. That is, depending on the degree of the color saturation level of the input sample and the requested value of the color saturation adjusting gain α, the resulting saturation adjusted RGB color vector {right arrow over (C)} o =(R o ,G o ,B o ) can be mapped to outside the color gamut of the R,G,B signals (i.e., R>255, G>255, and/or B>255). In other words, the saturation adjusted RGB color vector {right arrow over (C)} T o =α·{right arrow over (C T )} can be saturated depending on the saturation level of {right arrow over (C T )} and α. Hence, an optionally provided feature of the invention is the development of color saturation limiting functions that can be incorporated into the method for color saturation adjustment in an RGB color system.
We will calculate the magnitude of the color tone vector {right arrow over (C T )} and associate this magnitude with the saturation level of the color tone vector {right arrow over (C T )}. Remember that the color tone vector {right arrow over (C T )} has the components (R T ,G T ,B T ). We can calculate the magnitude, which we have associated with the saturation level of the color tone vector {right arrow over (C T )}, using the following equation:
S ({right arrow over ( C T )})=√{square root over ( R T 2 +G T 2 +B T 2 )}. (7)
We can alternatively approximate the saturation level using the following equation:
S ( {right arrow over (C)} T )=| R T |+|G T |+|B T |. (8a)
Depending upon the application, various different forms of calculating the saturation level can be defined and the invention should not be limited to any one particular way of calculating this saturation level. For example, some additional ways of calculating the saturation level include:
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Thus far, we have disclosed, two embodiments of the method for color saturation adjustment. Examples have been given in equations (3)-(5) of how to decompose the digital RGB color input sample vector {right arrow over (C)}=(R,G,B) into a white vector {right arrow over (w)} and a color tone vector C T , however, the invention should not be construed as being limited to these examples of the decomposition. Examples have been given in equations (7) and (8a)-(8e) of how to calculate the saturation level of the color tone vector {right arrow over (C T )}, however, as already discussed, the invention should not be construed as being limited to these examples of calculating the saturation level.
In the following text, four embodiments of a method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} will be disclosed. These embodiments of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} use different forms of the saturation adjustment parameter P. Any one of these embodiments for calculating the saturation adjusted color tone vector {right arrow over (C T o )} can be used together with the first and second embodiments of the method for color saturation adjustment.
The first embodiment of the method of calculating the saturation adjusted color tone vector {right arrow over (C T o )} includes developing a saturation limiting parameter β that will be multiplied together with α·{right arrow over (C T )} in order to limit the saturation level to a certain level. That is, the saturation adjusted color tone vector {right arrow over (C T o )} is given as:
{right arrow over (C)} T o =β·α·{right arrow over (C)} T . (9)
FIG. 8 shows two multipliers 60 and 62 connected to perform the operation described in equation (9). Accordingly, when using the first embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} in conjunction with the first embodiment of the method for color saturation adjustment as expressed in equation (2a), we define the saturation adjustment parameter P as being β·α. Similarly, when using the first embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} in conjunction with the second embodiment of the method for color saturation adjustment as expressed in equation (6a), we define the saturation adjustment parameter P as being β·α.
Now the question is how to formulate the saturation limiting parameter β. Note that the purpose of multiplying the saturation limiting parameter β with α·{right arrow over (C T )} as expressed in equation (9) is to prevent the saturation level of α·{right arrow over (C T )} from exceeding a certain saturation level.
If the saturation level S(α·{right arrow over (C)} T ) is less than a certain level, which implies that α·{right arrow over (C T )} is “not saturated”, then it is obvious from the purpose of introducing the saturation limiting parameter β that β should be equal to one. Hence, it can be stated that:
β=1 if S (α· {right arrow over (C)} T )≦ L, (10)
where L denotes a pre-determined saturation level to which we want to limit the color saturation level of the adjusted color samples. Hereinafter, L will be referred to as a predetermined limit value. It can be stated that:
{right arrow over (C)} T o =α·{right arrow over (C)} T , (11)
when S(α·{right arrow over (C)} T )≦L.
Now in the case when S(α·{right arrow over (C)} T )>L, we need to multiply α·{right arrow over (C)} T and the saturation limiting parameter β together so that the color saturation level of the resulting saturation adjusted color tone vector {right arrow over (C)} T o can be adjusted as a factor of β in order to prevent a possible saturation. The following constraint is imposed:
S ( {right arrow over (C)} T o )= L.
From the definition given in (7) or (8a), for example, it is noted that:
S ( {right arrow over (C)} T o )= S (β·α {right arrow over (C)} T )=β· S (α· {right arrow over (C)} T ).
We then obtain the following saturation limiting parameter:
β
=
L
S
(
α
·
C
→
T
)
.
(
12
)
In summary, the saturation adjustment parameter P is chosen to be the color saturation adjusting gain α multiplied by the saturation limiting parameter β. The saturation adjusted color tone vector {right arrow over (C T o )} is then calculated according to the following equation:
C
→
T
o
=
β
·
α
·
C
→
T
,
where
(
13
)
β
=
{
1
if
S
(
α
·
C
→
T
)
≤
L
L
S
(
α
·
C
→
T
)
else
(
14
)
FIG. 9 shows a block diagram of a circuit 70 for performing the first embodiment of the method of calculating the saturation adjusted color tone vector {right arrow over (C T o )}. The multiplier 72 multiplies the color tone vector {right arrow over (C T )} by the color saturation adjusting gain α. The saturation calculation circuit 74 calculates the saturation level S(α·{right arrow over (C)} T ) and the β-selection circuit 76 chooses the value of the saturation limiting parameter β in accordance with equation (14). The saturation adjusted color tone vector {right arrow over (C T o )} is obtained from the multiplier 78 , which multiplies β and α·{right arrow over (C)} T .
A second embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} will now be developed. If we note that S(α·{right arrow over (C)} T )=α·S({right arrow over (C)} T ) and combine it with equations (13) and (14), we obtain:
C → T o = r · C → T
where : ( 15 ) r = { α if S ( C → T ) ≤ L α L S ( C → T ) else ( 16 )
The result obtained when using equations (15) and (16) to calculate the saturation adjusted color tone vector {right arrow over (C T o )} is equivalent to the result obtained when using equations (13) and (14). Note, however, when equations (15) and (16) are used to calculate the saturation adjusted color tone vector {right arrow over (C T o )}, less computation is required than when using equations (13) and (14). Accordingly, when using the second embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} in conjunction with the first embodiment of the method for color saturation adjustment as expressed in equation (2a), or the second embodiment of the method for color saturation adjustment as expressed in equation (6a), we define the saturation adjustment parameter P as being r.
FIG. 10 shows a block diagram of a circuit 80 for performing the second method of calculating the saturation adjusted color tone vector {right arrow over (C T o )}. The saturation calculation circuit 82 calculates the saturation level S({right arrow over (C)} T ) and the r-selection circuit 84 chooses the value of r in accordance with equation (16). The saturation adjusted color tone vector {right arrow over (C T o )} is obtained from the multiplier 86 , which multiplies r and {right arrow over (C)} T .
A third embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} will now be developed. The saturation adjusted color tone vector {right arrow over (C T o )} can be expressed according to the following equation:
{right arrow over (C)} T o =x·{right arrow over (C)} T , (17)
where x denotes a real color adjusting gain defined by:
x = { α if 0 ≤ α ≤ 1 f ( S ( C → T ) ) if α > 1 ( 18 )
The mathematical function ƒ(S({right arrow over (C)} T )) can be any function that satisfies the following conditions:
ƒ(S({right arrow over (C)} T )) is a monotonically decreasing function with respect to S({right arrow over (C)} T ) for 0≦S({right arrow over (C)} T )≦L where L is a predetermined constant limit value; ƒ(0)=α; and ƒ(S({right arrow over (C)} T ))=1 for S({right arrow over (C)} T )≧L.
Note that the last condition ensures no change is made in the color saturation level of the input sample when its color saturation level exceeds a certain level even though the color saturation adjusting gain is large (α>1). Examples of ƒ(S({right arrow over (C)} T )) are shown in FIGS. 11 , 12 , and 13 . For instance, in FIG. 11 , x=ƒ(S({right arrow over (C)} T )) for 0≦S({right arrow over (C)} T )≦L can be expressed as:
x = 1 + ( α - 1 ) · ( L - S ( C → T ) ) · ( L + S ( C → T ) ) L 2 .
Because of the constraints on ƒ(S({right arrow over (C)} T )), when S({right arrow over (C)} T )≧L, the real color adjusting gain x becomes:
x = { α if 0 ≤ α ≤ 1 1 if α > 1
When using the third embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} in conjunction with the first embodiment of the method for color saturation adjustment as expressed in equation (2a) or with the second embodiment of the method for color saturation adjustment as expressed in equation (6a), we define the saturation adjustment parameter P as being the real color adjusting gain x.
FIG. 14 shows a block diagram of a circuit 90 for performing the third embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )}. The saturation calculation circuit 92 calculates the saturation level S({right arrow over (C)} T ). The circuit 94 for calculating ƒ(S({right arrow over (C)} T )) evaluates ƒ(S({right arrow over (C)} T )) at the saturation level S({right arrow over (C)} T ). The real color adjusting gain circuit 96 chooses the value of x in accordance with equation (18). The saturation adjusted color tone vector {right arrow over (C T o )} is obtained from the multiplier 98 , which multiplies x and {right arrow over (C)} T .
A fourth embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} will now be developed. We will limit the saturation level of the saturation adjusted color tone vector {right arrow over (C)} T o =x·{right arrow over (C)} T such that:
S ( {right arrow over (C)} T o )= x·S ( {right arrow over (C)} T )≦ L.
When S({right arrow over (C)} T )≦L and α>1, the following condition is obtained:
x ≤ L S ( C → T ) ( 19 )
By combining equations (18) and (19), we obtain the following relationship for the real color adjusting gain:
x = { α if 0 ≤ α ≤ 1 min ( f ( S ( C → T ) ) , L S ( C ⇀ T ) ) if α > 1 and S ( C → T ) ≤ L 1 if α > 1 and S ( C → T ) > L . ( 20 )
When using the fourth embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} in conjunction with the first embodiment of the method for color saturation adjustment as expressed in equation (2a) or with the second embodiment of the method for color saturation adjustment as expressed in equation (6a), we define the saturation adjustment parameter P as being the real color adjusting gain x.
FIG. 15 is a flowchart illustrating the steps used to implement the fourth embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} in accordance with equations (17) and (20). In step 1 , the color saturation adjusting gain α and the color tone vector {right arrow over (C T )} are acquired. In step 2 , it is determined whether the color saturation adjusting gain α is equal to or less than 1. If so, the real color adjusting gain x is set equal to α in step 9 . If the color saturation adjusting gain α is not equal to or less than 1, then in step 3 , the saturation level of the color tone vector {right arrow over (C T )} is determined. In step 4 , it is determined whether the saturation level of the color tone vector {right arrow over (C T )} is greater than the predetermined limit L. If the saturation level of the color tone vector {right arrow over (C T )} is greater than the predetermined limit L, then in step 5 , the real color adjusting gain x is set equal to 1. If the saturation level of the color tone vector {right arrow over (C T )} is not greater than the predetermined limit L, then in step 6 , a first value is obtained by evaluating the mathematical function ƒ at the value of the saturation level of the color tone vector {right arrow over (C T )}, and a second value is obtained by dividing the predetermined limit L by the saturation level of the color tone vector {right arrow over (C T )}. Additionally in step 6 , a minimum value is selected from the first value and the second value and the real color adjusting gain x is set equal to this minimum value. As can be seen in FIG. 15 , step 7 can follow either step 9 , 5 , or 6 . In step 7 , a saturation adjusted color tone vector {right arrow over (C T o )} is obtained by multiplying the real color adjusting gain x with the color tone vector {right arrow over (C T )}. The saturation adjusted color tone vector {right arrow over (C T o )} can then be used in equation (2a) to perform the first embodiment of the method for color saturation adjustment, or in equation (6a) to perform the second embodiment. Step 8 causes the procedure to loop back to step 1 to obtain the next color tone vector {right arrow over (C T )}, which may represent another pixel of the same input image, or which may possibly represent the first pixel of a subsequent input image.
A circuit for performing the fourth embodiment of the method for calculating the saturation adjusted color tone vector {right arrow over (C T o )} can be constructed similarly to the circuit 90 shown in FIG. 14 . The difference will be that the real color adjusting gain circuit 96 will choose the value of x in accordance with equation (20).
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The present invention relates to a method for adjusting the saturation levels of the pixels of a time varying image being represented by RGB color sample vectors {right arrow over (C)} in an RGB color system. The method does not require the RGB color sample vectors {right arrow over (C)} to be converted into YUV samples in order to subsequently perform saturation adjustment. The method includes steps of: decomposing an RGB color sample vector {right arrow over (C)} into a white vector {right arrow over (w)} and a color tone vector {right arrow over (C)} T ; obtaining a saturation adjusted color tone vector {right arrow over (C T o )} by multiplying the color tone vector {right arrow over (C)} T by a saturation adjustment parameter; obtaining a saturation adjusted RGB color sample vector {right arrow over (C)} o by adding the white vector {right arrow over (w)} and the saturation adjusted color tone vector {right arrow over (C T o )}; and using the saturation adjusted RGB color sample vector {right arrow over (C)} o to represent a color pixel of an output image.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention is related to air conditioning systems for vehicles, and particularly related to air conditioning systems for vehicles powered by internal combustion engine.
[0003] 2. Description of Related Art
[0004] An air conditioning system provides a human comfort environment by controlling a suitable range of air temperature and humidity in the living environment. The history of air conditioning systems is over one century old. In 1939, an air conditioning system for an automobile was developed by Packard Motor Car Company. By 1969 more than 50% of the automobiles sold in the United States were equipped with automobile air conditioning systems. Nowadays, automobile air conditioning systems have become one of the necessary items of equipments in automobiles.
[0005] In the conventional art, the long standing dilemma of vehicle air-conditioning faced by vehicles powered solely by internal combustion engines is that, when they are stopped for a short period, keeping the air-conditioning running requires continuous operation of the engine and hence increases fuel consumption and exhaust gas emission. Switching off the engine and hence the air-conditioning results in a temperature rise. In tropical and subtropical geographical areas such as South China, cabin temperatures can rise rapidly beyond a bearable level shortly after the air-conditioning is switched off. The advent of the hybrid electric vehicle provides an ideal platform to address this problem. Examples of such systems are disclosed in U.S. Pat. Nos. 6,840,055 and 6,516,621. However, these systems are not suitable for conventional internal engine powered vehicles.
[0006] FIG. 1 shows the basic structure of a conventional automobile air conditioning (A/C) system. In this system the A/C compressor 3 is driven by the engine 1 of the vehicle. The clutch 2 is an electromagnetic clutch which is integrated in most A/C compressors. A/C temperature control relies on switching the clutch off and on. This structure is simple and easy for maintenance. However, the speed of the engine changes frequently in a wide range of speeds when the vehicle is running on the road. The speed of the compressor changes independently of the A/C temperature and hence the A/C temperature fluctuates. Another disadvantage of the conventional air conditioning system is that the air conditioning system has to be shut down when the engine is shut down (vehicle off).
[0007] Accordingly, a need exists for an improved automobile air conditioning system to provide air-conditioning when the operation of the combustion engine is off, and to drive the speed of the compressor in such a manner as to provide a steady A/C temperature.
SUMMARY
[0008] Several aspects of the presently claimed invention have been developed with a view to substantially reduce or eliminate the drawbacks described hereinbefore and known to those skilled in the art and to provide an automobile hybrid air conditioning system that may be adopted to offer air-conditioning without the need to keep the vehicle combustion engine running, thus reducing fuel consumption and exhaust gas emission. Some embodiments of the invention provide steady temperature irrespective of speed changes in the combustion engine. The compressor of this system is driven by the internal combustion engine when the engine is running as a conventional automobile air conditioning system. When the engine is shut down, the A/C compressor of this system is driven by an electric machine, in some embodiments a brushless DC (BLDC) machine, powered by a rechargeable battery unit, in some embodiments a 24-volt lead acid battery. When the battery voltage level is low, resulting from partial discharge, the battery is recharged with electric power generated from the same electric machine driven by the engine. The A/C temperature may be controlled by varying the speed of the electric machine.
[0009] According to an aspect of the presently claimed invention, there is provided a hybrid air conditioning system for a combustion engine vehicle. The system includes a combustion engine mechanically coupled to the transmission system of the vehicle; a rechargeable battery unit selectively connected to a battery charger and a motor drive electrically; and an electric machine electrically connected to the battery charger and the motor drive. The electric machine is further selectively coupled to the combustion engine mechanically. A compressor for air conditioning is selectively coupled to the combustion engine and the electric machine mechanically. When the combustion engine is running and the rechargeable battery unit is low, the electric machine is configured by an MCU control unit as mechanically coupled to the combustion engine, and the battery charger is configured as electrically connected to the rechargeable battery unit such that the electric machine generates electric power to recharge the rechargeable battery unit. When the combustion engine stops and air conditioning is required, the rechargeable battery unit is configured by the MCU control unit as electrically connected to the motor drive, and the electric machine is configured as mechanically coupled to the compressor to provide mechanical power to drive the compressor.
[0010] In some embodiments the hybrid air conditioning system further includes a first clutch, a second clutch and a third clutch. The clutches are mechanically coupled with each other by pulleys and belt. The first clutch is mechanically coupled to the combustion engine, for example by pulleys and belt; the second clutch is mechanically coupled to the compressor; and the third clutch is mechanically coupled to the DC electric machine.
[0011] In some embodiments the hybrid air conditioning system further includes a first relay and a second relay. The first relay electrically connects the output of the battery charger to the rechargeable battery unit and the second relay electrically connects the motor drive to the rechargeable battery unit. In some embodiments the first relay and the second relay have normally-open switch contacts which provide electrical connection when the relay is energized.
[0012] In some embodiment, when the combustion engine is running and air conditioning is required, the compressor is configured as mechanically coupled to the combustion engine such that the combustion engine produces mechanical power for driving the compressor.
[0013] In some embodiments, the hybrid air conditioning system further includes a battery charger controller, for example in the MCU control unit, for monitoring both the rechargeable battery voltage and the speed of the electric machine. When the electric machine is generating electric power for charging the rechargeable battery unit, the charging current applied to the rechargeable battery unit is controlled by the battery charger controller to be directly proportional to the speed of the electric machine.
[0014] According to another aspect of the presently claimed invention, there is provided a hybrid air conditioning controller for a combustion engine vehicle. The combustion engine vehicle has a combustion engine, a rechargeable battery unit, a battery charger, a electric machine, and a compressor for air conditioning. When the combustion engine is running and the rechargeable battery unit is partly discharged, the hybrid air conditioning controller configures the electric machine as mechanically coupled to the combustion engine, and the hybrid air conditioning controller configures the battery charger as electrically connected to the rechargeable battery unit such that the electric machine generates electric power to recharge the rechargeable battery unit. When the combustion engine stops and air conditioning is required, the hybrid air conditioning controller configures the rechargeable battery unit as electrically connected to the motor drive and the electric machine as mechanically coupled to the compressor to provide mechanical power to drive the compressor.
[0015] In some embodiments, when the combustion engine is running and air conditioning is required, the hybrid air conditioning controller configures the compressor as mechanically coupled to the combustion engine such that the combustion engine produces mechanical power for driving the compressor.
[0016] In another embodiment, the hybrid air conditioning controller further includes a battery charger controller for monitoring both the rechargeable battery voltage and the speed of the electric machine. When the electric machine is generating electric power for charging the rechargeable battery unit, the charging current applied to the rechargeable battery unit is controlled by the battery charger controller to be directly proportional to the speed of the electric machine.
[0017] According to a further aspect of the presently claimed invention, there is provided a method of hybrid air conditioning for combustion engine vehicle, the combustion engine vehicle having a combustion engine, a rechargeable battery unit, a battery charger, a electric machine, and a compressor for air conditioning. The method includes, when the combustion engine is running and the rechargeable battery unit is low, configuring the electric machine as mechanically coupled to the combustion engine and the battery charger as electrically connected to the rechargeable battery unit such that the electric machine generates electric power to recharge the rechargeable battery unit. When the combustion engine stops and air conditioning is required, the method includes configuring the rechargeable battery unit as electrically connected to the motor drive, and the electric machine is configured as mechanically coupled to the compressor to provide mechanical power to drive the compressor.
[0018] In some embodiments the method further includes, when the combustion engine is running and air conditioning is required, configuring the compressor as mechanically coupled to the combustion engine such that the combustion engine produces mechanical power for driving the compressor.
[0019] In some embodiments the method also includes monitoring both the rechargeable battery voltage and the speed of the electric machine. When the electric machine is generating electric power for charging the rechargeable battery unit, the charging current applied to the rechargeable battery unit is controlled to be directly proportional to the speed of the electric machine.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is a system diagram of a conventional automobile air conditioning system according to the prior art.
[0021] FIG. 2 is a system diagram in accordance with an embodiment of the present invention.
[0022] FIG. 3 is an equivalent system diagram in accordance with an embodiment of the present invention in mode 1 operation.
[0023] FIG. 4 is an equivalent system diagram in accordance with an embodiment of the present invention in mode 2 operation.
[0024] FIG. 5 is an equivalent system diagram in accordance with an embodiment of the present invention in mode 3 operation.
[0025] FIG. 6 is an equivalent system diagram in accordance with an embodiment of the present invention in mode 4 operation.
[0026] FIG. 7 is an equivalent system diagram in accordance with an embodiment of the present invention in mode 5 operation.
[0027] FIG. 8 is a bi-directional drive in accordance with a further embodiment of the present invention.
[0028] FIG. 9 is a state diagram of the control flow in accordance with an embodiment of the present invention.
DESCRIPTION OF EMBODIMENTS
[0029] An automobile hybrid air conditioning system is described hereinafter. In the following description, numerous specific details, including electrical components, mechanical components, and the like are set forth. However, from this disclosure, it will be apparent to those skilled in the art that modifications and substitutions may be made without departing from the scope of the invention. In other circumstances, specific details may be omitted so as not to obscure the invention.
[0030] Where reference is made in any one or more of the accompanying drawings to steps and features which have the same reference numerals, those steps and features have for the purposes of this description the same function(s) or operation(s), unless the contrary intention appears.
[0031] The embodiments of the present invention provide automobile air conditioning systems that are capable of operating for a limited time period when the combustion engine vehicle stops. FIG. 2 shows an automobile air conditioning system diagram in accordance with an embodiment of the present invention. The system comprises an A/C compressor 18 integrated with an electromagnetic clutch 16 , two further electromagnetic clutches 16 , 17 , a valve 21 , a condenser 27 , an evaporator 22 , belts 11 , 12 and belt pulleys 27 , 28 , 29 , 30 , 31 , a brushless DC electric machine 19 , a motor drive 20 , a rechargeable battery 26 , a battery charger 25 , tubes in high pressure 14 , tubes in low pressure 13 , two relays 23 , 24 , and an MCU control unit 32 .
[0032] According to FIG. 2 , the clutches 15 , 16 , 17 are used for switching the mechanical power sources to the A/C compressor 18 between the combustion engine 10 and the electric machine 19 . Mechanical power is transmitted by the belt pulleys 27 , 28 , 29 , 30 , 31 and the belts 11 , 12 .
[0033] The rechargeable battery 26 is a deep cycle battery so that it is suitable for providing high current in long duration with long life cycles. It powers the motor drive 23 , the controller of the battery charger 24 and the MCU control unit 32 .
[0034] According to an embodiment of the present invention, the electric machine 19 is a brushless DC (BLDC) machine. This type of machine has fast response, high power density, robustness and high reliability. The electric machine 19 can serve as an electric motor as well as an electric generator. It is both for driving the compressor 18 and for generating electric power for charging the rechargeable battery 26 . When the BLDC machine 19 drives the A/C compressor 18 , it is driven by the motor drive 20 . The electric power for driving the BLDC machine is provided by the rechargeable battery 26 . The battery charger 25 is responsible for recharging the rechargeable battery 26 . The relay 23 is for switching the motor drive 20 on and off. The relay 24 is for connecting and disconnecting the rechargeable battery 26 and the battery charger 25 . In an exemplary embodiment of the present invention, the relays 23 and 24 are normally-open type relays. The relay 23 and the relay 24 should not be closed at the same moment.
[0035] The MCU control unit 32 is powered by the rechargeable battery 26 . It controls on/off states of the relays 23 , 24 and closed/open states of the clutches 15 , 16 , 17 . Relay drivers and clutch drivers are built into the MCU control unit 32 . It is also responsible for controlling the speed of the electric machine 19 with the motor drive 20 when the machine 19 is in motoring operation. It monitors the speed of the electric machine 19 by a Hall effect position sensor built in the machine 19 and the A/C temperature by a thermal sensor so that the speed of the electric machine 19 and the A/C temperature are under closed-loop control. It also monitors the rechargeable battery 26 voltage and the angular speed of the combustion engine 10 . When the speed of the combustion engine 10 is too high while the electric machine 19 is generating power for recharging the rechargeable battery 26 , the MCU control unit 32 opens clutch 3 17 in order to avoid damaging the electric machine 19 by over speed and the battery charger 25 by over input voltage.
[0036] The controller of the battery charger 25 monitors both the voltage of the rechargeable battery 26 and the speed of the electric machine 19 . When the electric machine 19 is generating electric power for recharging the rechargeable battery 26 , its output voltage of the electric machine 19 is substantially in direct proportion relationship with its angular speed. The charging current of the rechargeable battery 26 is controlled by the controller of the battery charger 25 . It is proportional to the speed of the electric machine 19 and hence, over input current of the battery charger 25 is prevented. The rechargeable battery 26 can be rechargeable even when the combustion engine is at low speed.
[0037] The operation of the automobile hybrid air conditioning system of the present invention shown in FIG. 1 is considered as 5 modes of operation. The equivalent system diagrams of the modes of operation of the present invention are shown in FIG. 3 , FIG. 4 , FIG. 5 , FIG. 6 and FIG. 7 . The modes of operation are described in the following:
Mode 1
[0038] FIG. 3 shows an equivalent system diagram in accordance with an embodiment in Mode 1 operation. In this mode of operation, the vehicle is on and the air conditioning system is on. The combustion engine 10 is running in Mode 1. The rechargeable battery 26 is fully charged. Clutch 1 15 is closed. Relay 1 23 , Relay 2 24 and Clutch 3 17 are open. The combustion engine 10 drives the A/C compressor 18 . The electric machine 19 is not operated. The rechargeable battery 26 is not recharged. The room temperature is controlled by switching on and off Clutch 2 16 , i.e., switching on and off of the A/C compressor 18 .
Mode 2
[0039] FIG. 4 shows an equivalent system diagram in accordance with an embodiment in Mode 2 operation. The vehicle stops in Mode 2. The air conditioning system of the present invention is on. The combustion engine 10 is not running in this moment. Clutch 1 15 and Relay 2 24 are open. Clutch 2 16 , Clutch 3 17 and Relay 1 23 are closed. The rechargeable battery 26 produces electric power to the motor drive 20 to drive the electric machine 19 , and the electric machine 19 drives the A/C compressor 18 . The room temperature is controlled by controlling the speed of the electric machine 19 by the motor drive 20 and the MCU control unit 32 . This obtains stable temperature and saves compressor starting energy. The electric machine 19 stops when the voltage of the rechargeable battery 26 reaches its minimum discharge voltage.
Mode 3
[0040] FIG. 5 shows an equivalent system diagram in accordance with an embodiment in Mode 3 operation. The vehicle is running in Mode 3 so that the combustion engine 10 is running in this moment. The rechargeable battery 26 voltage reaches its minimum battery voltage. The air conditioning system of the present invention is on. The rechargeable battery 26 is recharged by the battery charger 25 . Clutch 1 15 , Clutch 3 17 and Relay 2 24 are all closed. Relay 1 23 is open. The combustion engine 10 drives both the A/C compressor 18 and the electric machine 19 . The electric machine 19 generates electric power to the battery charger 25 to recharge the rechargeable battery 25 . The A/C temperature is controlled by switching on and off Clutch 2 16 .
Mode 4
[0041] FIG. 6 shows an equivalent system diagram in accordance with an embodiment in Mode 4 operation. The air conditioning system of the present invention is off in Mode 4. The combustion engine 10 is running. The rechargeable battery 26 is recharged because its voltage level is low. Clutch 1 15 , Clutch 3 17 and Relay 2 24 are closed. Clutch 2 16 and Relay 1 23 are open. The combustion engine 10 drives only the electric machine to generate electric power to the battery charger 25 and to recharge the rechargeable battery 26 .
Mode 5
[0042] FIG. 7 shows an equivalent system diagram in accordance with an embodiment in Mode 5 operation. The air conditioning system of the present invention is off in Mode 5. The combustion engine 10 is either running or stop. The rechargeable battery 26 is fully charged. The electric machine 19 neither drives the A/C compressor 18 nor generates electric power. Clutch 1 15 , Clutch 2 16 , Clutch 3 17 , Relay 1 23 and Relay 2 24 are all open.
[0043] According to another embodiment, the electric drive in FIG. 1 can be replaced by a bi-directional drive as depicted in FIG. 8 . The integration of motor drive and battery charger shares certain components of the power electronic circuitry and it eliminates the use of power relays. Thus, it can be made smaller with longer life cycle.
[0044] The status of the combustion engine, the air conditioning, and rechargeable battery under different modes are summarized in Table 1 below:
[0000]
TABLE 1
Mode
Engine
A/C
Batt
5
OFF
OFF
/
RUNS
OFF
FULL
1
RUNS
ON
FULL
2
OFF
ON
/
3
RUNS
ON
LOW
4
RUNS
OFF
LOW
[0045] FIG. 8 shows a bi-directional drive which replaces the electric drive in FIG. 2 according to a further embodiment of the present invention. The integration of motor drive and battery charger shares certain components of the power electronic circuitry and it eliminates the use of power relays. Thus, it can be made smaller with longer life cycle.
[0046] FIG. 9 is a state diagram of the control flow of the automobile hybrid air conditioning system in accordance with an embodiment. The control flow begins at Mode 5, state 901 when the system is started up, both the combustion engine and A/C are turned off in this mode. If the engine is then started to run and the A/C is switched on with full battery level, the state changes to Mode 1, state 902 . If the engine is started to run while the battery level is low, the state changes to Mode 4, state 905 . If the A/C is turned on while the engine remains off, then the state changes to Mode 2, state 903 .
[0047] At Mode 1, state 902 where both the engine and A/C are running, if the A/C is then turned off, the state changes to Mode 2, state 903 . If the battery level becomes low, the state changes to Mode 3, state 904 .
[0048] At Mode 2, state 903 where the engine is off and the A/C is running, if the engine is then started to run, the state changes to Mode 3, state 904 . If the A/C is turned off, the state changes back to Mode 5, state 901 .
[0049] At Mode 3, state 904 where both the engine and A/C are running with the battery being charged, if the A/C is then turned off, the state changes to Mode 4, state 905 . If the battery level becomes full, the state changes to Mode 1, state 902 . If the engine is stopped, the state returns to Mode 5, state 901 .
[0050] At Mode 4, state 905 where the engine is running, the battery is being charged and the A/C is off, if the A/C is then turned on, the state changes to Mode 3, state 904 . If the engine is turned off or the battery level becomes full, the state returns to Mode 5, state 901 .
[0051] Embodiments described hereinbefore provide air-conditioning when the operation of the vehicle combustion engine is off, and drive the speed of the compressor in such a manner as to provide steady A/C temperature.
[0052] The foregoing description provides exemplary embodiments only, and is not intended to limit the scope, applicability or configurations of the present invention. Rather, the description of the exemplary embodiments provides those skilled in the art with enabling descriptions for implementing embodiments of the invention. Various changes may be made in the function and arrangement of elements without departing from the scope of the invention as set forth in the claims hereinafter.
[0053] Where specific features, elements and steps referred to herein have known equivalents in the art to which the invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth. Furthermore, features, elements and steps referred to in respect of particular embodiments may optionally form part of any of the other embodiments unless stated to the contrary.
[0054] The term “comprising”, as used herein, is intended to have an open-ended, non-exclusive meaning. For example, the term is intended to mean: “including principally, but not necessarily solely” and not to mean “consisting essentially of” or “consisting only of”. Variations of the term “comprising”, such as “comprise”, “comprises” and “is comprised of”, have corresponding meanings.
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A hybrid air conditioning system for a combustion engine vehicle. When the combustion engine is running and a rechargeable battery unit is not at full charge, an electric machine is configured by an MCU control unit as mechanically coupled to the combustion engine, and a battery charger is configured as electrically connected to the rechargeable battery unit such that the electric machine generates electric power to recharge the rechargeable battery unit. When the combustion engine stops and air conditioning is required, the rechargeable battery unit is configured by the MCU control unit as electrically connected to a motor drive, and the electric machine is configured as mechanically coupled to the compressor to provide mechanical power to drive the compressor. This allows the automobile air conditioning system to operate for a limited period of time after the combustion engine stops.
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BACKGROUND OF THE INVENTION
1. Field of Invention
The invention relates to slat conveyor belts for slat conveyors.
2. Description of Prior Art
In slat conveyors, such as are used especially in the textile industry and also for the transporting of, for example, packages or the like, the conveyor belt possesses a plurality of carrying straps circulating parallel to one another in the conveying direction, on which are fixed closely spaced slats oriented transversely to the conveying direction. Teeth may also be mounted on the lower face of the carrying straps at predetermined intervals in general in the region of each slat, thus providing the action of toothed belts, which are driven by corresponding toothed rollers and ensure an extremely accurate synchronization of the conveyor belt.
For the fixing of the slats to the carrying straps, notch or snap connectors have proved eminently successful consisting of heads permanently fixed to the carrying straps, the slats being engaged onto these heads by means of a notch profile formed on their lower face. These permit very rapid assembly of the conveyor belt, and moreover it is also readily possible to replace individual slats in the case of a defect, by simply pulling the damaged slat off its head from the upper side of the conveyor belt and engaging a new slat.
There are many cases, however, in which such notch connectors can be used not at all or only to a limited extent. This applies especially where, during running, an upwardly directed moment can be exerted upon the slats, giving rise to a risk of the slats coming off their heads. In such cases, the fixing of the slats to the carrying straps is normally provided by means of screw connectors or rivet connectors, which are passed through corresponding bores in the slats and the carrying straps. With such connecting components however, the decisive advantages of the notch connection, in particular in regard to the easy replacement of individual slats are lost, since both the known types of screw connectors and also the rivets that are suitable for the fixing of the slats require access both to the upper side and also to the lower side of the conveyor belt for the replacement of a slat. Since in general, access to the under face of a conveyor belt can normally be obtained only with great difficulty, not least on account of the frequently large width and very flat construction of the slat conveyors under discussion here, the replacement of individual slats in the case of the known screw connectors or rivet connectors always presents a considerable problem.
SUMMARY OF THE INVENTION
The present invention seeks in its preferred embodiment to create a slat conveyor belt, wherein the preventing of unintentional loosening of the slats from the carrying straps is equally good as with the known screw connectors or rivet connectors, but in which also the replacement of individual slats can be carried out with access to the upper face only of the conveyor belt.
According to the present invention there is provided a slat conveyor belt for slat conveyors, comprising a plurality of carrying straps arranged to circulate in the conveying direction and slats extending transversely across the conveying direction and resting upon the carrying straps, said slats being fixed to the carrying straps by means of a plurality of screw connections passing through bores in the slats, wherein the nut for each screw connection is formed as a threaded nipple fixed to the surface of the corresponding carrying strap, which nipple receives the fixing screw passed from above through the bore in the slat and penetrates into a widened-out portion at the lower end of this bore.
In an embodiment of the invention there is provided for the purpose of fixing the slats, a special screw connector, the particular feature of which lies in the fact that the nut forming part of such a connector is formed, not as a free component laid against the under face of the carrying strap, but as a component in the form of a threaded nipple firmly anchored at a predetermined position on the carrying strap. If, in a slat conveyor constructed in this manner, a slat needs to be replaced, this can now be done from the upper side only of the conveyor belt, by first undoing all the fixing screws of this slat, then lifting the relevant slat, then replacing a new slat in position, and finally tightening up the fixing screws again into the threaded nipples. No operations on the lower face of the conveyor belt are necessary in this procedure.
The anchoring of the threaded nipples to the carrying straps can be effected in a great variety of ways. One useful method is to construct each threaded nipple as a tubular rivet, which is pushed from above through a bore in the carrying strap and is expanded on the lower face of this strap. Alternatively, the threaded nipples can be screwed onto the lower face of the carrying strap or can be glued to the carrying strap or, if they are of a plastic material, can be injected onto the carrying strap. If teeth are provided on the carrying strap, there are further advantageous possibilities in that the threaded nipples can also be incorporated as the fixing for these teeth, or the threaded nipples may be produced in one piece with the teeth and then connected in the form of this integral unit to the carrying strap.
The threaded nipples must not of course rotate when the fixing screws are operated. To meet this requirement, however, it is not essential to have an absolutely nonrotatable anchorage of the threaded nipple to the carrying strap, but the requirement can easily be satisfied by the threaded nipple additionally being connected by friction or in a close-fitting manner with the inner surface of the lower widened-out portion of the bore in the slat, into which it penetrates. Such an additional measure is especially suitable when single threaded nipples are used, the absolutely non-rotating anchorage of which to the carrying straps cannot always be adequately ensured. If by contrast, the threaded nipples are combined into pairs (for example when two threaded nipples together with one tooth are made from one component), or when an absolutely non-rotating anchorage of the threaded nipple to the carrying strap can be achieved in some other simple manner (for example when the threaded nipples are injection moulded through non-circular holes of the carrying strap), such an additional measure is not necessary.
For the purpose of securing the fixing screws passing through the individual bores in the slats, it may be advantageous to choose these bores slightly smaller than the external diameters of the screws, so that a certain interference is already present between these two components. The screws may also be formed as self-tapping screws, in which case they themselves form the thread inside the threaded nipple. Such a screw connection is in general, by its very nature also an interference fit, so that sufficient reliability against unintentional loosening of the fixing screws is provided, and moreover the advantage of a simpler form of construction of the threaded nipples results. Alternatively, the thread of the nipples may also be furnished with a bruising in the manner of a stop nut, or it can itself be formed as self-tapping, in which case the fixing screws can then be accordingly more simply constructed. Any other conventional measures for securing a screw connector are also possible.
The invention possesses other objects and features of advantage, some of which of the foregoing will be set forth in the following description of the preferred form of the invention which is illustrated in the drawings accompanying and forming part of this specification. It is to be understood, however, that variations in the showing made by the said drawings and description may be adopted within the scope of the invention as set forth in the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a perspective view of a portion of a slat conveyor belt from below.
FIG. 2 shows a cross-section through the means of fixing of a slat to the carrying strap lying below it.
FIG. 3 shows a cross-section of a further embodiment of a fixing means before assembly.
FIG. 4 shows a cross-section of a third embodiment of such fixing means before assembly.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a portion of a typical slat conveyor belt 1, viewed obliquely from below. It comprises carrying straps 2 and 2' onto which slats 4 are laid close together and transversely to the conveying direction and are fixed to the straps. In general, two fixing points 5 and 5' are provided per carrying strap and slat.
The carrying strap 2 at the lateral edge of the conveyor belt 1 is furnished with teeth 6, each of which is fixed approximately at the center of a slat on the lower face of the strap, and with advantage using the same fixing means as are used at fixing points 5 for fixing the slats. The second carrying strap 2' shown in FIG. 1 represents a form of construction without teeth. The conveyor belt may, depending upon its type, comprise exclusively toothed straps of the type of carrying strap 2 or exclusively simple carrying straps 2' or may possess both types of strap.
In FIG. 2, a first embodiment of one of the fixing points 5' is shown. Here, the slat 4 is constructed as a continuously extruded plastic section, which possesses in its center a cavity 8, into which a wooden batten 10 is pushed, for example to enable teeth to be attached to the slat 4 for the production of a toothed belt.
For each fixing point, a bore 12 is formed in the center of the slat 4, changing at its lower end into a widened-out portion 14. In this widened-out portion 14, a threaded nipple 16 is seated, which is furnished with a central bore and, in the example of FIG. 2, is riveted to the carrying strap 2'. For this purpose, the lower shank 17 of the threaded nipple 16 is formed as a tubular rivet and, after it has been pushed from above through an opening 19 in the carrying strap 2', is expanded to overlie the lower face of the carrying strap. If the carrying strap is additionally to be equipped with teeth 6, in other words the fixing points are to be those indicated at 5 in FIG. 1, then the lower shank 17 of the threaded nipple 16 is made correspondingly longer so that the teeth 6 can also be secured to the carrying strap 2 by the same riveted connection. The principle of this possibility is shown for another example of embodiment of the invention in FIG. 4.
The central bore of the threaded nipple 16 is furnished with a thread 20, which serves for seating a fixing screw 22. This screw extends from the upper side of the slat 4 through the bore 12 and into the threaded nipple 16 and is operated only from the upper side of the slat 4, without it being necessary to hold up the threaded nipple 16 or carry out any other operation at the lower side of the carrying strap 2'. To prevent an unintentional loosening of the screw 22, the diameter of the bore 12 may be kept slightly smaller than the external diameter of the screw, or other usual securing measures for screw connections can be used.
The riveted connection shown in FIG. 2 between the threaded nipple 16 and the carrying strap 2' can itself be formed to be absolutely non-rotating. In order that this riveted connection need not be unnecessarily complicated, and in addition to ensure that the threaded nipple 16 always remains non-rotating in a manner sufficient for the operating of the fixing screw 22, even under difficult conditions such as can occur, for instance, after long use of the conveyor belt, the threaded nipple 16 is additionally anchored as a close fit in the widened-out portion 14 of the bore 12. For this purpose, the outer surface of the threaded nipple 16 is furnished with longitudinal ribs 18, the diameter of which is chosen so that its tips penetrate into the inner surface of the widened-out portion 14, when the slat 4 is pressed with sufficient force onto the carrying strap 2'. In this manner, rotation of the threaded nipple 16 is prevented with sufficient reliability.
In the embodiment shown in FIG. 3, two adjacent threaded nipples 16' (only the front one is visible in this view) together with the tooth 6 provided below the carrying strap 2 comprise a single component. As shown the threaded nipples 16' are substantially cylindrical and possess, at their periphery, radially outward projecting ribs 24, which have a triangular shape and extend their maximum radial extent directly above the carrying strap 2. The dimensions of these ribs 24 are so chosen that the largest diameter formed by them is greater than the opening 19 in the carrying strap 2 and their common smallest diameter is just as large as this opening. Between the lower edges of the ribs 24 and the tooth 6 below them, a groove 26 is provided, the width of which is equal to the thickness of the carrying strap 2.
In order to fix the component consisting of the threaded nipples 16' and the tooth 6 to the carrying strap 2, the threaded nipples are pushed from below against the resistance provided by the diverging ribs 24 into the corresponding openings 19 of the carrying strap 2, until the edges of the openings 19 engage in the groove 26. The threaded nipples 16' can then be removed only by using exceptional force, which will never be reached in normal operation, in particular even when changing a slat 4.
In the embodiment of FIG. 3, no additional means to prevention of rotation of the threaded nipples 16' is required, since they remain non-rotating due to their paired connection by means of the tooth 6 to the carrying strap 2. Instead of the common tooth 6, however, each threaded nipple 16' can also be formed as a single nipple and furnished with its own flange, in which case the threaded nipples 16' are pushed individually either with or without simultaneous fixing of a tooth 6 into the corresponding openings 19 of the carrying strap 2. In such a case, a modification not shown in the drawing for securing the nipple against rotation is in general necessary. For this purpose, with great advantage, the ribs 24 can be used by making the lower widened-out portion 14 of the bore 12 of the slat 4 of such a size that the ribs 24, when the slat 4 is pressed on, can become connected in a form-fitting manner or as a frictional fit with the inner surface of the widened-out portion 14.
In the threaded nipple 16' a fixing screw (not shown in FIG. 3) is seated in the same manner as already explained with reference to FIG. 2. The use of self-tapping fixing screws has the advantage that the component consisting of the threaded nipples 16 and the tooth 6 can be produced as a plastic injection moulding, which requires no further finishing in respect of the seating for the fixing screws, since a central blind hole can be provided in the injection operation itself.
FIG. 4 shows a threaded nipple 16", the lower shank of which is formed, similarly to the example of FIG. 2, as a tubular rivet. In the present case the threaded nipple 16" is in addition used for fixing a tooth 6 to the carrying strap 2. In addition, the threaded nipple 16" shown in FIG. 4 no longer has a cylindrical shape with an external longitudinal grooving 18, but it is shaped so as to display the external form of a truncated cone. The widened-out portion 14" co-operating with the threaded nipple 16", at the lower end of the bore 12 in the slat 4, accordingly possesses a similar conical internal surface, and the dimensions are so selected that, just before the slat 4 comes to rest upon the carrying strap 2, a clamping effect occurs between the external cone of the threaded nipple 16" and the internal cone of the widened-out portion 14". As far as concerns the seating of the fixing screw 22, the description given with respect to the embodiments of FIGS. 2 and 3 also applies for FIG. 4.
As an alternative to the riveting or locking engagement, the threaded nipples can also be screwed to the carrying strap. Their lower shank is then furnished with an external thread for seating a threaded nut, or a short, wide-head holding screw is inserted from below into the internal thread of the central bore of the threaded nipple. A further possible method of fixing consists of glueing the threaded nipples to the carrying strap. For example, the retaining flange 21 or 21" which appears at the lower shank of the threaded nipple after a riveting operation, alternatively may be formed as a separate component which is secured by glueing after insertion of the threaded nipples into the carrying strap. Finally, the threaded nipples, if they are constructed as plastic injection mouldings, can also be injected directly onto the carrying strap by a procedure which can most simply be carried out by using the so-called through injection process. The carrying strap is previously furnished with the openings 19 and then placed in a two-part injection mould which then forms the threaded nipples and possibly also one tooth. Where the threaded nipples are thus injected onto the strap, they may be shaped in the manner shown, for example in FIGS. 2 and 4.
The fixing screws 22, which are pushed from above through the bores 12 in the slats 4 may also, if required, be utilized for holding further components onto the upper side of the slats. Such further components are, for instance, skid strips 24 (FIG. 4) which are frequently fitted to the lateral ends of the slats 4, to protect these against abrasion against lateral guide components of the slat conveyor. The skid strips 25 may then with advantage be formed the same as the teeth 6, i.e. a single component is used for the teeth 6 and for the skid strips 25.
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For slat conveyors in which transverse slats are supported on closed loop carrying straps which circulate in the conveying direction, there is the need to removably secure the slats to the conveying straps. Fixing means which allow the slat to be removable, such as nut and bolt pairs hitherto have been impractical due to the inaccessibility in the use of the lower one of the pair, i.e. from below the conveying strap (once it is installed in the conveyor). By now forming the nut as a threaded nipple embedded in the conveying strap the need for access to the nut is obviated. The nipple receives a fixing screw passed through the slat. The nipple is arranged to be rotationally locked relative to the strap, optionally by ribs. A pair of nipples and a tooth for engagement with a tooth-engaging-roller, may be formed integrally by injection moulding techniques and self-tapping screws may be employed.
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RELATED APPLICATION DATA
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/436,463, filed Jan. 26, 2011, which is incorporated herein in its entirety by reference.
FIELD OF THE INVENTION
[0002] This invention relates generally to positioning devices for positioning, holding and stabilizing dental x-ray film or digital sensors during implant surgery. More particularly the invention relates to an improved dental positioning and stabilizing device that does not require a patient to bite down or manually hold it in position in order to take an x-ray.
BACKGROUND OF THE INVENTION
[0003] Dentists typically use intra-oral radiographs (“x-rays”) to obtain images of their patients' teeth to aid in diagnosis and treatment. In traditional oral and dental radiography, an electronic sensor is placed in the patient's mouth behind the tooth to be examined. The electronic sensor or film is secured to a positioning device or is contained within a cartridge, typically cardboard or plastic. The sensor is placed behind the tooth while the holder extends through the bite area and the patient bites down on the holder to hold the sensor in place. The x-rays pass through the tooth and imprint on the sensor, which converts the x-rays into an electrical signal. The electrical signal is transmitted over a wire connected to a computer, either directly or though a module containing intermediate processing circuitry. The computer then processes the signal to produce an image on an associated output device, such as a monitor or a printer. Similarly, x-ray film can be exposed and developed to offer the same or similar view of the desired area
[0004] Numerous sensor holders have been marketed but in most conventional cases the patient must either bite down or use a finger to hold the sensor in place while the dentist or staff takes the x-ray.
[0005] Intra-oral x-rays are also required in dental implant surgery. Dental implant surgery is a procedure that replaces damaged or missing teeth with artificial teeth that look and function like real teeth. Dental implants are surgically placed in the jawbone, where they serve as the roots of missing teeth. To place the implant, the surgeon uses a dental drill including a driver and bit to drill through the patients' tissue and bone. The titanium implant includes a threaded outer portion that is screwed into the bone by the driver. An abutment portion is coupled to the titanium implant and extends out of the patient's gum and into the oral cavity. A cosmetic tooth is then attached to the abutment portion. Dental implants are often placed close to adjacent teeth and drilling into the roots of adjacent teeth while placing implants can cause irreparable harm. Consequently, it is critical for the implant to be placed as substantially parallel as possible to the roots of the adjacent teeth. It would be ideal for the dentist to take an x-ray prior to removing the drill and drill bit from the patient's jaw/bone so that she could ascertain correct and substantially parallel placement of the drilled hole. However, this task is complicated by several factors. First, the drill bit being x-rayed is high above the occlusal plane. Therefore, if a bite block sensor holder were used and a patient had to bite down in an attempt to stabilize the sensor/film holder, the drill bit would interfere with the biting action thus preventing stabilization. Second, if the patient is sedated, they are unable to follow commands to bite down or hold the sensor with their finger. Finally, asking the patient to hold the sensor/film holder may introduce bacteria into the surgical field, resulting in possible contamination of the implant and associated bone graft products.
[0006] Thus, there is a need for an x-ray positioning device that departs from the conventional methodology of having a patient bite down on or hold the sensor/film cartridge or holder in place (referred to herein as “patient interference”). There is also a need for an x-ray positioning device that improves patient comfort.
BRIEF SUMMARY OF THE INVENTION
[0007] Accordingly, this invention provides a sensor positioning and stabilizing device which overcomes the above-mentioned problems. More specifically, the invention provides a sensor/film positioning and stabilizing device wherein the device is operably coupled to the drill bit or implant driver shank after the dentist drills through the patient's jaw bone.
[0008] The invention also provides a sensor positioning and stabilizing device which does not require a patient to exert any force on the device to hold it in place.
[0009] The invention also provides a sensor positioning and stabilizing device that eliminates the need for a bite holder.
[0010] The invention also provides a sensor positioning and stabilizing device that allows for easy removal of the sensor.
[0011] The invention also provides a sensor positioning and stabilizing device that may be used with sensors of any width, length or size.
[0012] The invention includes a finger positioning tab that provides the surgeon with greater freedom in orienting the sensor.
[0013] Still further, the invention is relatively thin, which also contributes to the improved ergonomics of the sensor positioning and stabilizing device, and enables the sensor to get closer to the target area, thereby improving the image data transmitted by the sensor to the computer.
[0014] Still further, the positioning and stabilizing system includes an elongate receiving channel having a longitudinal axis, said elongate receiving channel configured to slidably receive a drill bit or a shank of an implant driver; and a dental sensor operably coupled to said elongate receiving channel such that said dental sensor is substantially parallel to the longitudinal axis of said elongate receiving channel.
[0015] Moreover, the invention includes a dental sensor operably coupled to a positioning and stabilizing system comprising an elongate receiving channel for receiving an implant drill bit or shank of an implant driver wherein the dental sensor is substantially parallel to said elongate receiving channel.
[0016] Further features of the present invention will become apparent from the following detailed description taken with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] For a better understanding of the invention, and to show how the same may be carried into effect, reference will now be made, by way of example, to the accompanying drawings, in which:
[0018] FIG. 1A shows a drill bit extending from the gums of a patient into the oral cavity.
[0019] FIG. 1B is an x-ray of the misaligned drill bit of FIG. 1A .
[0020] FIG. 2 is a perspective view of the dental sensor positioning and stabilizing device in accordance with the invention.
[0021] FIG. 3 is a perspective view of an alternative embodiment of the dental sensor positioning and stabilizing device in accordance with the invention.
[0022] FIG. 4 is a side view of the dental sensor positioning and stabilizing device in accordance with the invention.
[0023] FIG. 5 is a top view of the dental sensor positioning and stabilizing device in accordance with the invention.
[0024] FIG. 6A is a top view of the dental sensor positioning and stabilizing device in accordance with the invention attached to an implant driver with the sensor placed behind the dental arch.
[0025] FIG. 6B is a side view of the dental sensor positioning and stabilizing device in accordance with the invention with the device attached to a drill bit with the sensor place behind the dental arch.
[0026] FIG. 7 is an x-ray of an implant that is correctly aligned in relation to adjacent teeth.
DETAILED DESCRIPTION OF THE INVENTION
[0027] As described above, the invention comprises a dental sensor positioning and stabilizing device for positioning, stabilizing and aligning dental x-ray sensors. The positioning device does not require a bite holder, block or other mechanism or any patient interference such as the patient biting down on the device or holding the device in place. As used herein, we refer to a “sensor” as encompassing both sensors and film.
[0028] FIG. 1A shows the oral cavity of a sedated patient after the hole for the implant has been drilled. The shank portion of the drill bit can be seen extending into the oral cavity out from the gums by 1 to 2 centimeters and ostensibly appears parallel with adjacent teeth. As can be seen in FIG. 1B , however, the drill bit is not parallel with the roots of adjacent teeth. FIG. 1B is an x-ray of a misaligned drill bit during implant surgery and highlights the problem that the present invention is designed to solve. In this case, if the drill bit was removed and an implant permanently placed the adjacent tooth root would be damaged irreparably resulting in possible tooth loss. In addition, if the implant is placed to close to an adjacent tooth at the most coronal aspect (near the crown) excessive bone loss can occur resulting in a poor aesthetic outcome.
[0029] Referring now to FIGS. 2 through 5 an exemplary dental positioning and stabilizing device in accordance with an embodiment of the present invention is shown. Positioning and stabilizing device 10 includes integrally formed elongate arms 14 , 16 , body 18 having first 30 and second 32 sides thereof and finger tab portion 20 . Body 18 comprises an elongate receiving channel 19 having a longitudinal axis and includes aperture 21 . Aperture 21 is sized to receive the shank portion of the drill bit (as best seen in FIG. 1A ) that extends from the patient's gums and into the oral cavity after the implant hole has been drilled. Aperture 21 forms elongate receiving channel 19 . In an embodiment of the invention aperture 21 is sized such that the inner diameter is from approximately 2.45 mm to about 2.25 mm. Elongate receiving channel 19 is designed to slidably accommodate the shank portion of a dental drill bit or implant driver shank; however, elongate receiving channel is also designed to frictionally engage the shank portion of a dental drill bit or implant driver such that after the dental positioning and stabilizing device is in position on the drill bit, the device is securedly fixed on the drill bit.
[0030] Arms 14 , 16 each include resilient flanges 22 , 24 , respectively. Flanges 22 , 24 act to operably and resiliently connect elongate arms to cylindrical-shaped body 18 . Those of skill in the art will appreciate that while body 18 is depicted as being circular or cylindrical-shaped many other shapes are contemplated and fall within the scope of the invention. Elongate arms 14 , 16 are C-shaped in cross section and include sensor channels 26 which form clamps that are designed to grip the sensor and stabilize it in position. When stabilized in position, the sensor is substantially parallel to the longitudinal axis of elongate receiving channel 19 . By substantially parallel we mean that the sensor can be moved from being precisely parallel to the longitudinal axis of the elongate receiving channel to an acute angle off from the longitudinal axis of the elongate receiving channel 19 . In other words, the sensor can be positioned at an acute angle from the longitudinal axis of the elongate receiving channel, the acute angle being from 0.1 degrees to about 45 degrees.
[0031] Positioning device is formed from a resilient or flexible material such as polypropylene or the like such that flanges 22 , 24 resiliently and easily pivot elongate arms 14 , 16 from an initial position (shown) to a second open position. While in the second position, sensor channels 26 accommodate the dental sensor and then resiliently return to the initial position in which channels 26 snuggly surround the sensor so that it is stabilized within channels 26 . Arms 14 , 16 are integrally formed with flanges 22 , 24 . Flanges 22 , 24 are integrally fanned with and extend laterally from first side 30 of elongate channel 18 . Resilient flanges 22 , 24 accommodate the resilient and flexible movement of arms 14 , 16 from the initial position to a second position, as noted above. Those of skill in the art will appreciate that numerous embodiments that are within the scope of the invention are possible. For example, flanges 22 and 24 need not be integrally formed with body 18 but rather may be operably connected by adhesive, connecting tabs and other such means without departing from the scope of the invention. Similarly, one flange may extend laterally from a central body. Such one flange may include two resilient arms having channels which receive the sensor or film. Further, those of skill in the art will appreciate that any system designed to hold a dental sensor substantially parallel to the longitudinal axis of the elongate receiving channel and which does not require patient interference is within the scope of the invention.
[0032] Finger tab portion 20 is operably connected to and integrally formed with the second side 32 of body 18 . Those of skill in the art will appreciate that finger tab portion need not be integrally formed with circumferential body 18 but rather may be operably connected by adhesive, connecting tabs and other such means without departing from the scope of the invention. Finger tab portion 20 extends generally radially outward and slightly downward from said circumferential body 19 . Finger tab portion and includes upper 36 and lower 38 elements and tab portion 44 . Upper element 36 includes a first generally straight portion 34 that extends radially outward from second side 32 of circumferential body 18 . Lower element 38 includes curvilinear portion 40 and extends radially outward and downward from second side 32 of circumferential body 18 . Tab portion 44 extends laterally from upper and lower elements 36 , 38 . Upper and lower elements 36 , 38 and tab portion 44 are ergonomically designed so that the surgeon can easily grasp and precisely position the sensor positioning and stabilizing device 10 behind the teeth and an x-ray of the drill bit in the drilled hole can be taken (as best seen in FIG. 1B ).
[0033] FIG. 3 depicts an embodiment of a sensor positioning and stabilizing device 300 in accordance with the invention in which the elongate receiving channel 319 is substantially longer in length than the embodiment depicted in FIG. 2 and finger tab portion 320 extends radially outward and is substantially perpendicular to elongate arms 314 . 316 . Those of skill in the art will appreciate however that elongate receiving channel 319 may be of any length to accommodate varying drill bit lengths and patient dental profiles. Positioning device 310 includes integrally formed elongate arms 314 , 316 , body 318 having first 330 and second 332 sides thereof and finger tab portion 320 . Body 318 comprises an elongate receiving channel 319 with aperture 321 . Aperture 319 is sized to receive a drill bit or shank portion of an implant driver (as best seen in FIG. 1A ) that extends from the patient's gums and into the oral cavity after the implant hole has been drilled. Elongate receiving channel 319 is designed to slidably accommodate the shank portion of a dental drill bit.
[0034] Arms 314 , 316 each include resilient flanges 322 , 324 , respectively. Flanges 322 , 324 act to operably and resiliently connect elongate arms to circumferential body 318 . Elongate arms 314 , 316 are C-shaped in cross section and include sensor channels 326 which form clamps that are designed to grip the sensor and stabilize it in position. Positioning device is formed from a resilient or flexible material such as polypropylene or the like such that flanges 322 , 324 resiliently and easily pivot elongate arms 314 , 316 from an initial position (shown) to a second open position. While the arms are in the open position, sensor channels 326 accommodate the dental sensor or film and then resiliently return to the initial position in which channels 326 snuggly surround the sensor so that it is stabilized within channels 26 . Arms 314 , 316 may be integrally formed with flanges 322 , 324 . Flanges 322 , 324 in turn are integrally formed with and extend laterally from first side 330 of elongate channel 318 . Resilient flanges 322 , 324 accommodate the resilient and flexible movement of arms 314 , 316 from the initial position to a second position, as noted above. Those of skill in the art will appreciate that numerous embodiments that are within the scope of the invention are possible. For example, flanges 322 and 324 need not be integrally formed with body 318 but rather may be operably connected by adhesive, connecting tabs and other such means without departing from the scope of the invention. Similarly as described above, one flange may extend laterally from a central body. Such one flange may include two resilient arms having channels which receive the sensor or film.
[0035] As depicted in FIG. 3 , finger tab portion 320 is operably connected to and integrally formed with the second side of body 318 . Finger tab portion 320 extends radially outward from circumferential body 318 . Finger tab portion includes tab portion 344 . Tab portion 344 extends laterally from straight portion 334 and is designed so that the surgeon can easily grasp and precisely position the sensor positioning and stabilizing device 310 behind the teeth and an x-ray of the drill bit in the drilled hole can be taken (as best seen in FIG. 1B ).
[0036] FIG. 4 is a side view of the dental sensor positioning and stabilizing device 10 in accordance with the invention with detail regarding finger tab portion 20 . Finger tab portion 20 includes tab body 40 . Finger tab portion 20 extends generally radially outward and slightly downward from said circumferential body 19 . Finger tab portion and includes upper 36 and lower 38 elements and tab portion 44 . Upper element 36 includes a first generally straight portion 34 that extends radially outward from second side 32 of circumferential body 18 . Lower element 38 includes curvilinear portion 40 and extends radially outward and downward from second side 32 of circumferential body 18 . Tab portion 44 extends laterally from upper and lower elements 36 , 38 . Upper and lower elements 36 , 38 and tab portion 44 are ergonomically designed so that the surgeon can easily grasp and precisely position the sensor positioning and stabilizing device 10 behind the teeth and an x-ray of the drill bit in the drilled hole can be taken (as best seen in FIG. 1B ). Finger tab portion 20 and thus dental sensor position and stabilizing device 10 may be oriented upwards or downwards depending on where the implant will be located, i.e. upper or lower gum line. Optional raised ridge 46 surrounds tab portion 44 and is designed to allow the surgeon to securedly grip finger tab portion 20 .
[0037] FIG. 5 depicts a top view of the sensor positioning and stabilizing device 10 in accordance with the invention showing detail regarding aperture flanges 22 , 24 and C-shaped in cross section sensor channels 26 .
[0038] FIG. 6A is a top view of the dental sensor positioning and stabilizing device 10 in use in accordance with one aspect of the invention. As can be seen, the positioning and stabilizing device 10 has been slidably received by an implant drill bit 60 through aperture 21 and into elongate receiving channel 19 . Sensor 62 is received within and held by sensor channels 26 thus allowing it to be easily positioned behind the dental arch 64 above the occlusal plane 66 .
[0039] FIG. 6B is a side view of the dental sensor positioning and stabilizing device 10 in accordance the invention in operation. The dental surgeon first drills a hole through the patient's mucosa 70 and bone 68 as close as possible to a parallel position next to adjacent teeth. As can be seen, the positioning and stabilizing device 10 is then slidably received by the implant drill bit 60 as also seen in FIG. 6A . Sensor 62 is positioned within sensor channels 26 and is moveably positioned from left to right by the finger tab portion 20 behind the dental arch 64 above the occlusal plane 66 into the correct position for taking an x-ray of the drill bit. With the drill bit in position, the dental surgeon next takes an x-ray and views it on a computer screen. If the drill bit is positioned parallel to adjacent tooth structure, the dental sensor positioning device is removed from the drill bit 60 and a second, larger drill bit is used to enlarge the pre-existing hole. The process of taking an x-ray may be repeated as many times as the surgeon desires to ensure that the hole into which the dental implant will be secured is parallel to adjacent tooth structure. If the x-ray shows that the initial drilling of the drill bit is not parallel then the sensor positioning device is removed and a second, larger drill bit is used to drill through the pre-existing hole to correct the path of the hole. The sensor positioning device is then place on the drill bit (with the drill removed) and another x-ray is taken to verify position. The dental surgeon may repeat the process as many times as desired to verify that the drill bit is correctly positioned and substantially parallel to the adjacent teeth. The drill bit is then removed and replaced with implant 72 as best seen in FIG. 7 .
[0040] FIG. 7 depicts an x-ray taken with the sensor positioning and stabilizing device 10 in accordance with the invention. As can be seen and compared to the angled drill bit depicted in FIG. 1B the implant 72 can be seen to be correctly positioned and substantially parallel to the adjacent teeth.
[0041] Advantageously, the sensor positioning and stabilizing device in accordance with the invention is supported by a drill bit thus eliminating the need to have a patient bite down on, manually hold the sensor/film cartridge or holder in place, or otherwise stabilize the device. The sensor positioning and stabilizing device in accordance requires no patient interference.
[0042] While the invention has been particularly shown and describe with respect to exemplary embodiments thereof, those of ordinary skill in the art will appreciate and understand that changes in form and details may be made without departing from the scope and spirit of the invention.
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A sensor positioning and stabilizing device is provided. The sensor positioning and stabilizing device holds and stabilizes dental x-ray film or digital sensors during implant surgery with requiring a patient to bite down or manually hold it in position in order to take an x-ray.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a backlight module and a liquid crystal display (LCD) employing such a backlight module, and more particularly, to a backlight module for alternately driving lighting device and an LCD employing such a backlight module.
[0003] 2. Description of Prior Art
[0004] With a rapid development of monitor types, novel and colorful monitors with high resolution, e.g., liquid crystal displays (LCDs), are indispensable components used in various electronic products such as monitors for notebook computers, personal digital assistants (PDAs), digital cameras, and projectors. The demand for the novelty and colorful monitors has increased tremendously.
[0005] A backlight module is a key component of a liquid crystal display (LCD). The purpose of the backlight module is to provide a sufficient-brightness and an even-distribution light surface to the LCD panel. Because the LCD is widely used in various electronic products such as a monitor, a notebook computer, a digital camera, and a projector, the demand for the backlight module has increased tremendously.
[0006] In addition to cold cathode fluorescent lamps (CCFLs), backlight modules also utilize light emitting diodes (LEDs) as a light source. And in recent years, LEDs have gradually become the mainstream backlight light source for LCD televisions, because they are mercury-free and thus environmentally friendly and fast responding. However, some physical properties of LEDs also influence luminous efficiency and lifespan of LEDs. Temperature is such a physical property that affects LEDs most. So, a variety of radiating materials and relevant techniques start to be applied to LED backlighting. The application of such heat dissipation techniques, undoubtedly, attempts to reduce the influence of temperature on LEDs effectively. Referring to FIG. 1 , FIG. 1 shows that LEDs are activated by a traditional converter. A backlight module 1 comprises a power end 12 , a plurality of LEDs 14 , and a converter 16 . The converter 16 comprises an inductor element L, a transistor T, a diode D, and a capacitor element C. The power end 12 supplies the converter 16 with a direct current (DC) supply voltage V DC , and the transistor T switches to output a driving signal to the LEDs 14 in response to a switch signal V G . The LEDs 14 produce light based on the voltage difference of the driving signal. However, the traditional LED backlight module 1 merely utilizes a single converter 16 to simultaneously activate all of the LEDs 14 , which means that the converter 16 has to produce large current outputs to simultaneously activate all of the LEDs 14 . But, large currents may also cause some potential problems, such as excess temperature, which not only shortens the lifespan of the LEDs 14 but also reduce the luminous efficiency of the LEDs 14 .
SUMMARY OF THE INVENTION
[0007] It is therefore an object of the present invention to provide a backlight module and an LCD employing such a module by means of an alternate driving lighting device to reduce thermal power generation.
[0008] In another aspect of the present invention, a liquid crystal display comprises a power end for generating a supply voltage, a liquid crystal display panel comprising a liquid crystal layer for displaying images, a switch signal generator for generating a first switch signal and a second switch signal, a first inverter electrically connected to the power end for generating a first driving signal based on the first switch signal, a second inverter electrically connected to the power end for generating a second driving signal based on the second switch signal, a first lighting device for producing light based on the voltage difference of the first driving signal transmitted from the first inverter, a second lighting device for producing light based on the voltage difference of the second driving signal transmitted from the second inverter. The phase difference between the first driving signal and the second driving signal is 180 degrees.
[0009] In another aspect of the present invention, a backlight module comprises a power end for generating a supply voltage, a switch signal generator for generating a first switch signal and a second switch signal, a first inverter electrically connected to the power end for generating a first driving signal based on the first switch signal, a second inverter electrically connected to the power end for generating a second driving signal based on the second switch signal, a first lighting device for producing light based on the voltage difference of the first driving signal transmitted from the first inverter, and a second lighting device for producing light based on the voltage difference of the second driving signal transmitted from the second inverter. A phase difference between the first driving signal and the second driving signal is 180 degrees.
[0010] According to the present invention, the first lighting device or the second lighting device comprises a light emitting diode (LED) or a plurality of LEDs connected in serial.
[0011] According to the present invention, the first inverter comprises a capacitor element connected in parallel to the first lighting device, an inductor element comprising a first end electrically connected to a first electrode of the power end, a diode electrically connected between a second end of the inductor element and the first lighting device, and a first transistor comprising a first end electrically connected between the inductor element and the diode and a second end electrically connected to a second electrode of the power end for conducting upon receiving the first switch signal.
[0012] According to the present invention, the second inverter comprises a capacitor element connected in parallel to the second lighting device, an inductor element comprising a first end electrically connected to a first electrode of the power end, a diode electrically connected between a second end of the inductor element and the second lighting device, a second transistor comprising a first end electrically connected between the inductor element and the diode and a second end electrically connected to a second electrode of the power end for conducting upon receiving the second switch signal.
[0013] According to the present invention, a phase inverter for inverting a switch signal generated by the switch signal generator to generate another switch signal, the two switch signals act as the first switch signal and the second switch signal.
[0014] According to the present invention, the first transistor is a PMOS transistor and the second transistor is a NMOS transistor.
[0015] Compared with the prior art, the backlight module with the related LCD in the present invention activates LEDs by using an alternate control method. If a duty cycle is set at 50 percent during a switching cycle period, the LEDs in the same string will be in a closed state in a duty cycle of 50 percent. And, all of the switching frequencies are above 1 kHz, so human eyes cannot detect variations in brightness of the LEDs. Besides, excess temperature produced by the LEDs when lightened simultaneously and thermal power generated during the lighting of the LEDs can be effectively reduced for the reason that the LEDs are in a closed condition in half or even more of the time during the switching cycle period.
[0016] These and other objects of the claimed invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment that is illustrated in the various figures and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 shows that LEDs are activated by a traditional converter.
[0018] FIG. 2 is a schematic diagram of a liquid crystal display according to a first embodiment of the present invention.
[0019] FIG. 3 is a schematic diagram of an LCD according to the second embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] Referring to FIG. 2 , FIG. 2 is a schematic diagram of a liquid crystal display (LCD) 20 according to a first embodiment of the present invention. The LCD 20 comprises a power end 21 , an LCD panel 30 , and a backlight module 10 . The backlight module 10 produces light that the LCD panel 30 requires with a voltage provided by the power end 21 . The backlight module 10 comprises a first lighting device 22 , a second lighting device 24 , a switch signal generator 25 , a first inverter 26 , and a second inverter 28 . The power end 21 provides a DC supply voltage V DC . The LCD panel 30 comprises a liquid crystal (LC) layer for displaying images. The first lighting device 22 and the second lighting device 24 comprise a single LED 32 or a plurality of LEDs 32 in serial. The first lighting device 22 comprises one end electrically connected to the first inverter 26 and the other end electrically connected to a voltage end (a ground end in FIG. 2 ) for producing light based on the voltage difference of a first driving signal emitted by the first inverter 26 . The second lighting device 24 comprises one end electrically connected to the second inverter 28 and the other end electrically connected to the voltage end (the ground end in FIG. 2 ) for producing light based on the voltage difference of a second driving signal emitted by the second inverter 28 . The switch signal generator 25 generates a switch signal V G1 .
[0021] Please continue referring to FIG. 2 . The first inverter 26 and the second inverter 28 convert a DC voltage (12V) of the power end 21 into an alternating current (AC) high voltage. The first inverter 26 comprises a capacitor element 40 , an inductor element 42 , a diode 44 , and a first transistor 46 . The capacitor element 40 and the first lighting device 22 are connected in parallel. The inductor element 42 comprises a first end electrically connected to a first electrode of the power end 21 . The diode 44 is electrically connected between a second end of the inductor element 42 and the first lighting device 22 . The inductor element 42 is an charge storage element for reserving a DC supply voltage from the power end 21 . The first transistor 46 comprises a first end electrically connected to the inductor element 42 and to the diode 44 and a second end electrically connected to a second electrode of the power end 21 . In the present embodiment, the first transistor 46 is an N-type metal-oxide-semiconductor (MOS) transistor, having a gate connected to a first switch signal V G1 output by a square wave. When the first switch signal V G1 is at a high voltage level, the first transistor 46 conducts to make the first transistor 46 , the first lighting device 22 , and the diode 44 form a current loop. Meanwhile, the first lighting device 22 receives a first driving signal (i.e., a voltage level of an output end of the diode 44 ). The first lighting device 22 emits light because of the voltage difference of the first driving signal. When the first switch signal V G1 is at a low voltage level, the first transistor 46 is turned off. Meanwhile, the voltage level of the output end of the diode 44 is lowered to be identical to that of the ground end. So, the first driving signal is not transmitted to the first lighting device 22 at this time, causing that the first lighting device 22 cannot produce light due to no voltage difference of the first driving signal.
[0022] Similarly, the second inverter 28 comprises a capacitor element 50 , an inductor element 52 , a diode 54 , and a second transistor 56 . The capacitor element 50 and the second lighting device 24 are connected in parallel. The inductor element 52 comprises a first end electrically connected to the power end 21 . The diode 54 is electrically connected between a second end of the inductor element 52 and the second lighting device 24 . The inductor element 52 is an energy storage element for reserving a DC supply voltage from the power end 21 . The second transistor 56 comprises a first end electrically connected to the inductor element 52 and to the diode 54 and a second end electrically connected to a second electrode of the power end 21 . In the present embodiment, the second transistor 56 is an NMOS transistor, having a gate connected to a second switch signal V G2 output by a square wave. It is notified that, a phase inverter 58 inverts the first switch signal V G1 to form the second switch signal V G2 , so the phase difference between the first switch signal V G1 and the second switch signal V G2 is 180 degrees. Therefore, when the first switch signal V G1 is at a low voltage level, the second switch signal V G2 is at a high voltage level. When the second switch signal V G2 is at a high voltage level, the second transistor 56 conducts to make the second transistor 56 , the diode 54 , and the second lighting device 24 form a current loop. Meanwhile, the second lighting device 24 receives a second driving signal (i.e., a voltage level of an output end of the diode 54 ). The second lighting device 24 emits light because of the voltage difference of the second driving signal. When the second switch signal V G2 is at a low voltage level, the second transistor 56 is turned off. Meanwhile, the voltage level of the output end of the diode 54 is lowered to be identical to that of the ground end. So, the second driving signal is not transmitted to the second lighting device 24 at this time, causing that the second lighting device 24 cannot produce light due to no voltage difference of the second driving signal. The phase difference between the first switch signal V G1 and the second switch signal V G2 is 180 degrees, which causes that the phase difference between the first driving signal and the second driving signal is 180 degrees, too. In this way, the duration of lighting of the first lighting device 22 and that of the second lighting device 24 are alternate on account of the activations of the first and second driving signals; that is, either the first lighting device 22 or the second lighting device 24 is allowed to emit light at any point of time.
[0023] Referring to FIG. 3 , FIG. 3 is a schematic diagram of an LCD 60 according to the second embodiment of the present invention. The LCD 60 comprises a power end 21 , an LCD panel 30 , and a backlight module 70 . It is notified that, every element in FIG. 3 marked with the same code shown in FIG. 2 is given the same function. To simplify the description below, the functions of the same elements are not repeated in the following. Differing from the first embodiment in FIG. 2 , in this embodiment a second transistor 66 of the second inverter 28 is a p-type metal-oxide-semiconductor (PMOS) transistor; the gate of the second transistor 66 is also controlled by the first switch signal V G1 ; the phase inverter 58 is not needed. Opposite to the NMOS transistor, the PMOS transistor is turned on when the first switch signal V G1 is at a low voltage level and turned off when the first switch signal V G1 is at a high voltage level. In other words, even if both of the first transistor 46 and the second transistor 66 are controlled by the first switch signal V G1 at the same time, the second lighting device 24 will emit light upon receiving the second driving signal (i.e., the voltage level of the output end of the diode 54 ), and the first lighting device 22 will not receive the first driving signal and emit light (and vice versa). This is because the second transistor 66 (PMOS transistor) has opposite polarity of the threshold voltage from the first transistor 46 (NMOS transistor). In this way, the duration of lighting of the first lighting device 22 alternates with that of the second lighting device 24 owing to the activation of the first driving signal. In other words, either the first lighting device 22 or the second lighting device 24 is allowed to emit light at any point of time.
[0024] It is supposed that the one skilled in this art understand that, as long as the polarity of the turn-on voltage of the first transistor 46 is opposite to that of the second transistor 66 , an object of alternately lighting of the first lighting device 22 and the second lighting device 24 can be achieved by only using the same switch signal. It is not necessary to set the first transistor 46 and the second transistor 66 as an NMOS transistor or a PMOS transistor as the above-mentioned approach does.
[0025] Both of the first switch signal and the second switch signal have a 50% duty cycle in the above embodiments. Practically, the duty cycles of the first switch signal and the second switch signal can be adjusted to 60% to 40% or to other ratios depending on actual requirements. And, the duty cycles of the first driving signal and the second driving signal are modified with those of the first switch signal and the second switch signal, too.
[0026] Consequently, the backlight module with the LCD employing such a backlight module activates the first lighting device and the second lighting device by using an alternate method. So, if both of the first switch signal and the second switch signal have a 50% duty cycle during the same switching cycle period, the first lighting device and the second lighting device will be in a closed state in a duty cycle of 50 percent, which can effectively prevent temperature from being too high when the lighting devices are lightened simultaneously and can effectively reduce thermal power generation during the lighting of the lighting devices.
[0027] Although the present invention has been explained by the embodiments shown in the drawings described above, it should be understood to the ordinary skilled person in the art that the invention is not limited to the embodiments, but rather various changes or modifications thereof are possible without departing from the spirit of the invention. Accordingly, the scope of the invention shall be determined only by the appended claims and their equivalents.
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The present invention discloses a backlight module with a related liquid crystal display (LCD) which activates light emitting diodes (LEDs) by utilizing an alternate control method. The present invention utilizes two inverters to individually activate two sets of LEDs through an alternate method. During the same switching cycle period, the two sets of LEDs take turns turning on/off; that is, the two set of LEDs are in a closed state in a duty cycle of 50 percent. Since each set of the LEDs are in a closed condition in half the time during a switching cycle period, both of excess temperature produced by all of the LEDs when lightened simultaneously and thermal power generated during the lighting of the LEDs can be effectively reduced.
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TECHNICAL FIELD
[0001] The present invention is directed generally to a lighting unit having a plurality of substantially linearly arranged solid state light sources. More particularly, various inventive methods and apparatus disclosed herein relate to a lighting unit having a plurality of linearly arranged LEDs, a first and second reflector flanking the LEDs, and a lens provided over and spaced apart from the LEDs.
BACKGROUND
[0002] Digital lighting technologies, i.e. illumination based on semiconductor light sources, such as light-emitting diodes (LEDs), offer a viable alternative to traditional fluorescent, HID, and incandescent lamps. Functional advantages and benefits of LEDs include high energy conversion and optical efficiency, durability, lower operating costs, and many others. Recent advances in LED technology have provided efficient and robust full-spectrum lighting sources that enable a variety of lighting effects in many applications.
[0003] Many lighting fixtures have been designed that implement LEDs to reap one or more of the advantages and benefits of LEDs. For example, some lighting fixtures have been designed that implement a plurality of LEDs, with each individual LED having an associated LED optic thereover. For example, each individual LED may have an individual reflector that surrounds the LED and reflects light output from the LED into a desired beam distribution and an associated individual lens coupled to the reflector that refracts light output from the LED in a desired direction. The LEDs may be appropriately positioned and each LED optic may be appropriately paired with a desired of the LEDs in order to obtain a desired light output from the lighting fixture. While such lighting fixtures generally enable a desired light output to be obtained, they may cause individual imaging of each optic on the target illumination area, thereby causing a non-uniform illumination pattern. Likewise, such lighting fixtures may employ fixed, unremovable LED optics, thereby preventing the lighting fixtures from being easily adapted to provide a selected of a plurality of distinct optical outputs.
[0004] Thus, there is a need in the art for a lighting unit having a plurality of solid state light sources (e.g., LEDs), which has reduced imaging of individual LED optics on the target illumination area and which can provide a plurality of distinct optical outputs.
SUMMARY
[0005] The present disclosure is directed to inventive methods and apparatus for a lighting unit having a plurality of substantially linearly arranged solid state light sources such as, for example, LEDs. More particularly, various inventive methods and apparatus disclosed herein relate to a lighting unit having a plurality of linearly arranged LEDs, a first and second reflector flanking the LEDs, and a lens provided over and spaced apart from the LEDs. Optionally, the lens may be removably coupled over the LEDs, thereby allowing for interchanging with a lens having alternative optical characteristics. For example, a lens that has optical characteristics that provide for a spot target narrow distribution may be interchanged with a lens that provides for a distinct linear spot target distribution. The lens may be formed from a single longitudinally extending piece or may include a plurality of lens pieces. For example, the lens may include a plurality of longitudinally extending lens pieces and/or a plurality of non-longitudinally extending lens pieces that collectively form a longitudinally extending lens. Each lens piece may be provided over a single or multiple of the LEDs. The lighting unit may optionally be designed to enable the orientation of the LEDs to be selectively adjustable by a user. The present disclosure may provide a LED lighting unit that may be manipulated by a user (e.g., by changing out the lens and/or adjusting the orientation of the LEDs) to provide a desired optical output from the LED light unit, thereby allowing for a variety of lighting configurations from the lighting unit.
[0006] Generally, in one aspect, a LED-based lighting unit is provided that includes a plurality of substantially linearly arranged LEDs, a longitudinally extending first reflector, and a longitudinally extending second reflector. The longitudinally extending first reflector is along a first side of the LEDs and has a first generally concave reflective surface extending outward and away from adjacent the LEDs. The longitudinally extending second reflector is along a second side of the LEDs and has a second generally concave reflective surface extending outward and away from adjacent the LEDs. The lens is provided over and spaced apart from a plurality of the LEDs and extends between the first reflector and the second reflector. The lens is removably coupled over the LEDs.
[0007] In some embodiments the lens has a substantially planar first side facing the LEDs and a non-planar second side opposite the first side. In some versions of those embodiments the first concave reflective surface and the second concave reflective surface have substantially similar concavities. In some versions of those embodiments the first concave reflective surface extends outward a first distance from the LEDs and the second concave reflective surface extends outward a second distance from the LEDs; the second distance being at least one and a half times the first distance. In some versions of those embodiments the first concave reflective surface extends away from the LEDs approximately the same distance as the second concave reflective surface.
[0008] In some embodiments the lens is removably coupled to the first reflector and the second reflector.
[0009] In some embodiments the lens is a singular longitudinally extending piece provided over each of the plurality of LEDs.
[0010] In some embodiments the lens includes a plurality of adjacent individual lens pieces. In some versions of those embodiments each of the individual lens pieces is provided over a single of the LEDs.
[0011] Generally, in another aspect a LED-based lighting unit includes a support surface, a plurality of LEDs, a longitudinally extending first reflector, a longitudinally extending second reflector, and a lens. The plurality of LEDs are coupled to the support surface in a substantially linear arrangement. The longitudinally extending first reflector is coupled to the support surface on a first side of the LEDs and has a first generally concave reflective surface extending outward and away from adjacent the LEDs. The longitudinally extending second reflector is along a second side of the LEDs and has a second generally concave reflective surface extending outward and away from adjacent the LEDs. The lens is provided over and spaced apart from each of the LEDs. The lens extends between the first reflector and the second reflector and has a substantially planar first side facing the LEDs and a non-planar second side opposite the first side.
[0012] In some embodiments the lens is removably coupled over the LEDs. In some versions of those embodiments the lens is removably coupled to the first reflector and the second reflector.
[0013] In some embodiments the lens includes at least one longitudinally extending lens piece provided over each of the plurality of LEDs. In some versions of those embodiments the lens includes two the longitudinally extending lens piece, each the lens piece provided over at least a portion of each of the plurality of LEDs.
[0014] In some embodiments the lens includes a plurality of lens pieces. In some versions of those embodiments each of the lens pieces is provided over a single of the LEDs.
[0015] In some embodiments the support surface is repositionable to a plurality of user selectable orientations.
[0016] Generally, in another aspect A LED-based lighting unit system includes a plurality of LEDs, a longitudinally extending first reflector, a longitudinally extending second reflector, and a plurality of lens having unique optical characteristics. The LEDs are substantially linearly arranged and the first reflector and the second reflector flank the LEDs. The first reflector has a first reflective surface extending outward and away from adjacent the LEDs. The second reflector has a second reflective surface extending outward and away from adjacent the LEDs. Each lens may be removably coupled over and spaced apart from a plurality of the LEDs and extend between the first reflector and the second reflector.
[0017] As used herein for purposes of the present disclosure, the term “LED” should be understood to include any electroluminescent diode or other type of carrier injection/junction-based system that is capable of generating radiation in response to an electric signal. Thus, the term LED includes, but is not limited to, various semiconductor-based structures that emit light in response to current, light emitting polymers, organic light emitting diodes (OLEDs), electroluminescent strips, and the like. In particular, the term LED refers to light emitting diodes of all types (including semi-conductor and organic light emitting diodes) that may be configured to generate radiation in one or more of the infrared spectrum, ultraviolet spectrum, and various portions of the visible spectrum (generally including radiation wavelengths from approximately 400 nanometers to approximately 700 nanometers). It should also be understood that the term LED does not limit the physical and/or electrical package type of an LED.
[0018] The term “light source” should be understood to refer to any one or more of a variety of radiation sources, including, but not limited to, LED-based sources (including one or more LEDs as defined above), incandescent sources (e.g., filament lamps, halogen lamps), fluorescent sources, phosphorescent sources, high-intensity discharge sources (e.g., sodium vapor, mercury vapor, and metal halide lamps), lasers, other types of electroluminescent sources, pyro-luminescent sources (e.g., flames), candle-luminescent sources (e.g., gas mantles, carbon arc radiation sources), photo-luminescent sources (e.g., gaseous discharge sources), cathode luminescent sources using electronic satiation, galvano-luminescent sources, crystallo-luminescent sources, kine-luminescent sources, thermo-luminescent sources, triboluminescent sources, sonoluminescent sources, radioluminescent sources, and luminescent polymers.
[0019] The term “lighting fixture” is used herein to refer to an implementation or arrangement of one or more lighting units in a particular form factor, assembly, or package. The term “lighting unit” is used herein to refer to an apparatus including one or more light sources of same or different types. A given lighting unit may have any one of a variety of mounting arrangements for the light source(s), enclosure/housing arrangements and shapes, and/or electrical and mechanical connection configurations. Additionally, a given lighting unit optionally may be associated with (e.g., include, be coupled to and/or packaged together with) various other components (e.g., control circuitry) relating to the operation of the light source(s). An “LED-based lighting unit” refers to a lighting unit that includes one or more LED-based light sources as discussed above, alone or in combination with other non LED-based light sources.
[0020] It should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein. In particular, all combinations of claimed subject matter appearing at the end of this disclosure are contemplated as being part of the inventive subject matter disclosed herein. It should also be appreciated that terminology explicitly employed herein that also may appear in any disclosure incorporated by reference should be accorded a meaning most consistent with the particular concepts disclosed herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] In the drawings, like reference characters generally refer to the same parts throughout the different views. Also, the drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention.
[0022] FIG. 1 illustrates a bottom front exploded perspective view of a first embodiment of a lighting unit.
[0023] FIG. 2 illustrates a rear plan view of the first embodiment of the lighting unit.
[0024] FIG. 3 illustrates a section view of the first embodiment of the lighting unit taken along the section line 3 - 3 of FIG. 2 .
[0025] FIG. 4 illustrates a bottom front exploded perspective view of a second embodiment of a lighting unit.
[0026] FIG. 5 illustrates a front plan view of the second embodiment of the lighting unit.
[0027] FIG. 6 illustrates a section view of the second embodiment of the lighting unit taken along the section line 6 - 6 of FIG. 5 .
[0028] FIG. 7 illustrates a bottom front exploded perspective view of a third embodiment of a lighting unit.
[0029] FIG. 8 illustrates a front plan view of the third embodiment of the lighting unit.
[0030] FIG. 9 illustrates a section view of the third embodiment of the lighting unit taken along the section line 9 - 9 of FIG. 8 .
DETAILED DESCRIPTION
[0031] In the following detailed description, for purposes of explanation and not limitation, representative embodiments disclosing specific details are set forth in order to provide a thorough understanding of the claimed invention. However, it will be apparent to one having ordinary skill in the art having had the benefit of the present disclosure that other embodiments according to the present teachings that depart from the specific details disclosed herein remain within the scope of the appended claims. Moreover, descriptions of well-known apparatuses and methods may be omitted so as to not obscure the description of the representative embodiments. Such methods and apparatuses are clearly within the scope of the claimed invention. For example, various embodiments of the apparatus disclosed herein are particularly suited for installation in a ceiling grid, such as, for example, a ceiling grid employing a low-voltage ceiling grid power supply system. Accordingly, for illustrative purposes, the claimed invention is discussed in conjunction with a lighting unit that may be adapted for such installation. However, other configurations and applications of the apparatus are contemplated without deviating from the scope or spirit of the claimed invention.
[0032] Referring initially to FIG. 1 through FIG. 3 , a first embodiment of a lighting unit 110 is shown. The lighting unit 110 has a plurality of LEDs 134 mounted in a linear arrangement on a circuit board 132 . The circuit board 132 may be coupled to a support surface 112 of a heatsink 110 . A plurality of heat fins 114 extend rearwardly from the support surface of the heatsink 110 and assist in dissipation of heat generated by the LEDs 134 . Optionally, a thermal material (e.g., thermal paste and/or a thermal pad) may be interposed between the circuit board 132 and the support surface 112 . In alternative embodiments the LEDs 134 may each be mounted on individual circuit boards or may be mounted directly to the support surface 112 .
[0033] A longitudinally extending first reflector 140 is provided along a first side of the LEDs 134 . The first reflector 140 is a singular piece and extends longitudinally from a first end 141 to a second end 142 thereof along each of the LEDs 134 . In alternative embodiments the first reflector 140 may comprise multiple reflector pieces and/or may extend along less than all of the LEDs 134 . The first reflector 140 has an inner concave surface 144 that extends from adjacent the LEDs 134 in a direction outward and away from the LEDs 134 toward a flange 146 of the first reflector 140 . The away direction is the direction generally perpendicular to the surface on which the LEDs 134 are mounted. In other words, in the first embodiment of the lighting unit 10 the away direction is generally perpendicular to the surface of the circuit board 132 to which the LEDs 134 are mounted. The outward direction is the direction peripheral of the LEDs 134 . In other words, the outward direction is generally perpendicular to the away direction.
[0034] A longitudinally extending second reflector 150 is provided along a second side of the LEDs 134 . The second reflector 150 is a singular piece and extends longitudinally from a first end 151 thereof to a second end 152 thereof along each of the LEDs 134 . In alternative embodiments the second reflector 150 may comprise multiple reflector pieces and/or may extend along less than all of the LEDs 134 . The second reflector 150 has an inner concave surface 154 that extends from adjacent the LEDs 134 in a direction outward and away from the LEDs 134 . The inner concave surface 154 and the inner concave surface 144 extend away from the LEDs 134 approximately the same distance. However, the inner concave surface 154 extends outward from the LEDs 134 approximately twice the distance as the inner concave surface 144 . Accordingly, the inner concave surface 154 has a greater degree of curvature than the inner concave surface 144 .
[0035] First reflector 140 and/or second reflector 150 may, in some embodiments be coupled to the circuit board 132 . For example, in some embodiments the first reflector 140 and/or the second reflector 150 may be fixedly or removably coupled to the circuit board 132 using mechanical affixation methods, including, but not limited to adhesives, welding, soldering, prongs, fasteners, and/or structure that may extend from first reflector 140 , second reflector 150 , and/or circuit board 132 . In some other embodiments the first reflector 140 and/or the second reflector 150 may be coupled to a frame 120 using mechanical affixation methods. The frame 120 may be coupled to the heatsink 110 and includes a frame sidewall 122 that surrounds the first reflector 140 , the second reflector 150 , the LEDs 134 , and the circuit board 132 . A first flange 124 and a second flange 125 extend perpendicular to and peripherally of the frame sidewall 122 and are substantially co-planar with the edges of first reflector 140 and second reflector 150 that are distal the circuit board 132 . The frame 120 may be relatively small in some embodiments such as, for example, five inches in longitudinal length and one inch in latitudinal width. Optionally, the lighting unit 10 may be adapted to be attached to a ceiling grid such as, for example, a low voltage powered ceiling grid system currently being advanced by the Emerge Alliance.
[0036] A longitudinally extending lens 160 is provided over and spaced apart from the LEDs 134 . The lens 160 may be constructed from a proper optical medium. For example, in some embodiments the lens 160 may be molded optical grade acrylic. The lens 160 is longitudinally extending from a first end 161 thereof to a second end 162 thereof. A substantially planar first side 167 of the lens 160 extends between the first end 161 and second end 162 and faces the LEDs 134 . The first side 167 is substantially co-planar with the circuit board 132 . A non-planar second side 166 is provided opposite the first side 167 and extends between the first end 161 and the second end 162 . A front longitudinal side 165 and a rear longitudinal side 164 extend between the first side 167 and the second side 166 . The rear longitudinal side 164 and the front longitudinal side 165 are oriented substantially perpendicular to the first side 167 . The front longitudinal side 165 is taller (in a direction from the first side 167 to the second side 166 ) than respective longitudinal locations of the rear longitudinal side 164 . The lens 160 extends between and beyond the first reflector 140 and the second reflector 150 . The lens 160 may be coupled to the flange 146 , the edge of the second reflector 150 , and/or portions of the frame utilizing an adhesive, for example. In other embodiments the lens 160 may be coupled to the first reflector 140 , the second reflector 150 , and/or the frame 120 using alternative mechanical affixation methods, including, but not limited to welding, soldering, prongs, fasteners, and/or structure that may extend from first reflector 140 , second reflector 150 , and/or circuit board 132 . Optionally, the mechanical affixation methods may allow for the lens 160 to be removably coupled to respective structure. A Gaussian filter 169 may optionally extend between the first reflector 140 and the second reflector 150 and be interposed between the LEDs 134 and the lens 160 .
[0037] In operation, appropriate electrical connections (e.g. from a LED driver and/or a low voltage ceiling grid) may be made to LEDs 134 . Some light output from LEDs 134 will be directly incident on Gaussian filter 169 and then lens 160 . Some light output will first reflect off first reflector 140 , second reflector 150 , and/or an interior facing portion of frame sidewall 122 and redirected toward filter 169 and then lens 160 . The first reflector 140 , second reflector 150 , and the lens 160 are configured for wall washing. A majority of the light emitted from the LEDs 134 will be directed out front longitudinal side 165 and second side 166 and directed generally toward an area that is in a direction that front longitudinal side 165 faces. As will be understood by one of ordinary skill in the art, having had the benefit of the present disclosure, variations may be made to the first reflector 140 , second reflector 150 , and or lens 160 to achieve a desired light output that varies from the light output achieved by lighting unit 110 . For example, in some embodiments the degree of curvature of the first concave surface 144 may be decreased to increase forward throw of light output and/or the contour of second surface 166 may be altered to achieve a different amount of internal reflection and/or different characteristics of internal reflection.
[0038] Referring to FIG. 4 through FIG. 6 , a second embodiment of a lighting unit 210 is shown. The lighting unit 210 has a plurality of LEDs 234 mounted in a linear arrangement on a circuit board 232 . The circuit board 232 may be coupled to a support surface 212 of a heatsink 210 . Optionally, a thermal material (e.g., thermal paste and/or a thermal pad) may be interposed between the circuit board 232 and the support surface 212 . In alternative embodiments the LEDs 234 may be mounted directly to the support surface 212 . The heatsink 210 has a ball socket shaft 215 extending from a rear surface thereof that is coupled to a ball socket 216 . The ball socket 216 is movably coupleable to a ball 206 that is coupled to a ball shaft 205 extending from an attachment piece 204 . The attachment piece 204 may be configured for installation in a ceiling grid such as, for example, a low voltage powered ceiling grid system. The movable coupling between the ball 206 and ball socket 216 enables the heatsink 210 and the attached circuit board 232 to be movably positioned at a desired orientation by a user. In alternative embodiments one or more hinges may be utilized in lie of the ball 206 and ball socket 216 to enable circuit board 232 to be movably positioned at a desired orientation by a user.
[0039] A longitudinally extending first reflector 240 is provided along a first side of the LEDs 234 . The first reflector 240 is a singular piece and extends longitudinally from a first end 241 to a second end 242 thereof along each of the LEDs 234 . In alternative embodiment the first reflector 240 may comprise multiple reflector pieces and/or may extend along less than all of the LEDs 234 . The first reflector 240 has an inner concave surface 244 that extends from adjacent the LEDs 234 in a direction outward and away from the LEDs 234 toward a flange 246 of the first reflector 240 .
[0040] A longitudinally extending second reflector 250 is provided along a second side of the LEDs 234 . The second reflector 250 is a singular piece and extends longitudinally from a first end 251 thereof to a second end 252 thereof along each of the LEDs 234 . In alternative embodiments the second reflector 250 may comprise multiple reflector pieces and/or may extend along less than all of the LEDs 234 . The second reflector has an inner concave surface 254 that extends from adjacent the LEDs 234 in a direction outward and away from the LEDs 234 toward a flange 256 of the second reflector 250 . The inner concave surface 254 and the inner concave surface 244 share a substantially common degree of curvature and extend away from the LEDs 234 approximately the same distance and outward from the LEDs 234 approximately the same distance.
[0041] First reflector 240 and/or second reflector 250 may, in some embodiments be coupled to circuit board 232 . For example, in some embodiments the first reflector 240 and/or the second reflector 250 may be coupled to the circuit board 232 using mechanical affixation methods. In some other embodiments the first reflector 240 and/or the second reflector 250 may be coupled to the heatsink 210 using mechanical affixation methods. Although not depicted, an end plate may optionally be placed between first ends 241 and 251 of first and second reflectors 240 and 250 and/or second ends 242 and 252 of first and second reflectors 240 and 250 . The end plate may optionally be interiorly reflective or semi-reflective.
[0042] A longitudinally extending lens 260 is provided over and spaced apart from the LEDs 234 . The lens 260 is longitudinally extending from a first end 261 thereof to a second end 262 thereof. A substantially planar first side 267 of the lens 260 extends between the first end 261 and second end 262 and faces the LEDs 234 . The first side 267 is substantially co-planar with the circuit board 232 . A non-planar second side includes a first protruding portion 266 A and a second protruding portion 266 B that are substantially similar in shape, are provided opposite the first side 267 , and extend between the first end 261 and the second end 262 . A front longitudinal side 265 and a rear longitudinal side 264 extend between the first end 261 and the second end 262 . The front longitudinal side 265 and the rear longitudinal side 261 are substantially perpendicular to the first side 267 . The first protruding portion 266 A and the second protruding portion 266 B are substantially basin shaped. The distance between the outer surface of each protruding portion 266 A and 266 B and the first side 267 decreases when moving longitudinally (e.g., along longitudinal side 264 or 265 ) or latitudinally (e.g., along first end 261 or second end 262 ) from the longitudinal and latitudinal center point of each protruding portion 266 A and 266 B.
[0043] The lens 260 extends between and beyond the inner concave surfaces 244 and 254 . In some embodiments the lens 260 may optionally comprise a first longitudinally extending lens having the first protruding portion 266 A and a second longitudinally extending lens having the second protruding portion 266 B. A Gaussian filter 269 may optionally extend between the first reflector 240 and the second reflector 250 and be interposed between the LEDs 234 and the lens 260 . The lens 260 has four attachment legs 272 extending from the lens generally in a direction away from the protruding portions 266 A and 266 B. The attachment legs 272 are provided on each corner of the lens 260 and have a chamfered locking protrusion 274 extending therefrom. Lens 260 may be coupled to first and second reflectors 240 and 250 by engaging the chamfered locking protrusions 274 against respective of flanges 246 and 256 , thereby causing the attachment legs 272 to be forced outward until the chamfered locking protrusions 274 lock with respective of flanges 246 and 256 as depicted in FIG. 6 . The lens 260 may be removed from the first and second reflectors 240 and 250 by forcing the locking protrusions 274 outward by a hand, tool, or otherwise, and pulling the lens 260 away from the first and second reflectors 240 and 250 . The lens 260 may be interchanged with another lens having alternative optical characteristics (e.g., lens 160 ) and optionally having similar attachment legs.
[0044] In operation, the LEDs 234 may be electrically coupled to a power source. Some light output from LEDs 234 will be directly incident on Gaussian filter 269 and then lens 260 . Some light output will first reflect off first reflector 240 , second reflector 250 , and/or an interior facing portion of one or more endplates and redirected toward filter 269 and then lens 260 . The first reflector 240 , second reflector 250 , and the lens 260 are configured for a square target medium distribution. The light output may be directed in substantially a batwing distribution pattern. A majority of the light emitted from the LEDs 234 will be directed out first protruding portion 266 A and second protruding portion 266 B and directed generally toward an area in a direction that first protruding portion 266 A and second protruding portion 266 B face. As will be understood by one of ordinary skill in the art, having had the benefit of the present disclosure, variations may be made to the first reflector 240 , second reflector 250 , and or lens 260 to achieve a desired light output that varies from the light output achieved by lighting unit 210 .
[0045] Referring to FIG. 7 through FIG. 9 , a third embodiment of a lighting unit 310 is shown. The lighting unit 310 has a plurality of LEDs 334 mounted in a linear arrangement on a circuit board 332 . The circuit board 332 may optionally be coupled to a heatsink or other support surface. A longitudinally extending first reflector 340 is provided along a first side of the LEDs 334 . The first reflector 340 is a singular piece and extends longitudinally from a first end 341 to a second end 342 thereof along each of the LEDs 334 . In alternative embodiment the first reflector 340 may comprise multiple reflector pieces and/or may extend along less than all of the LEDs 334 . The first reflector 340 has an inner concave surface 344 that extends from adjacent the LEDs 334 in a direction outward and away from the LEDs 334 toward a flange 346 of the first reflector 340 . The flange 346 has a plurality of threaded apertures 349 extending therethrough.
[0046] A longitudinally extending second reflector 350 is provided along a second side of the LEDs 334 . The second reflector 350 is a singular piece and extends longitudinally from a first end 351 thereof to a second end 352 thereof along each of the LEDs 334 . In alternative embodiments the second reflector 350 may comprise multiple reflector pieces and/or may extend along less than all of the LEDs 334 . The second reflector has an inner concave surface 354 that extends from adjacent the LEDs 334 in a direction outward and away from the LEDs 334 toward a flange 356 of the second reflector 350 . The flange 356 has a plurality of threaded apertures 359 extending therethrough. The inner concave surface 354 and the inner concave surface 344 share a substantially common degree of curvature and extend away from the LEDs 334 approximately the same distance and outward from the LEDs 334 approximately the same distance. The inner concave surface 354 and the inner concave surface 344 also share a substantially common degree of curvature wither inner concave surfaces 244 and 254 of the lighting unit 310 .
[0047] First reflector 340 and/or second reflector 350 may, in some embodiments be coupled to circuit board 332 . For example, in some embodiments the first reflector 340 and/or the second reflector 350 may be coupled to the circuit board 332 using mechanical affixation methods. Although not depicted, an end plate may optionally be placed between first ends 341 and 351 of first and second reflectors 340 and 350 and/or second ends 342 and 352 of first and second reflectors 340 and 350 . The end plate may optionally be interiorly reflective or semi-reflective.
[0048] A longitudinally extending lens 360 is provided over and spaced apart from the LEDs 334 . The lens 360 includes five individual lens pieces 360 A-E placed adjacent one another in a longitudinal relationship. The lens 360 is longitudinally extending from lens 360 A thereof to lens 360 E thereof. Each of the individual lens pieces 360 A-E share a common configuration and are placed over a single of the LEDs 334 . For ease and clarity in description, individual lens piece 360 A is the only of the individual lens pieces 360 A-E that is numbered in additional detail in the Figures and that will be described in additional detail herein. Individual lens piece 360 A is placed over a single of the LEDs 334 . A substantially planar first side 367 A of the individual lens piece 360 A extends between a first end 361 A and second end 362 A and faces the single of the LEDs 334 . The first side 367 A is substantially co-planar with the circuit board 332 . A non-planar second side 366 A has a substantially half-barrel shape, is provided opposite the first side 367 A and extends between the first end 361 A and the second end 362 A. A front longitudinal side 365 A and a rear longitudinal side 364 A extend between the first side 367 A and the second side 366 A. The front longitudinal side 365 A and the rear longitudinal side 364 A are substantially perpendicular to the first side 367 A.
[0049] A pair of flanges 368 A extend peripherally of the rear longitudinal side 364 A and front longitudinal side 365 A and each have a fastener aperture 369 A provided therethrough. The individual lens piece 360 A may be coupled to first reflector 340 and second reflector 350 by placing threaded fasteners 309 through fastener apertures 369 A and threading the threaded fasteners 309 into respective of the threaded apertures 349 and 359 . The individual lens piece 360 A may be removed from first reflector 340 and second reflector 350 by unthreading the threaded fasteners 309 from respective of the threaded apertures 349 and 359 . The lens 360 may be interchanged with another lens having alternative optical characteristics and optionally having similar apertures for receiving threaded fasteners 309 . For example, the lens 360 may be interchanged with lens 160 or lens 260 , either of which may optionally incorporate apertures for receiving threaded fasteners 309 . One or more individual lens pieces 360 A-E may be interchanged with other lens pieces having alternative characteristics and optionally having similar apertures for receiving threaded fasteners 309 . In some embodiments a Gaussian filter may optionally be interposed between the LEDs 334 and at least some of the lens 360 .
[0050] In operation, the LEDs 334 may be electrically coupled to a power source. Some light output from LEDs 334 will be directly incident on the lens 360 . Some light output will first reflect off first reflector 340 , second reflector 350 , and/or an interior facing portion of one or more end plates and redirected toward lens 360 . The first reflector 340 , second reflector 350 , and the lens 360 are configured for a spot target narrow distribution. A majority of the light emitted from the LEDs 334 will be directed out the second sides 366 A-E of the individual lens pieces 360 A-E and directed generally toward an area generally in a direction that the second sides 366 A-E face. As will be understood by one of ordinary skill in the art, having had the benefit of the present disclosure, variations may be made to the first reflector 340 , second reflector 350 , and or one or more of individual lens pieces 360 A-E to achieve a desired light output that varies from the light output achieved by lighting unit 310 .
[0051] While several inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the inventive teachings is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.
[0052] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
[0053] The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”
[0054] The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
[0055] As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
[0056] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
[0057] In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.
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The present disclosure is directed to inventive methods and apparatus for a lighting unit having a plurality of substantially linearly arranged solid state light sources ( 34, 134, 234, 334 ). A first reflector ( 40, 140, 240, 340 ) and a second reflector ( 50, 150, 250, 350 ) flank the solid state light sources ( 34, 134, 234, 334 ). A lens ( 60, 160, 260, 360 ) is provided over and spaced apart from a plurality of the solid state light sources ( 34, 134, 234, 334 ).
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to power generation and, more specifically, to a system for generating electricity utilizing continuous reusable energy.
[0003] The energy generating system of the present invention produces low cost electric power without consumption of limited natural resources, pollution, or greenhouse gas emission, and is independent of wind conditions. In turn, the energy generating system of the present invention provides improved means over existing coal and gas fixed power generation as well as nuclear plants and wind mill farms.
[0004] The present invention is a system for generating electricity comprising a plurality of towers in communication with a base level conduit housing having a section of smaller diameter containing an air driven turbine connected to a power storage system used to power a generator.
[0005] The towers are unified at the lower end with a single base enclosure providing means to maximize air speed. The venturi throat with the undershot air wheel is affixed within the single base enclosure. The upper end of each tower can include a venturi like collar to increase air suction.
[0006] An air compressor or pump is connected to the shaft of the aforementioned under shot air wheel by means of belt and/or gear system. The compressed air is then transferred to a storage tank suitable for high pressure. A plurality of air compressors and/or storage tanks may be utilized to suit power requirements to run the generator. Additionally, a fluid pump(s) may be utilized in lieu of the air compressor(s).
[0007] The compressed air is released and transferred to the generators whirling wheel providing necessary mechanical energy to turn the generator rotor and in turn, means to convert the mechanical energy into electrical energy. Pressure valves and an automatic controller provide means to regulate air flow between the store tanks and to the generator.
[0008] 2. Description of the Prior Art
[0009] There are other energy generating systems. Typical of these is U.S. Pat. No. 1,600,105 issued to Fonkiewicz on Jul. 12, 1923.
[0010] Another patent was issued to Carlson on Jul. 15, 1975 as U.S. Pat. No. 3,894,393. Yet another U.S. Pat. No. 3,936,652 was issued to Levine on Feb. 3, 1976 and still yet another was issued on Apr. 12, 1977 to Fiss as U.S. Pat. No. 4,016,725.
[0011] Another patent was issued to Payne on Apr. 2, 1985 as U.S. Pat. No. 4,508,973. Yet another U.S. Pat. No. 5,483,798 was issued to Prueitt on Jan. 16, 1996. Another was issued to Preito Santiago on Jul. 8, 2003 as U.S. Pat. No. 6,590,300 and still yet another was issued on Apr. 6, 2004 to Ferraro as U.S. Pat. No. 6,717,285.
[0012] Internationally, a patent was issued to Branczik on Dec. 24, 1930 as U.K. Patent No. GB340,127. Yet another U.K. Patent No. GB524680 was issued to Honig on Aug. 13, 1940. An International Patent Application was issued to Drucker on Dec. 20, 2001 as WO01/96740. Another International Patent Application was issued to Coustou on Feb. 23, 2006 as WO2006/018587.
U.S. Pat. No. 1,600,105
Inventor: Joseph Fonkiewicz
Issued: Sep. 14, 1926
[0013] This invention relates to new and useful improvements in power generators of the air propelled turbine type. An important object of this invention is, to provide means for making use of the old, well established principle of the upward draft of heated air through a hot stack, for the purpose of generating power. A further object of the invention is to provide a novel form of turbine wheel and draft with suitable anti-friction supporting means for the same. A still further object of the invention is to provide suitable means for relieving the weight of the turbine wheel and shaft from their supporting means when repairs to the latter are necessary.
U.S. Pat. No. 3,894,393
Inventor: Phillip R. Carlson
Issued: Jul. 15, 1975
[0014] A method and means for the generation of power from a controlled air flow, wherein an enclosed air mass is cooled at high altitude below the temperature of the surrounding air. The air is isolated from the surrounding air by means of a large duct. The resulting cooler, denser air flows down the duct toward lower altitude, and the energy of the falling air mass is extracted by means of a turbine generator.
U.S. Pat. No. 3,936,652
Inventor: Steven K. Levine
Issued: Feb. 3, 1976
[0015] A heat source heats air which rises in a duct having at least a one hundred meter vertical rise. Cold air enters the bottom of the duct through one or more horizontal passages containing vanes driven by moving air as a power source. The heat source may be a heat exchanger connected to an atomic reactor, a fossil fuel plant, a solar collector, or a geothermal heat supply. The heat exchanger may be located in the duct or in the one or more horizontal passages. In some applications, solar energy may directly heat the duct or a grid therein to cause an air flow.
U.S. Pat. No. 4,016,725
Inventor: Edward C. Fiss
Issued: Apr. 12, 1977
[0016] In a thermoelectric generating plant utilizing heat to generate electric energy and having a recirculating water system in which the water is heated during passage through the plant and must be cooled before recirculation to the plant thus causing a heat loss and resultant loss of energy; the combination therein of apparatus for recapturing a portion of the normally lost energy. The apparatus includes a natural air draft, cooling tower for the flow of air from the bottom to the top thereof and disposed in the recirculating water system for receiving the heated water and passing the heated water through the flow of air at generally the bottom thereof for cooling the heated water and heating the air to cause a natural draft flow of air up through the tower. A rotor is positioned within the cooling tower for being rotated by the natural draft flow of air therethrough and an electric generator is driven by the rotor to generate electric energy and thus recapture a portion of the normally lost energy from the plant.
U.S. Pat. No. 4,508,973
Inventor: James M. Payne
Issued: Apr. 2, 1985
[0017] A wind-operated electric generator system of simple design including a stationary circular arrangement of segmental wind inlet passages extending around a vertical axis and having vertical inlet openings at the outer ends, the inlet openings having inwardly and upwardly curving walls extending from the inlet openings toward the central axis, the lower walls sloping upwardly an appreciably greater extent than the upper walls to form an inwardly and upwardly extending convergence with the inner portions of the upper walls to form constricted upwardly directed exit passages that merge into a Venturi throat in which a bladed impeller is mounted upon a vertical shaft which is connected to an electric generator, and the sides of the segmental inlet passages also converging toward the central axis and cooperating with the converging upper and lower walls to form an efficient Venturi effect to increase the speed of air currents directed to the impeller.
U.S. Pat. No. 5,483,798
Inventor: Kurt P. Prueitt
Issued: Jan. 16, 1996
[0018] Convection towers which are capable of cleaning the pollution from large quantities of air, of generating electricity, and of producing fresh water utilize the evaporation of water sprayed into the towers to create strong airflows and to remove pollution from the air. Turbines in tunnels at the skirt section of the towers generate electricity, and condensers produce fresh water.
U.S. Pat. No. 6,590,300
Inventor: Preito Santiago
Issued: Jul. 8, 2003
[0019] A cyclonic or anti-cyclonic conversion tower which consists of a central vortical duct, and at least one convector made up of two vertical membranes or screens and, generated by a curve and which are limited at one of their sides by the central vortical duct, and at least tow stiffeners and per convector, there being a blocking device per convector, a diffuser, a deflector, and means for converting kinetic energy into electrical or mechanical energy, the blocking devices having the shape of a guiding crown and can turn on the outer circumference of the central vortical duct, the general context adopting the shape of a cylinder or a cylinder ending in an inverted cone trunk.
U.S. Pat. No. 6,717,285
Inventor: Michael Ferraro
Issued: Apr. 6, 2004
[0020] A wind powered generating device comprises a tube cluster, a collector assembly, and a turbine assembly. The collector assemblies utilize sails that can be rotated to direct wind down through an inlet tube to a central outlet tube. The central outlet tube is narrowed at a portion, and a turbine is mounted at this narrowed portion to take advantage of the Venturi effect that accelerates the air as it passes the turbine. This permits reliable and efficient operation in areas that were not formerly considered windy enough to be economically feasible for the deployment of wind powered generating devices. Alternative embodiments of the invention include mechanisms for dealing with violent weather conditions, a first of which allows excess wind to bleed off beneath and between the sails, and a second which collapses and covers the sail with a protective sheath/sock.
U.K. Patent Number GB340127
Inventor: Karl Wladimir Branczik
Issued: Dec. 24, 1930
[0021] This invention relates to cooling towers, and has for its object to provide improved and cheaper constructions, cheap and simple to erect and covering a minimum amount of ground space. The tower according to the present invention is of venturi form, having a straight line elevation from the ground to the neck. Preferably the wall constituting this part of the tower is made of concrete which may be reinforced and the wall may be of gradually decreasing thickness from the ground to the neck.
U.K. Patent Number GB524680
Inventor: Edgar Honig
Issued: Aug. 13, 1940
[0022] A cooling tower comprises an outer shell, of substantially venturi section and an inner shell with supports leaving an annular space open at both ends. The velocity of the ascending moist air is greater in the shell, and expansion takes place at the upper end so that moisture is mainly precipitated in the flared portion of the outer shell. An outer shell is mounted on an annular support on an inner shell, and apertures are provided in the inner shell at the base of the annular space. Apertures may also be provided in the outer shell at the top and at intermediate points.
International Patent Application Number WO01/96740
Inventor: Ernest R. Drucker
Issued: Dec. 20, 2001
[0023] A solar energy power plant comprises at least one vertical tower with an open top mounted on a base structure. Each tower has a height of at least 100 meters with a plurality of outwardly projecting heating chambers mounted externally around the lower end of the vertical tower. Each heating chamber is a generally hollow chamber with walls formed of thin metal sheeting for absorbing solar energy, a closeable opening in a lower region of the chamber for introducing ambient air into the chamber and a closeable opening in an upper region of the chamber for releasing heated air accumulated in the chamber into the tower. A constricted zone, e.g. Venturi chamber, within the tower above the heated air inlet openings is adapted to increase the velocity of the heated air moving up the tower, and a wind powered turbine is mounted within the constricted zone and adapted to drive an electrical generating unit. The height of each tower and the number and size of the heating chambers connected thereto are sufficient to provide a substantially continuous updraft in the tower for driving the turbine.
International Patent Application Number WO2006/018587
Inventor: Alain Coustou
Issued: Feb. 23, 2006
[0024] The invention relates to continuously mass-producing electric power with a low cost, without pollution, greenhouse gas emission, consumption of limited natural resources, wastes and independently of irregularity of wind conditions. The invention is embodied in the form of a hollow tower-shaped structure flared at the base thereof, surrounded by a greenhouse area and is optimized in order to combine the four following natural forces and effects: a chimney effect, greenhouse effect, Coriolis force and a Venturi effect. The inventive plant comprises, in particular curved structures for activating an artificial and self-sustaining vertex, peripheral flap shutters for involving a wind quantity and pools optimized for storing calories supplied by sun and optionally by effluents of nuclear power plants, different industrial activities or geothermal waters. The production capacity of the inventive power plant is of several hundreds of MW and the production cost of one KW/hour could be substantially low.
[0025] While these energy generating systems may be suitable for the purposes for which they were designed, they would not be as suitable for the purposes of the present invention, as hereinafter described.
SUMMARY OF THE PRESENT INVENTION
[0026] A primary object of the present invention is to provide a system for generating electricity utilizing continuous reusable energy.
[0027] Another object of the present invention is to provide a system comprising a plurality of towers in communication with a base level conduit housing having a section of smaller diameter with a turbine connected to a power storage system used to power a generator.
[0028] Yet another object of the present invention is to provide a system that produces electric power without consumption of limited natural resources, pollution, or greenhouse gas emission, and is independent of wind conditions.
[0029] Still yet another object of the present invention is to provide a system that produces electric power at a low cost.
[0030] Yet another object of the present invention is to provide a system wherein the towers are unified at the lower end with a single base enclosure providing means to maximize air speed.
[0031] Another object of the present invention is to provide a system wherein the venturi throat with the undershot air wheel is affixed within the single base enclosure.
[0032] Still yet another object of the present invention is to provide a system wherein the upper end of each tower can include a venturi like collar to increase air suction.
[0033] Additional objects of the present invention will appear as the description proceeds.
[0034] The present invention overcomes the shortcomings of the prior art by providing low cost electric power without consumption of limited natural resources, pollution, or greenhouse gas emission, and is independent of wind conditions. Additionally, the system of the present invention includes a venturi-like collar positioned at the top of one or more stacks increasing air flow.
[0035] The foregoing and other objects and advantages will appear from the description to follow. In the description reference is made to the accompanying drawing, which forms a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. These embodiments will be described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural changes may be made without departing from the scope of the invention. In the accompanying drawing, like reference characters designate the same or similar parts throughout the several views.
[0036] The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is best defined by the appended claims.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
[0037] In order that the invention may be more fully understood, it will now be described, by way of example, with reference to the accompanying drawing in which:
[0038] FIG. 1 is an illustrative view of the present invention in use;
[0039] FIG. 2 is a perspective view of the present invention;
[0040] FIG. 3 is a sectional view of the present invention;
[0041] FIG. 4 is a sectional view of the conduit of the present invention;
[0042] FIG. 5 is a top sectional view of the present invention;
[0043] FIG. 6 is a flow chart of the present invention;
[0044] FIG. 7 is a detailed view of the air wheel of the present invention; and
[0045] FIG. 8 is a detailed view of the whirling wheel of the present invention.
DESCRIPTION OF THE REFERENCED NUMERALS
[0046] Turning now descriptively to the drawings, in which similar reference characters denote similar elements throughout the several views, the figures illustrate the Electric Generating System of the present invention. With regard to the reference numerals used, the following numbering is used throughout the various drawing figures.
10 Electric Generating System of the present invention 12 base 14 tower 16 air intake venture conduit 18 turbine 20 power storage unit 22 air compressor 24 liquid pump 26 generator 28 venturi throat 30 air intake port 32 whirling wheel 34 power storage tank 36 mountain top 38 drive shaft from venturi 40 pressure valve 42 automatic controller 44 pedal member 46 fins of 18 48 venturi-like collar 50 rotor of 26
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0068] The following discussion describes in detail one embodiment of the invention (and several variations of that embodiment). This discussion should not be construed, however, as limiting the invention to those particular embodiments, practitioners skilled in the art will recognize numerous other embodiments as well. For definition of the complete scope of the invention, the reader is directed to appended claims.
[0069] FIG. 1 is an illustrative view of the present invention 10 in use. The present invention 10 is a system for generating electricity comprising a plurality of towers 14 in communication with a common base with an air intake venturi conduit 16 extending centrally and horizontally therefrom. The air intake venturi 16 with an air intake port 30 leading to a central venturi throat 28 of smaller diameter containing an air driven turbine connected to a power storage unit 20 used to power rotor 50 of generator 26 . The power storage unit 20 is comprised of an air compressor 22 or liquid pump 24 in communication with a power storage tank 34 . Additionally providing for an optional venturi-like collar positioned at the top of one or more stacks 14 . Ideally the present invention 10 is situated at a high altitude such as a mountain top 36 to take advantage of the high winds which are prevalent in such conditions.
[0070] FIG. 2 is a perspective view of the present invention 10 . The present invention 10 is a system and method for generating power from a controlled air flow wherein air flow above a plurality of towers 14 draws ground air into the base 12 through an air intake port 30 and venturi throat 28 , turning a turbine air wheel that has a drive shaft 38 leading to a power storage unit 20 for powering an air compressor 22 or liquid pump 23 , power storage tank 34 and generator 26 . Pressure valves 40 and an automatic controller 42 provide means to regulate air flow between the store tanks 34 and to the rotor 50 of generator 26 .
[0071] FIG. 3 is a sectional view of the present invention 10 . Shown is a sectional view of the present invention 10 , a system for generating electricity comprising a plurality of towers 14 in communication with a common base 12 having a venturi conduit 16 extending centrally therefrom. A pedal member 44 is disposed in the venturi throat 28 between the air intake port 30 and the turbine wheel 18 and angularly descends from the top of the conduit 16 towards the turbine wheel 18 to deflect air flow to strike the lower fins 46 thereof to effectively rotate the wheel 18 . The turbine undershot air wheel 18 is connected to a power storage system used to power a compressor or pump. Also shown is the venturi-like collar 48 positioned at the top of the tower 14 .
[0072] FIG. 4 is a sectional view of the air intake venturi conduit 16 . Shown is a sectional view of the conduit 16 housing having a venturi throat 28 of smaller diameter with an undershot turbine wheel 18 that is driven by the air flow passing through the air intake port 30 and deflected downward by the pedal 44 to drive the fins 46 and rotate the turbine wheel 18 .
[0073] FIG. 5 is a top sectional view of the present invention 10 . Shown is a top sectional view of the present invention 10 for generating power from a controlled air flow through air current passing over a plurality of towers 14 that draws ground air through a common base 12 via a single venturi conduit 16 housing an air driven turbine wheel 18 used for powering a generator. The venturi conduit 16 comprises a venturi throat 28 of smaller diameter with an undershot turbine wheel 18 that is driven by the air flow passing through the air intake port 30 and deflected downward by the pedal 44 to drive the fins 46 and rotate the turbine wheel 18 . The rotation of the turbine wheel 18 drives a power shaft 38 leading to a power storage unit 20 to energize an air compressor 22 or a liquid pump 24 and store the potential energy derived therefrom in a power storage tank 34 . The potential energy is used to power the generator.
[0074] FIG. 6 is a flow chart of the present invention 10 . The present invention 10 is a system for generating electricity from a controlled air flow through air current passing over a plurality of towers 14 that draws ground air through a common base 12 via a single venturi conduit 16 housing an air driven turbine wheel 18 used for powering a generator 26 . The venturi conduit 16 comprises a venturi throat 28 of smaller diameter with an undershot turbine wheel 18 that is driven by the air flow passing through the air intake port 30 and deflected downward by the pedal 44 to drive the fins 46 and rotate the turbine wheel 18 . The rotation of the turbine wheel 18 drives a power shaft 38 leading to a power storage unit 20 to energize at least one air compressor 22 or a liquid pump 24 and store the potential energy derived therefrom in at least one power storage tank 34 . Compressed air is released from the storage tank 34 and transferred to the generators whirling wheel 32 providing necessary mechanical energy to turn the rotor 50 of the generator 26 and in turn, means to convert the mechanical energy into electrical energy.
[0075] FIG. 7 is a perspective view of the air wheel of the present invention. Shown is a detailed view of the turbine wheel 18 of the present invention. Air flow above a plurality of towers draws ground air through a conduit housing with a smaller diameter section containing an air driven turbine wheel 18 with fins 46 for generating energy through a drive shaft 38 to power a generator through a power storage facility.
[0076] FIG. 8 is a detailed view of the whirling wheel 32 of the present invention. The present invention is a system for generating electricity comprising a plurality of towers in communication with a base level conduit housing having a centrally disposed section of smaller diameter housing an air driven turbine and an interiorly positioned deflector for deflecting air flow to a desired portion of the air wheel having a drive shaft for powering a generator 26 through a power storage facility.
[0077] It will be understood that each of the elements described above, or two or more together may also find a useful application in other types of methods differing from the type described above.
[0078] While certain novel features of this invention have been shown and described and are pointed out in the annexed claims, it is not intended to be limited to the details above, since it will be understood that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation can be made by those skilled in the art without departing in any way from the spirit of the present invention.
[0079] Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention
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A system for providing low cost electric power without consumption of limited natural resources, pollution, or greenhouse gas emission, and is independent of wind conditions. Additionally, the system of the present invention includes a venturi-like collar positioned at the top of one or more stacks increasing air flow.
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RELATED APPLICATIONS
This application is a divisional of U.S. application Ser. No. 11/124,247, filed May 6, 2005, now U.S. Pat. No. 7,427,551 which is a divisional of U.S. application Ser. No. 10/707,863 filed Jan. 19, 2004, now U.S. Pat. No. 6,969,903.
BACKGROUND OF INVENTION
1. Field of the Invention
The present invention relates to semiconductor devices and methods of manufacturing thereof, and more particularly to a semiconductor resistor structure optimized for tolerance and high current and a method of fabrication thereof. More specifically, the present invention provides a high tolerance Temperature Coefficient of Resistance (TCR) balanced high current resistor for RF CMOS and RE SiGe BICMOS applications and a computer aided design kit for designing the same.
2. Background of the Invention
Optimization of passive elements for tolerance and high current is valuable for RF technologies. In RF circuit applications, precision resistors are needed for I/O circuitry implementing both radio frequency (RF) CMOS an RF SiGe technology. High tolerance resistors are important for accurate prediction of models and statistical control. Moreover, in RF devices and circuits, high tolerance resistors are needed that have good linearity; a low temperature coefficient of resistance (TCR) which is the normalized first derivative of resistance and temperature, and provides an adequate means to measure the performance of a resistor; a high quality factor (Q); and are suitable for high current applications.
In high current RF applications, it is desirable that resistors maintain their structural integrity at high currents. In current multiple inter-level dielectric film stack structures, there exist materials with potentially different thermal and mechanical properties which can influence the temperature distribution within the resistor element and also the mechanical stress and strain in metal and insulation regions. Conventional metal resistor structures subjected to high currents above a critical current-to-failure point, can result in metal blistering, extrusion, and melting of the metal resistor regions. Additionally, subjecting a conventional resistor to high current may result in a thermal gradient in the surrounding insulator that may exceed the yield stress and result in insulator cracking. The above phenomena both reduce the integrity of the dielectric and semiconductor chips when subjected to high current.
Further, in RF CMOS, or RF SiGe, the usage of resistors in series with RF MOSFETs for resistor ballasting in source, drain, and gate regions are valuable for ESD protection. For an RF MOSFET, series resistance is important to minimize for RE performance. Hence, having a low resistance in the source and the drain are important for good RF characteristics. Source and drain resistance are lowered using salicide regions on the source and drain diffusion regions, but salicide near the gate impacts the ESD robustness of the device. For an RF MOSFET device, it is key to provide ballasting effects as well as low resistance. Adding extra resistor elements increase the loading capacitance on the circuit and impacts area. Hence, finding a means to provide low resistance for RE functionality but ballasting for ESD robustness is key to providing a good RF MOSFET.
It is also well known that current drive in devices at high current is not uniform, largely due to non-uniform temperature distribution in such devices when driven at high currents. Thus, to provide uniformity of current drive, a device which has a more uniform current distribution as a function of device dimensions is an advantage.
Moreover, for RF bipolar and SiGe transistors, a means for establishing uniform current in a transistor to maximize its high current capability is key for power amplifier applications, ESD networks and other applications. Current uniformity can lead to an improved net performance by avoiding increasing a structure size to provide an equivalent drive strength. Additionally, using resistor ballasting in a base region can lead to uniformity of input current. Additionally, using a resistor ballasting in an emitter structure can provide both thermal and electrical stability in a circuit. Additionally, it is important that the element does not structurally fail due to high currents. For differential circuits, it is important that good matching characteristics are present in the physical elements.
It would therefore be highly desirable to provide a semiconductor resistor structure and method of fabrication that is customized to achieve a desired (optimized) TCR, and preferably, a low net Temperature Coefficient of Resistance (TCR) value at high currents and in a joule-heating regime of operation. To this end, it would be desirable to provide a semiconductor resistor element structure and method of fabrication for power amplifiers, and ESD applications that provides a tunable Temperature Coefficient of Resistance for circuit linearity.
It would furthermore be highly desirable to provide a semiconductor resistor element structure and method of fabrication, wherein the resistor element is capable of carrying high currents without failure, and is designed to exhibit internal self-resistor ballasting to maintain a uniform current density and thermal gradient for uniform current distribution and minimization of thermal stress.
It would moreover be highly desirable to provide a semiconductor RF MOSFET device implementing a high resistance element that is physically small, provides a high Q factor, and renders the device electrically and thermally stable at high temperatures and high currents.
ESD protection circuits for input nodes must also support quality de, ac, and RF model capability in order to co-design ESD circuits for analog and RF circuits. With the growth of the high-speed data rate transmission, optical interconnect, wireless and wired marketplaces, the breadth of applications and requirements is broad. Each type of application space has a wide range of power supply conditions, number of independent power domains, and circuit performance objectives. As a result, an ESD design system which has dc and RF characterized models, design flexibility, automation, ESD characterization, and satisfies digital, analog and RF circuits is required to design and co-synthesize ESD needs of mixed signal RF technology.
The ability to design a resistor element so that co-synthesis of the ESD and the functional RF needs to insure integrity of the resistor element is critical in future technologies.
Much effort has been expended by industry to protect electronic devices from ESD damage. Traditionally, ESD designs are custom designed using graphical systems. ESD ground rules and structures are typically built into the designs requiring a custom layout. This has lead to custom design for digital products such as DRAMs, SRAMs, microprocessors, ASIC development and foundry technologies. This design practice does not allow for the flexibility needed for RF applications. A difficulty in the design of RF ESD solutions is that traditionally, specific designs are fixed in size in order to achieve verifiable ESD results for a technology. The difficulty with analog and RF technology is that a wide range of circuit applications exists where one ESP size structure is not suitable due to loading of the circuit. A second issue is that the co-synthesis of the circuit and the circuit must be done to properly evaluate the RE performance objectives of a resistor element. RF characterization of the resistor or network that is flexible with the device size is important for the evaluation of the tradeoffs of RF performance and ESD. A third issue for RE mixed signal designs, there are analog and digital circuits.
In this environment, the verification and checking is necessary to evaluate ESD robustness of the resistor element and the ESD robustness of the semiconductor chip. The verification of the existence of the ballast resistor elements, the pads, the ESD input circuit, the ESD power clamp circuit, ESD rail-to-rail circuits, interconnects between the input pad and the ESD circuits, interconnects between power pads and the ESD power rails, the interconnects between two power rails for rail-to-rail ESD networks, the verification of ESD rail-to-rail type designs between functional blocks, verification of type of ESD networks on analog, digital and RF circuits, verification of the correct ESD network for a given chip circuit, verification of the critical size of the resistor, and the interconnects, verification of the size and adequacy of the ESD network are all important to provide ESD protection of RF BiCMOS, RF BiCMOS Silicon Germanium and RF CMOS applications.
It would thus be further highly desirable to provide a computer aided design tool with the ability to provide customization and personalization of the internal ballasting (both lateral and vertical), variable TCR, TCR matching, high current robustness, electrothermal optimization and ESD robustness.
It would additionally be desirable to provide a computer aided design tool with graphical and schematic features hierarchical parameterized cell for a resistor element with the ability to provide customization, personalization and tunability of TCR, TCR matching, and high current robustness and ESD robustness.
It would further be highly desirable to provide a computer aided design tool with graphical and schematic features hierarchical parameterized cell which allows graphical or schematic optimization and autogeneration of the resistor element.
SUMMARY OF INVENTION
It is an object of the present invention to provide a resistor structure that maintains structural and material integrity at high current and temperature, and has a low net thermal coefficient of resistance and a high melting temperature.
It is a further objective to provide a resistor structure that provides a uniform current within the structure and provides self-ballasting within the physical resistor structure to maintain a uniform current density within the resistor itself especially at high frequencies including RF frequencies.
It is a further objective to provide a semiconductor resistor structure and method of fabrication that is customized to achieve a desired (optimized) TCR, and preferably, a low net Temperature Coefficient of Resistance (TCR) value at high currents and in a joule-heating regime of operation. To this end, it is advantageous to provide a semiconductor resistor element structure and method of fabrication for use in power amplifiers, and ESD circuit applications that provides a tunable Temperature Coefficient of Resistance for circuit linearity.
It is a further objective to provide a semiconductor resistor element structure and method of fabrication, wherein the resistor element is capable of carrying high currents without failure, and is designed to exhibit internal self-resistor ballasting (both laterally and vertically) to maintain a uniform current density and thermal gradient for uniform current distribution and minimization of thermal stress.
It is a further objective to provide a semiconductor RF MOSFET device implementing a high resistance value element that is physically small, provides a high Q factor, and renders the device electrically and thermally stable at high temperatures and high currents.
In accordance with these and other objectives, there is provided a semiconductor resistor device structure and method of manufacture therefore, wherein the semiconductor resistor device structure invention includes a plurality of alternating conductive film and insulative film layers, at least two of the conductive film layers being electrically connected in parallel to provide for high current flow through the resistor device at RF frequencies with increased temperature and mechanical stability. The alternating conductive film and insulative film layers may be of a planar or non-planar geometric spatial orientation. The alternating conductive film and insulative film layers may include lateral and vertical portions designed to enable a uniform current density flow within the structure itself through a self-ballasting effect within the physical resistor element. This enables maintenance of a uniform current density within the resistor itself at high frequencies (RF frequencies), e.g., in the vertical and lateral portions of the resistor element. The self-ballasting effect is produced by a plurality of thin conductive and insulating films, wherein the thin insulator films minimize the thermal gradients between successive conductive and insulating films. The resistor element of thin conductive and insulating films are deposited atop a planar surface or non-planar surface such as a trough or a grooved structure.
Further in the achievement of the above-mentioned objects, there is additionally provided a computer-aided design system and methodology having graphical and schematic features enabling generation of a hierarchical parameterized cell for a resistor element with the ability to provide customization, personalization of the lateral and vertical ballasting and tunability of TCR, TCR matching, and high current robustness and ESD robustness and electrothermal optimization. Such a computer aided design tool includes a graphical and schematic hierarchical parameterized cell which allows graphical or schematic optimization and autogeneration of the resistor element and circuits including the resistor element.
Specifically, the computer-aided design system and methodology enables the generation of parameterized cells (p-cells) that are data structures used in the design of semiconductor devices and circuits and particularly, design of semiconductor resistor device structures having a plurality of alternating conductive film and insulator film layers according to the present invention. The system and methodology enables the autogeneration of a semiconductor resistor device structure utilizing the p-cells in a manner that enables the formed resistor device to exhibit optimized TCR value by enabling customization which provides a TCR utilizing a plurality of conductive films of different physical size, thicknesses and TCR material values in either planar or non-planar geometric spatial orientation, and a plurality of insulative films having different thermal properties; i.e., Low-K materials, SiO.sub.2, porous Si, and SiLK in corresponding planar or non-planar geometric spatial orientation.
Advantageously, the novel resistive element designed according to the methodology of the invention may be integrated with interlevel dielectric films and other conductive wires and via structures in an integrated semiconductor chip or be integrated with a passive or active structural element; i.e., inductors, capacitors, MOSFETs, NPN transistor, varacator or other RF CMOS and RF SiGe elements well known within the ordinary skill of the art.
BRIEF DESCRIPTION OF DRAWINGS
Further features, aspects and advantages of the structures and methods of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where:
FIGS. 1( a )- 1 ( d ) depict various embodiments of the resistor element of the present invention (through cross sectional views) that includes conductive elements in a trough configuration;
FIGS. 2( a )- 2 ( c ) depict various embodiments of the resistor element of the present invention (through cross sectional views) that comprises a multitude of dielectric and conductive layers deposited in a planar configuration;
FIG. 3 depicts a flow chart including the steps of the present invention for fabricating the resistor structure of trough configuration as depicted in FIGS. 1( a )- 1 ( d );
FIG. 4 depicts a flow chart including the steps of the present invention for fabricating the resistor structure of planar configuration as depicted in FIGS. 2( a )- 2 ( c );
FIG. 5 depicts a CAD design tool concept whereby a computer is implemented that interacts with Graphical generator and Schematic generator sub-systems according to the present invention;
FIG. 6 depicts the graphical and schematic design sub-systems accessible via a user interface for designing a resistor p-cell according to the present invention;
FIG. 7 depicts an implementation of the design system of the present invention implemented in CADENCE for designing the resistor p-cell elements and generating circuits employing the resistor p-cells;
FIG. 8( a ) depicts conceptually the p-cell graphical design system 350 according to the invention and, FIG. 8( b ) depicts conceptually, the p-cell schematic design system 370 according to the invention;
FIG. 9( a ) depicts an exemplary schematic editing graphical unit interface (GUI) 330 , invoking functionality for constructing a variety of p-cell elements;
FIG. 9( b ) depicts a pull-down design panel that requests the designer to input parameters in the design of a resistor p-cell;
FIG. 9( c ) illustrates an example resistor p-cell GUI panel showing a built resistor P-cell having attributes including: a resistor cell type, a type of technology, a library name, a resistor value, a TCR value and an ESD value;
FIG. 10 illustrates hierarchical p-cell information included in a “translation box” that includes a plurality of input connections and output connections that may be later specified for connection in a circuit to achieve a certain performance; and
FIG. 11 depicts a symbol view representing a designed resistor that may be specified for connection in an RF circuit, for example.
DETAILED DESCRIPTION
Referring now to the drawings, and more particularly to FIG. 1( a ), there is depicted a novel resistive structure 10 according to a first embodiment of the invention. In this embodiment, the resistive structure 10 is formed in a trough 11 , for example, formed in a substrate (not shown) having a layer of dielectric material conforming to the base and sidewalls. The trough structure 11 comprises a bottom portion of dielectric material 12 a and two parallel sidewall formations 12 b , 12 c of dielectric material. Examples of insulative dielectric materials for the portions 12 a - 12 c include, but are not limited to: low-k materials, SiLK®, an oxide, nitride, oxynitride or any combination thereof including multilayers, porous or non-porous inorganic and/or organic dielectrics formed by a deposition process such as CVD, PECVD, chemical solution deposition, atomic layer deposition and other like deposition processes. Thus, the dielectric material may be comprised of SiN, SiO.sub.2, a polyimide polymer, a siloxane polymer, a silsesquioxane polymer, diamond-like carbon materials, fluorinated diamond-like carbon materials and the like including combinations and multilayers thereof.
In the embodiment depicted in FIG. 1( a ), resistive elements are formed within the trough structure 11 by utilizing a deposition process such as, for example, sputtering, plating, evaporation, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), chemical solution deposition, atomic layer deposition and other like deposition processes. The first resistor material 15 typically has a thickness, after deposition, of from about 50 to about 1000 Å, with a thickness of from about 50 to about 500 Å being more preferred and includes an outer conductor portion including lateral conductive film 115 a and two parallel vertical formations 15 b , 15 c of conductive material. The resistive structure further comprises an inner conductive portion 16 . The outer and inner conductor portions 15 a , 15 b , 15 c and 16 preferably comprise a resistive material including but not limited to: Ta, TaN, Ti, TiN, W, WN. In this structure, refractory metal films are ideal because of the high melting temperature, however, the material chosen may also be chosen for the TCR values. The conductive material forming outer conductor portions 15 a , 15 b , 15 c has a first sheet resistance value and a first TCR value and, the conductive material forming inner conductor portions 16 may have a second sheet resistance value and a second TCR value. The TCR values may be positive or negative depending on the type of resistor material used, and the sheet resistance is also dependent on the type of material used as well as its length and area. As shown in FIG. 1 , the resistive structure 10 may be formed as part of an interlevel circuit or comprise part of an interconnect structure as shown connected to another wire level 19 by a conducting via 18 . As shown in FIG. 1( a ), the via connects all conductive materials of the resistive element 10 .
With respect to the embodiment depicted in FIG. 10 b ), the thin film resistor 20 includes alternating conductive and insulating films in a trough configuration by repeating resistor material deposition and insulating material formation steps. In the structure depicted in FIG. 1( b ), a plurality of alternating refractory metal films 25 a,b,c in trough configuration having lateral and vertical formations and alternating insulator films 22 a,b,c formed between the conductive layers is shown. As mentioned, this resistive element may be formed as part of an interlevel circuit or comprise part of an interconnect structure as shown connected to another wire level 29 by a conducting via 28 which is electrically connected to each of the conductor layers 25 a,b,c . It is understood that the via may alternately connect some or all of the conductors in the achievement of a desired design parameter, e.g., resistance. In this structure, the plurality of film types may be chosen to have different thicknesses and widths to provide a desired matching of current carrying capability and TCR values. The insulator films and materials can also be chosen to provide the adhesion, thermal and mechanical desired features.
In an alternate embodiment, a resistive structure 30 depicted in the cross-section view of FIG. 1( c ) includes a structure similar to that depicted in FIG. 1( b ) comprising alternating conductive and insulative films in a trough configuration. In the embodiment depicted in FIG. 1( c ), the conductor layers 35 a,b,c having lateral and vertical formations each comprise a different material, e.g., having different TCR values, and designed to achieve a net TCR value, e.g., zero, In the resistive structure of FIG. 1( c ), alternating insulator films 32 a,b,c are formed between the conductive layers with each layer being the same material including, but not limited to: an oxide, nitride, oxynitride or any combination thereof including multilayers, porous or non-porous inorganic and/or organic dielectrics formed by a deposition process, including low-k materials and SiLK® The alternating conductive layers include a resistive material including but not limited to: Ta, TaN, Ti, TiN, W, WN or other refractory metal films. As mentioned, this resistive element may be formed as part of an interlevel circuit or comprise part of an interconnect structure as shown connected to another wire level 39 by a conducting via 38 which is electrically connected to each of the conductor layers 35 a,b,c . It is understood that the via may alternately connect some or all of the conductor layers of the trough to the adjacent wire level in the achievement of a desired design parameter, e.g., resistance.
In another alternate embodiment, a resistive structure 40 depicted in the cross-section view of FIG. 1( d ) includes a structure similar to that depicted in FIG. 1( b ) comprising alternating conductive and insulative films in a trough configuration. In the embodiment depicted in FIG. 1( d ), the conductor layers 45 a,b,c having lateral and vertical formations with each layer comprising a different material, e.g., having different TCR values capable of being designed to achieve a desired net TCR value, e.g., zero. In the resistive structure of FIG. 1( d ), alternating insulator films 42 a,b,c are formed between the conductive layers with each layer comprising a different material including, but not limited to: an oxide, nitride, oxynitride or any combination thereof including multilayers, porous or non-porous inorganic and/or organic dielectrics formed by a deposition process. The alternating conductive layers include a resistive material including but not limited to: Ta, TaN, Ti, TiN, W, WN or other refractory metal films. As mentioned, this resistive element may be formed as part of an interlevel circuit or comprise part of an interconnect structure as shown connected to another wire level 49 by a conducting via 48 which is electrically connected to each of the conductor layers 45 a,b,c . It is understood that the via may alternately connect some or all of the conductor layers of the trough to the adjacent wire level in the achievement of a desired design parameter, e.g., resistance.
A methodology 100 for forming the resistive structures depicted in FIGS. 1( a )- 1 ( d ) is shown in FIG. 3 which includes a first step 102 of depositing a first interlevel dielectric layer, and, a further step 105 of implementing a conventional photolithographic technique for etching (e.g., Reactive Ion Etching) the trough structure, as depicted, and cleaning it. Then, as next depicted at step 110 , a resistor film may then be deposited using an atomic layer deposition technique known in the art. Additionally, alternate dielectric levels may be deposited with alternating resistor films within the trough structure. Then, as depicted at step 120 , a chemical mechanical polish (CMP) technique is used to planarize and clean the structure. As shown in further step 125 , a top metal wire structure is deposited and etched Known single or dual damascene techniques may be employed.
It should be understood that, in each of the resistive structures depicted in FIGS. 1( b )- 1 ( d ), due to the resistive nature of many of the refractory metals, a resistor film thickness may be chosen to provide lateral resistor ballasting across the resistor film. The lateral resistor ballasting is established if the material exhibits a lateral resistance of greater than 10 to 50 Ohms. Lateral ballasting can provide lower peak current and distributes the current and thermal stress at the insulator sidewalls. At high frequencies, the skin depth alters the current distribution. However, using thin films that are resistive and wide prevents redistribution of current. Vertical ballasting is additionally provided by the presence of insulator films between the conductive films. The vertical ballasting is achieved since the current does not flow between the films. To avoid skin effect vertical redistribution, the insulators serve as a means of preventing vertical current redistribution. By using resistive materials of different TCR values, the TCR value of the net resistor element can be tuned. The magnitude of the different contributions is preferably balanced by both material and width or thickness contributions to the net resistor element. To control the temperature rise in the resistor, various materials can be used to influence the thermal resistance and thermal capacitance. The net temperature rise is a function of the distance from the substrate (what metal level the resistor is on), the insulating layer type and thickness.
In another embodiment of the invention, depicted in the cross-section view of FIG. 2( a ), there is shown a resistive structure 50 including multiple alternating conductive and insulating layers. In this embodiment, the resistive structure 50 is a planar stack of conductive layers 55 a,b,c and insulating layers 52 a,b,c,d , for example. In the resistive structure 50 of FIG. 2( a ), the alternating conductive films are of the same material and may comprise a resistive material including but not limited to: Ta, TaN, Ti, TiN, W, WN or other refractory metal films. Further, the alternating insulating films are of the same material and may comprise a dielectric material including, but not limited to: an oxide, nitride, oxynitride or any combination thereof including multilayers, porous or non-porous inorganic and/or organic dielectrics formed by a deposition process. The resistive element may be formed as part of an interlevel circuit or comprise part of an interconnect structure as shown connected to another wire level 59 by one or more conducting vias 58 a,b,c which electrically connects each conductor layer 55 a,b,c to the adjacent wire level. It is understood that the vias may alternately connect some or all of the conductor layers of the multi-layer planar resistive structure 50 to the adjacent wire level 59 in the achievement of a desired design parameter.
In another embodiment depicted in the cross-section view of FIG. 2( b ), there is shown a resistive structure 60 including multiple alternating conductive and insulating layers. In this embodiment, the resistive structure 60 is a planar stack of conductive layers 65 a,b,c and insulating layers 62 a,b,c,d , for example. In the resistive structure 60 of FIG. 2( b ), the alternating conductive films each comprise a different conductive material and each alternating insulating film may comprise the same dielectric material. As in the other embodiments depicted herein, vias 68 a,b,c , may alternately connect some or all of the conductor layers of the multi-layer planar resistive structure 60 to the adjacent wire level 69 in the achievement of a desired design parameter.
In another embodiment depicted in the cross-section view of FIG. 2( c ), there is shown a resistive structure 70 including multiple alternating conductive and insulating layers. In this embodiment, the resistive structure 70 is a planar stack of conductive layers 75 a,b,c and insulating layers 72 a,b,c,d , for example. In the resistive structure 70 of FIG. 2( c ), the alternating conductive films each comprise a same conductive material and each alternating insulating film may comprise a different dielectric material. The vias 78 a,b,c may connect some or all of the conductor layers of the multi-layer planar resistive structure 70 to an adjacent wire level 79 in the achievement of a desired design parameter.
A methodology 200 for forming the resistive structures depicted in FIGS. 2( a )- 2 ( c ) include a first step 202 of depositing a first interlevel dielectric layer, and, a further step 205 of implementing an atomic layer deposition technique known in the art depositing a resistor film. Next at step 210 , using convention photolithographic techniques, the resistor layer is then etched and stripped at designed locations to accommodate the formed via structures. Then, as depicted at step 220 , a further interlevel dielectric level may be deposited with alternating resistor films within the trough structure. These steps may be repeated to form the alternating conductive and insulating structures with the formed via structures. Then, as depicted at step 230 , a chemical mechanical polish (CMP) technique is used to planarize and clean the structure. As shown in further step 235 , a top metal wire structure is deposited and etched with via fill. Known single or dual damascene techniques may be employed.
It should be understood that, in each of the resistive structures depicted in FIGS. 2( a )- 2 ( c ), the lateral resistor ballasting is established if the conductive materials exhibit a lateral resistance of greater than 10 to 50 Ohms. Lateral ballasting can provide lower peak current and distributes the current and thermal stress at the insulator sidewalls. At high frequencies, the skin depth alters the current distribution. However, using thin films that are resistive and wide prevents redistribution of current. Vertical ballasting is additionally provided by the presence of insulator films between the conductive films. The vertical ballasting is achieved since the current does not flow between the films. To avoid skin effect vertical redistribution, the insulators serve as a means of preventing vertical current redistribution, i.e., serves as a means for limiting current flow perpendicular to the insulator film surfaces. Further, by using resistive materials of different TCR values, the TCR value of the net resistor element can be tuned. The magnitude of the different contributions is preferably balanced by both material and width or thickness contributions to the net resistor element. Moreover, to control the temperature rise in the resistor, various materials can be used to influence the thermal resistance and thermal capacitance. The net temperature rise is a function of the distance from the substrate (what metal level the resistor is on), the insulating layer type and thickness. For instance, it is desired that the insulator film layers are thinner than the adjacent conductive layers so that the thermal conductivity difference and temperature gradient, from one conductor to another, is reduced or negligible. This is desirable because the more uniform the temperature is across the physical structure the less temperature gradient and hence, less thermal stress which can cause cracking. By making thin dielectric layers, the thermal gradient is very small laterally thus maintaining temperature uniformity because of the self-ballasting of the film. Furthermore, it is desired that the insulator layers are uniform is undesirable because, difference in thickness may contribute to bad modeling in the modeling techniques described hereinafter.
The present invention additionally provides for a Computer Aided Design (CAD) methodology and structure for providing design, verification and checking of high current characteristics and ESD robustness of a resistor element in an analog, digital, and RF circuits, system-on-a-chip environment in a design environment which utilizes parameterized cells. That is, a CAD strategy is implemented that provides design flexibility, RF characterization and ESD robustness of the resistor element. This resistor element may be constructed in a primitive or hierarchical “parameterized” cell, hereinafter referred to as a “p-cell”, which may be constructed into a higher level resistor element. This resistor element may further be integrated into a hierarchical structure that includes other elements which do not necessarily include resistor elements, and becomes a component within the hierarchical structure of the network. These resistor elements may be the lowest order p-cells and capable of RF and de characterization. High current analysis, ESD verification, dc characterization, schematics and LVS (Logical Verification to Schematic) are completed on the resistor element. Elements that may be integrated into a hierarchical network may comprise diode, bipolar and MOSFET hierarchical cells. The parameterized cells, or “p-cells”, may be constructed in a commercially available CAD software environment such as CADENCE®-(Cadence Design Systems, Inc., San Jose, Calif.), e.g., in the form of a kit.
FIG. 5 illustrates a CAD design tool concept whereby a computer 300 is implemented that interacts with Graphical generator and Schematic generator processing sub-systems 305 , 310 , respectively. These graphical and schematic generator sub-systems interact with each other to aid in the generation of resistor p-cells, e.g., including the resistor structures as described herein. For instance, the graphical generator 305 generates a physical layout of a resistor structure and the schematic generator 310 will generate a schematic view of the structure that is suitable for specification in a designed circuit. All designs generated by the system are subject to a verification checking sub-system 320 to verify design integrity and ensure no technology rules are violated. Thus, for instance, as shown in detail in FIG. 6 , via a user interface, a resistor p-cell 325 is designed via the graphical and schematic design sub-systems 305 , 310 and the design system and the verification checking sub-system 320 will implement design checking rules, e.g., check the physical layout of the p-cell and ensure that it conforms to physical layout rules or violates any technology rules, for example.
FIG. 7 depicts an implementation of the design system of the present invention implemented in CADENCE. Via the graphical user interface (GUI) 330 of computer device 300 , create generator module 340 and placement generator module 345 are implemented for designing the resistor p-cell elements and generating circuits employing the resistor p-cells, respectively. In the design of the resistor p-cell element, several views are possible including a layout (graphical) view, a schematic view and/or a symbol view which enables generation of a symbol, for instance, having associated stored physical information.
FIG. 8( a ) depicts conceptually, the p-cell graphical design system 350 according to the invention. As shown in FIG. 8( a ), functionality provided via graphical generator 305 is invoked to design graphic p-cells, e.g., a resistor p-cell 350 . P-cell elements 351 , 352 may be combined and merged by a compile function to generate a hierarchical graphical p-cell 360 , or a higher order element. Thus, for instance, a second order resistor element may be generated inheriting parameters of a lower p-cell (e.g. a single order) resistor element. The same analysis is applicable for the schematic generation sub-system. FIG. 8( b ) depicts conceptually, the p-cell schematic design system 370 according to the invention. As shown in FIG. 8( b ), functionality provided via schematic generator 310 is invoked to design schematic p-cells, e.g., a resistor circuit element p-cell 370 . Circuit p-cell elements 371 , 372 may be combined and merged by the compile function 355 to generate a hierarchical schematic p-cell, or a higher order circuit element 365 . The p-cells 360 , 365 are hierarchical and built from device primitives which have been RF characterized and modeled. Without the need for additional RF characterization, the design kit development cycle is compressed. Auto-generation also allows for DRC (Design Rule Checking) correct layouts and LVS correct circuits.
Thus, as exemplified in FIGS. 8( a ) and 8 ( b ), resistor p-cells are “growable” elements such that they can form repetition groups of an underlying p-cell element to accommodate the design parameters. That is, they can be changed in physical size based on the criteria autogenerated. The p-cells fix some variables, and pass some variables to higher order p-cell circuits through inheritance. For example, from a base resistor p-cell 350 , there can be constructed a plurality of p-cells 351 , 352 where each conductive layer is a p-cell and the composite resistor element 360 is a hierarchical p-cell comprising of the plurality of conductive films such as described herein with respect to FIGS. 1 and 2 . The plurality of films can be constructed within a given primitive p-cell.
As an example of the schematic methodology, FIG. 9( a ) depicts an exemplary schematic editing graphical unit interface (GUI) 330 , invoking functionality for constructing a transistor p-cell 331 , a capacitor p-cell 332 , or a resistor p-cell 335 or, for invoking an AMS (Analog Mixed Signal) utility choice 336 . For example, upon selection of the resistor p-cell 335 , a resistor pull-down menu 380 is displayed providing design options including: Create a resistor element choice 381 , Create and place a resistor element choice 382 , place an existing resistor element choice 383 , and place a resistor schematic choice 384 . In the CAD design system aspect of the invention, the schematic p-cell is generated by the input variables to account for the inherited parameters input values. To retain resistor circuit variability, a design flow has been built around the schematic p-cell.
As an example, the selection of “Create a resistor element” function 381 initiates creation of a schematic for a parameterized resistor cell (resistor p-cell). To generate the electrical schematic, via the pull-down menu 390 depicted in FIG. 9( b ), the design panel requests the designer to input parameters, such as: TCR 391 , Ballasting 392 , ESD protection 393 and a net resistance value 394 . Other parameters of interest or desired features that may be entered via the GUI include, but are not limited to: the width, the length, the net total resistance, the maximum mechanical stress integrity value, the maximum peak temperature thermal integrity value, the mechanical or thermal strain limit, the resistance, the worst case capacitance, the worst case inductance, the Q (quality factor), the worst case TCR, the high current limit the worst case ESD robustness level (e.g., human body model (HBM)), machine model (MM), charged device model (CDM), transmission line pulse current (TLP)), and other design parameters. This implementation and definition is performed via input from the GUI to define the parameters. It is understood that other resistor parameters may additionally be integrated with the design system.
These input parameters are passed into a procedure that will build a resistor p-cell with the schematic p-cell built according to the input parameters and placed in the designated resistor cell. An instance of the resistor layout p-cell will also be placed in the designated resistor cell. For example, FIG. 9( c ) illustrates an example resistor p-cell GUI panel showing a built resistor P-cell having attributes including: a resistor cell type 396 , a type of technology 397 , a library name 398 , a resistor value (e.g. 50 Ohms), a TCR value (e.g., 1%) and an ESD value (e.g., 4000 V).
In the computer aided design (CAD) system and methodology, a parameterized cell (p-cell) is thus constructed as a primary cell or a hierarchical cell consisting of a plurality of primitive cells to generate the resistor element. The resistor element parameters can be chosen from electrical circuit values, and/or RF features desired. From the electrical schematic, a symbol function can be created representing and containing all the information of the resistor p-cell. In the case of the resistor p-cell, the hierarchical p-cell information is included in a “translation box” 400 such as shown in FIG. 10 that include a plurality of input connections 402 and output connections 404 that may be later specified for connection in a circuit to achieve a certain performance or parameter value, e.g., a resistance or ESD robustness value, when included in a circuit application. For instance, a symbol view 400 , representing the built resistor, may be specified for connection in an RF circuit 500 such as shown in FIG. 11 , for example, by selecting a “Place an resistor circuit” option (not shown) via the GUI. Generation of the graphical implementation is achievable using the translation box that generates the graphical implementation of the resistor element. The graphical implementation will have the information stored in the translation box and may reconstruct the multi-film resistor design implementing the variable information stored constraints contained in the translation box.
The CAD design kit of the present invention further enables the automated building of a resistor library by creating and storing both schematic, layout, and symbol views of the p-cell element including associated specified input parameters and physical models.
For instance, as electrical and thermal characteristics of a design are additionally influenced by the surrounding insulator films, and “fill shapes” placed around the film, in the implementation of the invention, the physical model for evaluation of the electrical and thermal characteristics include algorithms or physical models that characterize the physical structure. These can also be obtained from experimental work and a “look-up table” that may be placed in the design system as a GUI to assist the user in choosing the parameters of interest. For example, the Smith-Littau model is used to determine the maximum current and voltage across a resistor element as a function of an applied pulse width or energy. As known to skilled artisans, various models exist that allow quantification of the electrical and thermal failure of the structure. The p-cell may be a GUI that allows generation of the fill-shapes to modify the thermal characteristics of the resistor film. The GUI may be used also to choose whether the surrounding interlevel dielectric films are high-k or low-k materials.
The resistor element design may further allow for “Cheesing” which is a process where holes are placed in a film to establish mechanical stability of the element. If the user desires the resistor element may be auto-cheesed. This will allow thermal and mechanical stability wherein the design would auto-adjust to the correct size to achieve the other desired parameters.
The design system further provides a tunable thermal resistance feature that attempts to satisfy the desired characteristic by material changes, widths, dielectric film spacing, and material types. Additionally, it can change the thermal impedance, thermal resistance and thermal capacitance as well as Quality Factor (QF) or Q of the resistor by adjusting the electrical capacitance, inductance and other parasitic features.
Further, according to the invention, a methodology is provided that allows for the auto-generation of the schematic circuit to be placed directly into the design. This procedure is available with a “Place a resistor schematic” option (not shown) via the user GUI that enables the designer to auto-generate the circuit and place it in the schematic. Since these cells are hierarchical, the primitive devices and auto-wiring are placed by creating an instance of the schematic p-cell and then flattening the element.
To maintain the hierarchy during the layout phase of the design, an instance box is placed in the schematic retaining the input parameters and device names and characteristics as properties and the elements are recognized and the primitives are replaced with the hierarchical p-cell.
To produce multiple implementations using different inherited parameter variable inputs, different embodiments of the same circuit type may be created by the methodology of the invention. In this process, the schematic is renamed to be able to produce multiple implementations in a common chip or design; the renaming process allows for the design system to distinguish multiple cell views to be present in a common design.
When the inherited parameters are defined, the circuit schematic is generated according to the selected variables. For example, substrate, ground and pin connections are established for the system to identify the connectivity of the circuit.
The design system may additionally auto-generate the layout from the electrical schematic which will appear as equivalent to the previously discussed graphical implementation.
The physical layout of the resistors circuits is implemented with p-cells using existing primitives in the reference library. The circuit topology is formed within the p-cell including wiring such that all parasitics may be accounted for.
It should be understood that the design system and methodology permits for change of circuit topology as well as structure size of the resistor structure in an automated fashion. Layout and circuit schematics are auto-generated with the user varying the number of elements in the circuit. The circuit topology automation allows for the customer to auto-generate new resistor elements without additional design work. Interconnects and wiring to and between the resistor elements are also auto-generated.
The resistor elements described herein with respect to FIGS. 1 and 2 and embodied as a hierarchical parameterized cell designed via the CAD tool kit of the invention, may thus be designed with the following achievable design objectives including, but not limited to: 1) verification of the connection between a first and second element by verifying and checking electrical connectivity wherein the first element is a p-cell and the second element is a p-cell; 2) verification of the width requirements to maintain high current and ESD robustness to a minimum level; 3) verify that based on the high current or ESD robustness of the ESD network that the resistor width and via number is such to avoid electrical interconnect failure prior to the ESD network failure; 4) allow for parallel resistors whose cross section can be maintained and evaluated as a set of parallel resistors; 5) allow for “resistor ballasting” by dividing into a plurality or array of resistors; 6) allow for calculation of the high current robustness of the resistor based on pulse width, surrounding insulator materials (e.g. SiO.sub.2 or low K materials), metal level and distance from the substrate (thermal resistance based on the metal level or underlying structures; 7) account for surrounding fill shapes around the resistor p-cell; and, 8) account and adjust for “cheesing” (removal of interconnect material inside the interconnect) of the resistor element.
Various modifications may be made to the structures of the invention as set forth above without departing from the spirit and scope of the invention as described and claimed. Various aspects of the embodiments described above may be combined and/or modified.
While the invention has been particularly shown and described with respect to illustrative and preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in form and details may be made therein without departing from the spirit and scope of the invention that should be limited only by the scope of the appended claims.
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A resistor device structure and method of manufacture therefore, wherein the resistor device structure invention includes a plurality of alternating conductive film and insulative film layers, at least two of the conductive film layers being electrically connected in parallel to provide for high current flow through the resistor device at high frequencies with increased temperature and mechanical stability. The alternating conductive film and insulative film layers may be of a planar or non-planar geometric spatial orientation. The alternating conductive film and insulative film layers may include lateral and vertical portions designed to enable a uniform current density flow within the structure itself through a self-ballasting effect within the physical resistor. A computer aided design tool with graphical and schematic features is provided to enable generation of hierarchical parameterized cells for a resistor element with the ability to provide customization, personalization and tunability of TCR, TCR matching, and high current and ESD robustness.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of U.S. Provisional Patent Application No. 61/204,059, filed Dec. 31, 2008, and is incorporated herein by reference.
GOVERNMENT RIGHTS
[0002] The present application was made with the United States government support under Contract No. N88858, awarded by the United States Navy. The United States government has certain rights in the present application.
FIELD OF THE INVENTION
[0003] The present invention relates generally to gas turbine engines and more particularly to systems, apparatuses, and methods of harnessing thermal energy of gas turbine engine(s).
BACKGROUND
[0004] Gas turbine engines are an efficient source of energy and have proven useful to propel aircraft and other flying machines, for electricity generation, as well as for other uses. One aspect of gas turbine engines is that they produce significant amounts of thermal energy during operation. It is well understood that some thermal energy is harnessed by a gas turbine engine during its operation; however, a significant amount of thermal energy is not harnessed or put to use and is lost. Thus, there remains a need for systems, apparatuses, and methods of harnessing thermal energy of gas turbine engine(s).
SUMMARY
[0005] One embodiment according to the present invention is a unique system for harnessing thermal energy of a gas turbine engine. Other embodiments include unique apparatuses, systems, devices, and methods relating to gas turbine engines. Further embodiments, forms, objects, features, advantages, aspects, and benefits of the present invention shall become apparent from the following description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is an illustrative view of an aircraft propelled by two gas turbine engines.
[0007] FIG. 2 is a schematic representation of a gas turbine engine.
[0008] FIG. 3 is a system schematic according to one embodiment of the present invention.
[0009] FIG. 4 is a schematic timeline of an apparatus in several states according to one embodiment of the present invention.
DETAILED DESCRIPTION
[0010] For purposes of promoting an understanding of the principles of the invention, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same. It will 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.
[0011] With reference to FIG. 1 , there is shown airplane 100 including gas turbine engine engines 110 and 120 which operate to propel airplane 100 . Airplane 100 is one example of a use to which gas turbine engines can be put. There are a variety of additional applications for gas turbine engines, including, for example, electricity generation, pumping sets for gas and oil transmission lines, land and naval propulsion, and still other applications. It should be appreciated that systems, apparatuses, and methods according to the present invention can be used in connection with the gamut of gas turbine engine applications. Thus, while the following description is in the context of one embodiment of a gas turbine engine suitable for aircraft propulsion, the invention broadly applies to the aforementioned applications and others.
[0012] With reference to FIG. 2 , there is illustrated a schematic view of a gas turbine engine 200 which includes a compression system 215 , a combustor section 223 , and a turbine section 224 that are integrated together to produce an aircraft flight propulsion engine. In one form, the compression system 215 includes a fan section 221 and a compressor section 222 . This type of gas turbine engine is generally referred to as a turbo-fan. One alternate form of a gas turbine engine includes a compressor, a combustor, and a turbine that have been integrated together to produce an aircraft flight propulsion engine without-the fan section. The term aircraft broadly includes helicopters, airplanes, missiles, unmanned space devices and any other substantially similar devices. It is important to appreciate that there are a multitude of ways in which the gas turbine engine components can be linked together. For example, additional compressors and turbines could be added with intercoolers connecting between the compressors and reheat combustion chambers could be added between the turbines. A wide variety of additional configurations and variations are also possible.
[0013] The compressor section 222 includes a rotor 219 having a plurality of compressor blades 228 coupled thereto. The rotor 219 is affixed to a shaft 225 that is rotatable within the gas turbine engine 220 . A plurality of compressor vanes 229 are positioned within the compressor section 222 to direct the fluid flow relative to blades 228 . Turbine section 224 includes a plurality of turbine blades 230 that are coupled to a rotor disk 231 . The rotor disk 231 is affixed to the shaft 225 , which is rotatable within the gas turbine engine 220 . Energy extracted in the turbine section 224 from the hot gas exiting the combustor section 223 is transmitted through shaft 225 to drive the compressor section 222 . Further, a plurality of turbine vanes 232 are positioned within the turbine section 224 to direct the hot gaseous flow stream exiting the combustor section 223 .
[0014] The turbine section 224 provides power to a fan shaft 226 , which drives the fan section 221 . The fan section 221 includes a fan 218 having a plurality of fan blades 233 . Air enters the gas turbine engine 220 in the direction of arrows A and passes through the fan section 221 into the compressor section 222 and a bypass duct 227 . The term airfoil will be utilized herein to refer to fan blades, fan vanes, compressor blades, turbine blades, compressor vanes, and turbine vanes unless specifically stated otherwise. Further details related to the principles and components of a conventional gas turbine engine will not be described herein as they are known to one of ordinary skill in the art.
[0015] With reference to FIG. 3 there is shown a system 300 according to one embodiment of the present invention. System 300 includes a gas turbine engine 310 which includes a housing 312 . A chamber 314 is coupled to housing 312 and contains water 316 . In an operational state, engine 310 rapidly becomes hot (for example up to 3000° C. or more) as indicates by letter H. In a non operational state engine 310 can be at room temperature, or at other non-operational temperatures as indicated by letters RT. At room temperature water 316 is in a substantially liquid physical phase; however, at an operational temperature, water 316 will undergo a phase change to become super heated steam. Given the high operating temperature of engine 310 this phase change can occur very rapidly, and can be nearly instantaneous upon engine operation. In certain applications, such as aircraft, additional heat can be generated on or about housing 314 through air drag. Such heat resulting from engine operation can be harnessed according to various embodiments of the present invention.
[0016] It should be appreciated that the illustrated coupling of engine 310 and chamber 314 where housing 312 and chamber 314 share a common wall is only one exemplary configuration. A number of other embodiments are contemplated, for example, coupling where the chamber is separated from the housing by one or more additional walls or other structures, or a portion of the chamber or some intermediate heat transfer structure extends into or through housing 312 . Regardless of the particular configuration, system 300 includes thermal coupling of engine 310 and water 316 effective to promote or cause a phase change of water 316 . Thermal coupling can include conduction, convention, radiation, or combination of these and other modes of heat transfer. It should also be appreciated that a variety of materials having the capacity to change phases within the operational/non-operational range of engine 310 could be used instead of or in addition to water. For example, materials such as other motive fluids for gas turbine engines or combinations of these or other materials could also be used. There may also be provided one or more devices to introduce additional water to chamber 314 .
[0017] Chamber 314 is coupled to valve 320 by conduit 318 . Though not illustrated, an additional valve, such as a steam valve or one way flow valve, can optionally be provided between chamber 314 and valve 320 to control movement of matter from chamber 314 to or at some position along conduit 318 . Several such additional valves and other intermediate parts or pathways could also be included. Once water 316 changes phase to steam, assuming no barrier exists, it travels to or pressurizes a flow passage within conduit 318 as indicated by arrow S 1 . Steam then travels through conduit 318 and ultimately encounters valve 320 as indicated by arrow S 2 . Valve 320 can be closed, open to the right so that steam travels to conduit 322 in the direction indicated by arrow S 3 , open to the left so that steam travels to conduit 324 in the direction indicated by arrow S 4 , partially open in either or both directions, or open to provide external venting such as in the case of an emergency vent.
[0018] Conduits 322 and 324 are coupled to actuator 330 . Conduit 322 leads to chamber 333 as illustrated by arrow S 5 . Conduit 324 leads to chamber 332 as illustrated by arrow S 6 . Thus, depending upon the setting of valve 320 , the relative pressure of chambers 332 and 333 can be varied. Such variation can cause movement of piston 331 which in turn can move rod 333 and ultimately act upon load 350 . As arrow M-M shows, this motion can be reciprocation. A variety or other movement can also occur, for example, rotation, vibration, twisting, torque, orbital motion, bending, and virtually any other manner of movement, force or action. It should also be appreciated that a variety of other actuators could be used to accomplish a variety of other purposes. For example, the actuator could include or could be coupled to a variable geometry actuator, such as a piston, operable to drive the variable geometry of a compressor. The actuator could include or could be coupled to an injector for direct injection into one or more locations in a gas turbine engine which could result in a variety of pollution and performance improvements. Furthermore, the actuator could include or could be coupled to an electrical generator such as a small steam turbine or other generation device. Additionally, the actuator could include or could be coupled to an injector for injection into the exhaust stream for IR or noise suppression purposes. Thus it will be understood that actuators according to various embodiments of the present invention include the foregoing and other devices operable to move, apply force, transfer matter such as steam or other motive fluid, and/or do some work.
[0019] With reference to FIG. 4 there is shown a timeline 400 illustrating an apparatus 410 in several states 410 A, 410 B, 410 C, 410 D, 410 E, and 410 F. Each state corresponds to a time along timeline T O -T N , specifically, state 410 A is at or about time T O , state 410 B is at or about time T 1 , state 410 C is at or about time T 2 , state 410 D is at or about time T 3 , state 410 E is at or about time T 4 , and state 410 F is at or about time T 5 . The several states of apparatus 410 each include a gas turbine engine including a housing 412 which is coupled to a chamber 414 which contains a liquid or other phase excitable material. A flow path 418 can interconnect chamber 414 and actuator 430 . There is also provided a triggerable pressure inducement element 490 which could be, for example, an explosive, a combustible, a valve opening to a pressure source such as a tank of flow passage, a cartridge, a compressor, an injector or any other source of pressure or combination of sources. For convenience element 490 is illustrated as an explosive; however, the foregoing and other alternatives are also contemplated.
[0020] Along the timeline T O -T N apparatus 410 begins at T O in a room temperature or other non-operational state. Water or other matter 416 is in a liquid phase. Explosive 490 is un-exploded, but triggerable by a variety of techniques. Then at T 1 explosive 490 is triggered. At T 2 explosive force begins traveling along pathway 418 as shown by the arrows. At T 3 the explosive force reaches actuator 430 . At T 4 (which could be simultaneous or subsequent to T 3 ) actuator 430 is actuated. Also at (or before or subsequent to) T 4 , the engine is started and moves from non-operational temperature to a hot operating state. Through transfer across a heat transfer interface, such as the illustrated intermediate metal wall structure, but optionally any of a wide variety of heat transfer structures including sinks, conductors, piping, counter flow, and/or combinations of these ant other interfaces, a phase change or excitement in matter 416 occurs. At T 5 the phase change or excitement reaches and actuates actuator 430 .
[0021] While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment(s), but rather, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as permitted under the law. Furthermore it should be understood that while the use of the word preferable, preferably, or preferred in the description above indicates that feature so described may be more desirable, it nonetheless may not be necessary and any embodiment lacking the same may be contemplated as within the scope of the invention, that scope being defined by the claims that follow. In reading the claims it is intended that when words such as “a,” “an,” “at least one” and “at least a portion” are used, there is no intention to limit the claim to only one item unless specifically stated to the contrary in the claim. Further, when the language “at least a portion” and/or “a portion” is used the item may include a portion and/or the entire item unless specifically stated to the contrary.
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One embodiment according to the present invention is a unique system for harnessing thermal energy of a gas turbine engine. Other embodiments include unique apparatuses, systems, devices, and methods relating to gas turbine engines. Further embodiments, forms, objects, features, advantages, aspects, and benefits of the present invention shall become apparent from the following description and drawings.
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BACKGROUND OF THE INVENTION
This invention relates to a method of producing graphite fluoride in the form of ultrafine particles excellent in dispersibility by direct fluorination of carbon black.
Graphite fluoride is a common name of polycarbon fluorides represented by (CF x ) n , wherein x is up to about 1.3. At present, most of graphite fluorides on the market are either (CF) n or (C 2 F) n . Graphite fluoride possesses distinctive properties including unusually low surface energy and has acquired importance as a widely applicable industrial material. For example, graphite fluoride is of use as lubricant, as water- and oil-repellent and also as an active material for cell electrodes.
Graphite fluoride is obtained by directly fluorinating a solid carbon material with fluorine gas usually diluted with an inactive gas. However, mainly for the following reasons, the gas-solid contact reaction to form a desired polycarbon fluoride is not easy to industrially carry out and must be carried out under deliberately chosen and strictly controlled conditions, which are considerably variable depending on the kind and physical form of the carbon material. The reaction between solid carbon and fluorine gas to form, for example, (CF) n or (C 2 F) n is highly exothermic, and the formed polycarbon fluoride is liable to further react with fluorine gas to decompose into solid carbon and gaseous fluorocarbons such as CF 4 and C 2 F 6 . Such decomposition reaction is also exothermic. Besides, some side reactions are likely to take place between solid carbon and fluorine gas to form gaseous perfluorocarbons. As a matter of inconvenience, both the decomposition reaction and side reactions can proceed at temperatures near the temperature suitable for the intended reaction.
As to the starting material, a wide selection can be made from various forms of carbon such as natural or synthetic graphite, petroleum coke, pitch coke, carbon black, activated carbon and carbon fibers. In most cases coke or graphite is used by reason of relative ease of converting into graphite fluoride, and the fluorination reaction is carried out at 300°-500° C. Usually, graphite fluoride powders produced in this way are 1-50 μm in mean particle size.
Recently it is expanding to utilize excellent lubricity or water- and oil-repellency of graphite fluoride in composite materials comprising plastics, aqueous liquid or organic liquid as a principal component. For such applications, dispersibility of graphite fluoride becomes a very important factor. Since dispersibility of a powdery material depends greatly on the particle size, there is a keen demand for ultrafine particles, i.e. submicron particles, of graphite fluoride.
A conceivable way to obtain very fine particles of graphite fluoride is reducing the particle size of graphite fluoride powder obtained by the conventional synthesis process with a pulverizing machine. However, by this method it is very difficult and almost impracticable to obtain submicron particles of graphite fluoride. Even though the pulverizing operation is combined with classification operations, the ultimate particle is about 1 μm at best. Besides, this method entails considerable cost.
Another way is fluorinating a carbon material in the form of ultrafine particles. In this case consideration must be given to the fact that the particle size of the obtained graphite becomes more than twice the particle size of the starting carbon material by reason of intrusion of fluorine atoms between the carbon network layers. That is, the particle size of the starting material needs to be smaller than 0.5 μm for obtaining submicron particles of graphite fluoride. Therefore, the starting carbon material is limited to carbon black. However, it is not easy to industrially produce graphite fluoride from carbon black primarily because ultrafine particles of carbon black exhibit very high activity with fluorine and readily undergo the aforementioned side reactions to form gaseous perfluorocarbons. Accordingly the fluorination operation has to be performed with a countermeasure against the obstructive side reactions even though productivity of the operation is inevitably sacrificed. For example, JP-A 58-167414 proposes diluting 100 parts by weight of carbon black to be fluorinated with more than 50 parts by weight of graphite fluoride powder.
However, experiments have revealed that graphite fluoride carefully produced from carbon black does not greatly differ from ordinary graphite fluoride produced from petroleum coke in respect of dispersibility in water containing a surfactant or organic liquids such as alcohols and oils. Furthermore, even graphite fluoride produced from carbon black has a mean particle size larger than 1 μm when measured by a sedimentation method using correlation of particle size with settling velocity of particles well dispersed in a liquid.
In JP-A 61-218697, we have shown that graphite fluoride excellent in lubricity and improved in dispersibility is obtained by using, as the starting material, a graphitized carbon black having in its crystalline structure interlayer spacings of 3.38-3.55 Å determined by the X-ray diffraction (002). However, the particles of this graphite fluoride are not submicron when measured by a sedimentation method.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method for easily and efficiently producing graphite fluoride in the form of ultrafine or submicron particles excellent in dispersibility.
To accomplish the above object the present invention provides a method of producing graphite fluoride, which belongs to direct fluorination of a carbon black with fluorine gas at an elevated temperature and is characterized in that acetylene black is used as said carbon black.
The method according to the invention, like known methods using carbon black as the starting material, provides graphite fluoride of the type represented by (CF) n .
Graphite fluoride produced by the method of the invention is far smaller than 1 μm in mean particle size measured by a sedimentation method and exhibits excellent dispersibility in various dispersion media. This graphite fluoride is excellent also in lubricity and water- and oil-repellency. Furthermore, the fluorination reaction can easily be accomplished with very high yield of graphite fluoride with little formation of gaseous perfluorocarbons. We have confirmed that such advantages can be gained exclusively when acetylene black is used as the starting carbon material. Use of any other type of carbon black does not produce comparably good results.
Probably the advantages of the method according to the invention are attributed to uniqueness of acetylene black in both chemical composition and crystalline structure. Compared with other carbon blacks, acetylene black is significantly higher in the content of carbon and considerably lower in the contents of hydrogen and other volatile matter. As to physiochemical nature, it is distinctive of acetylene black that the primary particles are closely joining with each other to provide a well-developed chain structure. Furthermore, by virtue of its very high purity acetylene black has layers of well-developed hexagonal network with carbon atoms and, hence, is high in crystallinity. Needless to mention, acetylene black has a mean particle size far smaller than 1 μm.
DETAILED DESCRIPTION OF THE INVENTION
Carbon black is produced from hydrocarbons by incomplete combustion or by thermal decomposition. The incomplete combustion method is classified into four types, viz., gas furnace process to which natural gas is the principal feed, oil furnace process using heavy petroleum oils such as creosote oil and ethylene bottom oil, channel process using natural gas and lamp process using coal or heavy oils. The thermal decomposition method is classified into so-called thermal process decomposing natural gas and acetylene process employing exclusively acetylene as the feed. Currently, oil furnace black and gas furnace black, and particularly the former, constitute more than 90% of industrially produced carbon black, and it is not exaggeration to say that in practical sense "carbon black" refers to furnace black unless otherwise noted.
Mean particle sizes of available carbon blacks range from about 8 nm to about 500 nm. However, conversion of carbon black into graphite fluoride is accompanied by great enlargement of particle size as mentioned hereinbefore, and we have found that use of acetylene black is essential to the acquirement of graphite fluoride very excellent in dispersibility and smaller than 1000 nm in mean particle size measured by a sedimentation method.
For example, in the case of producing graphite fluoride from a furnace black the yield of the fluorination reaction is not good, and, even though the primary particles of the employed furnace black are smaller than 50 nm, the obtained graphite fluoride is larger than 1000 nm in mean particle size measured by a sedimentation method and in this regard does not distinctly differ from graphite fluoride produced from petroleum coke. Presumably this is because of very strong cohesion of the graphite fluoride particles. The channel process can provide carbon black smaller in particle size than furnace blacks, but this process suffers from very low yield and high cost and is not likely to stably supply carbon black of a given quality on an industrial scale. Lamp black is highly active to fluorine, and experiments have revealed impracticability of stably producing graphite fluoride from lamp black. Thermal black is relatively large (larger than 100 nm) in the size of primary particles and has proved inferior to acetylene black as a carbon material for producing graphite fluoride.
As a fluorinating gas in the method according to the invention, it is suitable to employ a mixture of not more than 30% by volume of fluorine gas and the balance of an inactive gas such as argon or nitrogen is suitable. When the concentration of fluorine in the employed gas is more than 30% the rate of the reaction between carbon (acetylene black) and fluorine becomes too high, and the side reactions to form perfluorocarbons and/or decomposition of the formed graphite fluoride into carbon and perfluorocarbons are likely to take place. It is preferred to use a mixed gas containing not more than 20% by volume of fluorine gas.
It is suitable to carry out the fluorination reaction at temperatures in the range from 320° to 400° C. When the reaction temperature is below 320° C. the rate of reaction is very low so that a very long time is needed to practically complete the reaction. When the reaction temperature is above 400° C. the rate of reaction becomes too high, and the adverse influence of the aforementioned decomposition and side reactions on the yield of graphite fluoride augments.
EXAMPLE
A commercial acetylene black (supplied from Denki Kagaku Kogyo Co., Ltd.) having a mean particle size (primary particles) of 42 nm was used as the starting material. According to the specifications this acetylene black was as high as 99.8% in carbon content and as low as 0.4% in hydrogen content. By powder X-ray diffractometry with Cu-K.sub.α line using silicon as standard, the acetylene black had interlayer spacings d 002 of 3.53 Å.
To synthesize graphite fluoride, 10 g of the acetylene black was charged in a reactor made of nickel, and the atmosphere in the apparatus was replaced by a mixed gas consisting of 20 vol% of fluorine and 80 vol% of argon. At room temperature the mixed gas pressure in the apparatus was regulated to the atmospheric pressure. After that the mixed gas was continuously passed through the reactor at a flow rate of 100 ml/min, while the temperature in the reactor was gradually raised at a rate of 5° C./min until the temperature reached 380° C. Thereafter the feed of the mixed gas was continued for 30 hr while the temperature was maintained at 380° C. to thereby accomplish fluorination of the acetylene black to (CF) n .
The weight of the obtained graphite fluoride, W p , and the content of fluorine, C F (%), were measured to calculate the yield of the graphite fluoride on the basis of the weight of the starting carbon material, W c , by the following equation: ##EQU1## The yield was 99%.
As to mean particle size of the obtained graphite fluoride, a particle size distribution analyzer of the centrifugal sedimentation type was used for measurement in view of the fact that dispersibility of the analyzed powder too is reflected in the result of this analysis. Ethyl alcohol was employed as the liquid medium. As the result, the graphite fluoride had a mean particle size of 380 nm.
As Comparative Examples 1 to 3, two kinds of furnace blacks and a graphitized carbon black were respectively fluorinated by the same method as in the foregoing Example except that the fluorinating reaction temperature was varied as shown in Table 1. The graphitized carbon black was obtained by heat treatment (above 2000° C.) of a furnace black. The interlayer spacings d 002 and mean particle size of each carbon black were as shown in Table 1. In Comparative Examples 1-3, the yield and mean particle size of each product were determined by the same methods as in Example. The results are shown in Table 1.
TABLE 1______________________________________ GraphiteCarbon Black Fluoride Mean Mean Parti- Fluorination Parti- cle Conditions cle d.sub.002 Size.sup.(*) Temp. Time Yield SizeKind (Å) (nm) (°C.) (hr) (%) (nm)______________________________________acetyleneblack 3.53 42 380 30 99 380(Example)furnaceblack 3.60 30 260 30 75 2950(Comp. Ex. 1)furnaceblack 3.58 40 260 30 78 3200(Comp. Ex. 2)graphitizedcarbon black 3.44 94 420 30 99 1050(Comp. Ex. 3)______________________________________ .sup.(*) primary particles
As can be seen clearly in the Table, when acetylene black was used as the starting carbon material graphite fluoride was obtained at very high yield, and the particle size of the obtained graphite fluoride was remarkably small. In contrast, the graphite fluorides produced from furnace blacks were very larger in particle size though the primary particles of the furnace blacks were fairly small.
Furthermore, dispersibilities of the graphite fluorides obtained in the above Example and Comparative Examples were examined by the following test method.
First, 1 g of the graphite fluoride for testing was added to 99 g of an organic liquid, which was alternatively selected from ethanol, acetone and butyl ether, and was dispersed in the liquid by an ultrasonic agitation method. The resultant dispersion was put into a 100 ml test tube (25 mm in inner diameter and 250 mm in length) and was left standing. As the graphite fluoride particles slowly settled an upper layer of the liquid in the test tube gradually became clear and almost transparent. The vertical distance between the liquid surface in the test tube and the interface between the clear liquid layer and the lower layer in which graphite fluoride particles were still dispersed slowly increased as time elapsed. The measurements were as shown in Tables 2 to 4, wherein "settling level" refers to the aforementioned interface.
The results of this test are clearly indicative of superiority in dispersibility of the graphite fluoride produced from acetylene black.
TABLE 2______________________________________Settling in Ethanol Distance of Settling Level from Liquid Surface (mm)Graphite Elapsed Time (days)Fluoride 1 2 4 8 20______________________________________Example -- -- 2 9 20Comp. Ex. 1 4 11 21 44 >100Comp. Ex. 2 4 11 22 50 >100Comp. Ex. 3 1 3 7 18 45______________________________________
TABLE 3______________________________________Settling in Acetone Distance of Settling Level from Liquid Surface (mm)Graphite Elapsed Time (days)Fluoride 1 2 4 8 20______________________________________Example 3 6 12 24 60Comp. Ex. 1 25 40 70 >100Comp. Ex. 2 30 42 75 >100Comp. Ex. 3 10 16 30 58 >100______________________________________
TABLE 4______________________________________Settling in Butyl Ether Distance of Settling Level from Liquid Surface (mm)Graphite Elapsed Time (days)Fluoride 1 2 4 8 20______________________________________Example -- -- 1 4 20Comp. Ex. 1 2 6 15 28 >100Comp. Ex. 2 2 9 17 30 >100Comp. Ex. 3 -- 2 5 12 50______________________________________
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Graphite fluoride in the form of submicron particles is easily obtained at high yield by using, exclusively, acetylene black as the carbon material to be fluorinated with fluorine gas. Use of any other type of carbon black does not give comparable results. Graphite fluoride produced from acetylene black is superior in dispersibility.
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FIELD OF THE INVENTION
This invention relates to a novel silicone resin composition capable of endowing articles fabricated therewith with very much improved mechanical properties, such as, flexural strength as well as excellent antisolvent resistance and thermal stability.
DESCRIPTION OF THE PRIOR ART
Silicone resins have become widely employed in a wide variety of commercial applications including the manufacture of electric insulation materials by virtue of their excellent thermal stability and electric insulation despite the defect of articles made therefrom, i.e., relatively poor mechanical strength. In fact, articles fabricated with conventional silicone resin compositions have rather poor mechanical strengths at room temperature, but superior mechanical strengths after prolonged heating at 300°C or higher, compared to articles fabricated with such resins as phenol resins, epoxy resins and unsaturated polyester resins that are usually employed as constructive materials. The conventional silicone resin articles used as parts for electric insulation or high-temperature duty often become cracked or broken off at the corners when they are fastened or connected to other devices or parts by caulking, bolting, or by other means. For purposes of improving the mechanical strength of the finished articles, it have been proposed to impregnate the silicone resins with glass fibers. However, the silicone resin compositions which are loaded with as high as 50% by weight of glass fiber required for satisfactory improvement of the mechanical strength are so bulky that their workability becomes very poor and makes fabrication with these materials very difficult and troublesome. In addition, such fabricated articles loaded with the reinforcing glass fiber can exhibit a considerably improved impact strength, but their flexural strength is improved only by 1.5 to 2 times which is unsatisfactory, or is about the same or lower than that of articles made from ordinary organic resin other than silicone resins with no impregnated reinforcing material.
Furthermore the silicone resin articles have rather a poor anti-solvent resistance, and are not suitable for use as, for example, laminated products which are used in places in contact with an organic solvent.
OBJECTS OF THE INVENTION
Therefore, it is an object of this invention to provide silicone resin compositions having good workability for molding, laminating and other fabricating means. A further object of the invention is to provide silicone resin compositions that are capable of endowing articles made therefrom with excellent properties with respect to thermal stability, electric characteristics, and anti-solvent resistance as well as mechanical strength.
SUMMARY OF THE INVENTION
The present invention provides silicone resin compositions free from the above drawbacks and comprising the following components.
a. 100 parts by weight of an organopolysiloxane resin represented by the average unit formula ##EQU1## where R 1 is a substituted or unsubstituted monovalent hydrocarbon group and m is a positive number from 0.5 to 1.8 having at least 0.25% by weight of residual hydroxy groups directly bonded to silicon atoms,
b. from 5 to 300 parts by weight of a phenolic prepolymer represented by the general formula ##SPC1##
where A is a halogen atom, an alkoxy group, or a phenolic group of the general formula ##SPC2##
R 2 is an organic group or an amino group, a is 1, 2 or 3, b is 0, 1 or 2 with the proviso that the total value of a and b is equal to or less than 4 and n is a positive integer,
c. a silanol-condensation catalyst, and
d. a curing catalyst for phenol resins.
DETAILED DESCRIPTION OF THE INVENTION
To describe the invention in detail, component (a) contained in its composition is a conventional organopolysiloxane resin represented by the average unit formula (I) above. The organopolysiloxane is composed of several siloxane units, such as, C 6 H 5 SiO 1 .5, (C 6 H 5 ) 2 SiO, CH 3 SiO 1 .5, (CH 3 ) 2 SiO, (CH 3 )(C 6 H 5 )SiO, CH 2 =CHSiO 1 .5, (CH 2 =CH)(CH 3 )SiO, C 2 H 5 SiO 1 .5, SiO 2 and CF 3 CH 2 CH 2 CH 2 SiO 1 .5. It is formed by cohydrolysis of a mixture of corresponding chlorosilanes or alkoxysilanes, followed by the dehydration condensation of the hydrolyzate. In the organopolysiloxane according to the invention, the ratio of the number of organic groups R 1 bonded to silicon atoms to the number of the silicon atoms Si, vig., R 1 /Si, must be within the range from 0.5 to 1.8. Further it is required that the organopolysiloxane has at least 0.25% by weight of residual hydroxy groups directly bonded to the silicon atoms. When the R 1 /Si ratio is smaller than 0.5, the siloxane resins have such high functionality that they tend to gel during the preparation of the proposed composition, and articles fabricated therefrom usually exhibit a very high brittleness. On the contrary, when the R 1 /Si ratio is larger than 1.8, the compositions have an extremely low curing velocity, and articles fabricated therefrom are inferior in hardness and thermal stability. Further, if the amount of the silicon-bonded residual hydroxy groups is smaller than 0.25% by weight, the curing velocity of the resin composition is unduly low, and fabricated articles made from such composition have poor mechanical strengths as well as heat softening properties. Its preferable range is from 1 to 5% by weight.
Component (b) contained in the compositions of the present invention is a phenolic prepolymer represented by formula (II) above, being the most characteristic component for the composition to be endowed with the desirable properties. This component (b) may be prepared by a condensation reaction in the presence of a Friedel-Crafts catalyst, e.g., SnCl 4 , between a phenolic compound and an α,α'-dialkoxyxylene according to the following reaction formula: ##SPC3##
or by a dehydrohalogenation reaction in the presence of the same catalyst between a phenolic compound and an α,α'-dihalogenoxylene according to the following reaction formula: ##SPC4##
In the above reaction formulas, the symbols A, R 2 , a, b and n have the same meanings as in the definition of formula (II), and R' denotes an alkyl group, such as, methyl, ethyl, propyl and butyl, and X is a halogen atom. The groups denoted by R 2 are exemplified by organic groups, such as, --CH 3 , --C 2 H 5 , --C 3 H 7 , --C(CH 3 ) 3 , --C(C 2 H 5 ) 2 (C 3 H 7 ), --C(CH 3 )(C 3 H 7 ) 2 , --C(CH 3 )(C 2 H 5 )(C 4 H 9 ), --C(CH 3 ) 2 (C 6 H 11 ), --C 6 H 5 , --CH(C 6 H 4 OH)(C 2 H 5 ) and --CH 2 (C 6 H 4 OH), and an amino group --NH 2 .
Component (b) has a molecular weight in a range such that it may be appropriately called a prepolymer with n having a value not exceeding 12 at the highest or most usually up to 7. Values of n which are too high lead to poor workability or flow behavior for the resin compositions concerned.
Component (b) has a curing mechanisms similar to those of novolac-type phenol resins, for it is a prepolymer of a thermo-setting resin which is curable to three-dimensional structure by the action of a curing catalyst such as hexamethylenetetramine. Component (b) itself is usually employed in the form of powdery or granular molding materials or prepregs for lamination capable of giving fabricated articles with mechanical strengths 2 to 3 times higher than those of articles formed of conventional silicone resins, as well as with excellent anti-solvent resistance.
Generally, materials for fabrication prepared from such a phenolic prepolymer introduce several problems to the processes of fabrication. Namely, the materials cannot attain complete curing even with a sufficient amount, e.g. up to 10 to 20% by weight, of a curing catalyst in the fabrication process at 160° to 180°C, leading to the necessity of postcuring at 200° to 250°C in order to complete the final curing. Because of the large volume of gas evolution in the fabrication step, fabricated articles are apt to become blistered on release of pressure by opening the metal mold which has been operated with heating in a closed condition. The undesired blistering phenomenon should be avoided by carrying out troublesome degassing during the initial 1 to 2 minutes of the molding operation at a rate of 2 to 3 times per minute. Furthermore, postcuring has to be conducted very carefully in an oven under a precise temperature control, beginning with about 170°C and ending at 250°C after about 24 hours, the temperatures being elevated in a stepwise manner. This is because the fabricated articles to be postcured tend to become blistered or cracked when abruptly and directly put into an atmosphere at a temperature higher than 200°C, and possess very poor mechanical strengths and electric insulation.
On the other hand, it is the usual understanding that the direct blending of two different kinds of thermosetting resins does not produce a favorable effect to the properties of the resultant mixed resins, but rather lead to an unexpected enlargement of the defects in both resins. One of the widely adopted techniques in resin blending is the addition of a third substance with relatively good compatibility with each of the resins to be blended. Alternatively, the resins are chemically combined in advance by cocondensation or copolymerization. Both techniques are sometimes impractical due to complexity in the processing along with the adverse effects, such as, lower curability due to decreased functional groups and poorer workability in the fabrication due to decreased flowing.
The resin composition prepared by blending components (a) and (b) with the addition of a silanol-condensation catalyst and a curing catalyst for phenol resins in accordance with the present invention can be cured satisfactorily by heating to form fabricated articles endowed with ideally excellent properties, i.e., thermal stability and electric properties that are ascribable to the existence of component (a) and mechanical strengths and anti-solvent resistance that are ascribable to the existence of component (b), regardless of the completely dissimilar molecular structures and curing mechanisms of the two components.
The fabrication process of the composition in accordance with the present invention may be the same as that of the conventional silicone resin-based compositions. The workability of the compositions of the invention is very good with no blistering even when they are fabricated into rather thick articles. Further, the postcuring of fabricated articles can satisfactorily be carried out by directly putting them into an atmosphere of a temperature ranging from 200° to 250°C without stepwise temperature elevation. The remarkable advantages of the present invention described above cannot be expected from the knowledge in the prior art.
The silanol-condensation catalyst as component (c) included in the composition of the present invention may be any of the conventional ones, for example, organic amines, such as, monoethanolamine, diethanolamine, ethylenediamine, triethylenediamine and triethanolamine, heavy metal compounds, such as, lead oxides, lead carbonate, lead octoate, carboxylic acids including acetic acid, stearic acid and octylic acid, and salts of carboxylic acids and heavy metals (for example, iron, lead, zinc, cobalt and manganese), and quaternary ammonium compounds, such as, tetramethylammonium hydroxide. This component (c) is present in an amount of from 0.01 to 3% by weight based on the amount of component (a).
The curing catalyst for phenol resins as component (d) may also be any of the conventional ones, but the most preferred is hexamethylenetetramine. This component (d) is present in an amount of from 1 to 20% by weight, preferably from 5 to 15% by weight, based on the amount of component (b). Larger amounts of component (d) usually result in a poorer flow to the fabricating composition. In particular, when hexamethylenetetramine is used as the curing catalyst in excess amounts, there arises the undesired blistering phenomenon due to the generation of ammonia gas in large amounts when it is decomposed, and also the deterioration of the electric properties due to ammonia remaining in the finished articles.
The silicone resin composition of the present invention may be optionally admixed with inorganic fillers, thermally-stable pigments, lubricants and other additives. Illustrative of the inorganic fillers are powdery fillers, such as, diatomaceous earth, clay, powdered quartz, powdered fused quartz, glass powder, glass beads, magnesia, titanium dioxide and alumina, and fibrous fillers, such as, glass fiber, asbestos fiber and carbon fiber. The fibrous fillers include those represented by chopped strands having a relatively short length of fibers, say, in the range of from 1 to 10 mm, those represented by rovings and yarns shaped into fluxes of sufficiently long filaments and those represented by cloths and mats that are sheet-shaped.
The silicone resin compositions of the present invention are obtained in the form of powdery or granular molding material or in the form of sheet-like material for lamination. According to the invention, components (a) to (d) are optionally blended with other additives, such as, fillers, pigments, and lubricants by means of, for example, a two-roller mill heated at a temperature higher than the softening temperature of either component (a) or (b), and the blended composition is cooled and crushed into powders or granules. In an alternative method, the mixture of components (c), (d) and, optionally, the other additives are added to a solution of components (a) and (b) in an organic solvent, such as, ketones (e.g., acetone and methylethylketone) or ethers of ethyleneglycol (e.g., ethyleneglycol monoethylether) to produce a dispersion, and with the dispersion thus produced, rovings, yarns, cloths or mats of glass, asbestos or carbon fibers are impregnated by spraying or dipping. The thus impregnated fibrous materials are then dried and finished into materials suitable for filament winding techniques using long filaments, materials suitable for compression molding using filaments 3 to 10 mm long cut and sheet-like materials suitable for lamination.
The molding techniques for the silicone resin compositions of the present invention may include compression molding, transfer molding, injection molding and the like. Recommended conditions for compression molding involve the temperature of the metal mold being from 160° to 200°C, the pressure being from 10 to 400 kg/cm 2 and the molding time being from 3 to 5 minutes; those for transfer molding involve the temperature of the metal mold being from 160° to 200°C and the molding time being from 1 to 3 minutes; and those for injection molding involve the temperature of the metal mold being from 170° to 220°C and the molding time being from 30 seconds to 2 minutes. In any of the fabrication techniques, postcuring is indispensable in order to obtain articles having the highest mechanical strengths and other physical properties. The temperature at which the postcuring is carried out is preferably in the range of from 200° to 250°C, and fabricated articles to be postcured may be put directly into the atmosphere kept at the above temperature. Since the postcuring process can be carried out in an atmosphere without the necessity of the stepwise temperature elevation as in the fabrication of the conventional silicone resin compositions, the compositions of the present invention can offer a very high productivity of fabricated articles.
The finished articles obtained from the compositions of the present invention in accordance with the above-described procedure have mechanical strengths sufficient to withstand cracking due to any stress in the fastening by caulking, bolting or by other means, as well as excellent thermal stability and anti-solvent resistance.
The following examples are to illustrate the present invention. The parts and percentages in the examples are all parts and percentages by weight, if not otherwise indicated.
Example 1
Mixtures (Samples 1, 2, 3 and 4) were formulated by adding, to 100 parts of a silicone resin composed of 50 mole % of CH 3 SiO 1 .5 units, 35 mole % of C 6 H 5 SiO 1 .5 units and 15 mole % of (C 6 H 5 ) 2 SiO units and having 4.2% of residual hydroxy groups directly bonded to the silicon atoms, a phenolic prepolymer obtained by the condensation reaction between α,α'-dimethoxyparaxylene and phenol in the presence of SnCl 4 as a Friedel-Crafts catalyst and expressed by the formula ##SPC5##
in varied amounts as set out in Table I, together with 1 part of lead carbonate, 1 part of benzoic acid, 11% of hexamethylenetetramine based on the amount of the phenolic prepolymer, 200% of quartz powder based on the total amount of the silicone resin and the phenolic prepolymer and 1% of calcium stearate based on the total amount of the silicone resin and the phenolic prepolymer. The resulting mixtures were kneaded on a hot roller mill at 90°C for 10 minutes to form compositions, which were then cooled and crushed to give molding compositions.
As controls, Samples 5 and 6 were similarly formulated, however one excluded the phenolic prepolymer and the other excluded the silicone resin.
Each of the molding compositions thus obtained were fabricated by compression molding at 180°C under a pressure of 100 kg/cm 2 for 5 minutes with subsequent postcuring at 200°C for 2 hours. The thus fabricated articles were tested to determine the various properties. The results are shown in Table I.
Table I______________________________________Sample No. 1 2 3 4 5 6**______________________________________Silicone resin,parts 100 100 100 100 100 0Phenolic prepolymer,parts 10 50 100 200 0 100Flexural strength,determined at roomtemperature, kg/mm.sup.2 Initially 7.5 8.9 9.4 10.3 6.0 11.5 After aging of: 24 hrs. at 300°C 7.3 8.5 9.0 9.7 5.8 6.7 48 hrs. at 300°C 7.0 8.1 8.5 9.3 5.8 2.3Dielectric strength,× 10.sup..sup.-3 5.3 7.8 8.5 9.2 3.3 13.0Anti-arc resistance,sec. 250 240 240 230 250 185Anti-solventresistance, %* 90 95 95 100 85 100______________________________________ *Test pieces immersed in toluene at 90°C for 100 hours were tested for flexural strength and the results were given in percent of the value before immersion in toluene. **Lead carbonate and benzoic acid were omitted.
Example 2
A mixture (Sample No. 7) was formulated by adding, to 100 parts of a silicone resin composed of 30 mole % of CH 3 SiO 1 .5 units, 10 mole % of (CH 3 ) 2 SiO units, 10 mole % of (CH 3 ) (C 6 H 5 )SiO units and 50 mole % of C 6 H 5 SiO 1 .5 units and having 1.6% of residual hydroxy groups directly bonded to the silicon atoms, 100 parts of a phenolic prepolymer prepared by the condensation reaction between α,α'-dimethoxyparaxylene and p-phenylphenol in the presence of SnCl 4 as a Friedel-Crafts catalyst and expressed by the formula ##SPC6##
80 parts of diatomaceous earth, 0.2 part of triethanolamine, 13 parts of hexamethylenetetramine, 0.2 part of propionic acid and 2 parts of calcium stearate. The resulting mixture was put into 300 parts of methylethylketone and well blended together on a ball mill for 16 hours to form a uniform dispersion, having a viscosity of 100 centipoise at 20°C.
Into the dispersion thus obtained, a piece of glass cloth (WE-17-104B, Nitto Spinning Co., Japan) was dipped, followed by taking it out and drying at 130°C for 1 minute to remove the solvent (methylethylketone) and produce prepregs with 50% solid pick up. 30 Sheets of these prepregs were pressed together at 170°C under pressure of 80 kg/cm 2 for 15 minutes with subsequent postcuring at 200°C for 2 hours, to form a laminated plate 3.5 mm thick. The properties of the laminate thus obtained are shown in Table II.
As controls, Samples 8 and 9, one excluding the phenolic prepolymer and the other excluding the silicone resin, were formulated as follows. Sample 8 was formulated by mixing 100 parts of the silicone resin, 1 part of lead carbonate, 1 part of benzoic acid, 40 parts of diatomaceous earth and 1 part of calcium stearate, and putting the resulting mixture into 150 parts of methylethylketone, to form a uniform dispersion having a viscosity of 105 centipoise at 20°C. Sample 9 was formulated by mixing 100 parts of phenolic prepolymer, 40 parts of diatomaceous earth, 12 parts of hexamethylenetetramine and 1 part of calcium stearate and putting the resulting mixture into 150 parts of methylethylketone to form a uniform dispersion having a viscosity of 120 centipoise at 20°C.
These control samples 8 and 9 were subjected to the same procedure as Sample 7, and the resulting laminates were tested to determine their properties. The results are set out in Table II.
Table II______________________________________Sample No. 7 8 9______________________________________Flexural strength,determined at roomtemperature, kg/mm.sup.2 Initially 38 18 50 After aging of: 24 hrs. at 300°C 31 17 13 48 hrs. at 300°C 28 17 6Dielectric strength,× 10.sup..sup.-3 7.3 2.7 15Anti-arc resistance,sec. 230 250 180Anti-solventresistance, % 95 75 100______________________________________
Example 3
Into a Henschel mixer were charged 100 parts of a silicone resin composed of 30 mole % of CH 3 SiO 1 .5 units, 30 mole % of (CH 3 ) (CH 6 H 5 )SiO units, 20 mole % of (C 6 H 5 ) 2 SiO units and 20 mole % of C 6 H 5 SiO 1 .5 units and having 3.7% of residual hydroxy groups directly bonded to the silicon atoms, 300 parts of a phenolic prepolymer prepared by the dehydrochlorination reaction between α,α'-dichloroparaxylene and phenol in the presence of SnCl 4 as a Friedel-Crafts catalyst and expressed by the formula ##SPC7##
and further 300 parts of powdery fused quartz, 100 parts of alumina powder, 100 parts of glass chopped strands having fibers 6 mm long, 1 part of lead carbonate, 1 part of lauric acid, 30 parts of hexamethylenetetramine and 1.2 parts of calcium stearate. The mixer thus loaded was operated for 7 minutes at a velocity of 1,200 r.p.m. with its jacket heated at 50°C, to form a granular composition having an average particle size of about 15 mesh (Tyler).
The molding composition (Sample 10) thus prepared was then fabricated with a screw-in-line type injection molding machine (Model KI-50, Matsuda Works Co., Japan) with the metal mold heated at 190°C at a rate of 1 shot per 1.5 minutes. The various properties of the thus fabricated articles are shown in Table III.
As controls, samples 11 and 12 were prepared as follows. Sample 11 was formulated with the silicone resin only, excluding the phenolic prepolymer and hexamethylenetetramine, the amounts of the silicone resin, lead carbonate and lauric acid being increased to 400 parts, 4 parts and 4 parts, respectively. Sample 12 was formulated with the phenolic prepolymer only, excluding the silicone resin, lead carbonate and lauric acid, the amounts of the phenolic resin and hexamethylenetetramine being increased to 400 parts and 40 parts, respectively, and those of the other components being the same as used in the formulation of Sample 10.
Table III______________________________________Sample No. 10 11 12______________________________________Flexural strength,determined at roomtemperature, kg/mm.sup.2 Initially 10.5 6.5 12.3 After aging of: 24 hrs. at 300°C 9.8 6.3 6.7 48 hrs. at 300°C 8.3 6.0 2.2Dielectric strength,× 10.sup..sup.-3 9.4 3.7 12Anti-arc resistance,sec. 200 250 180Anti-solventresistance, % 95 80 100______________________________________
Example 4
A dispersion in ethyleneglycol monoethylether, having a 55% solid content was prepared by dispersing the same phenolic prepolymer as employed in Example 1 and a silicone resin composed of 20 mole % of SiO 2 units, 20 mole % of CH 3 SiO 1 .5 units, 50 mole % of C 6 H 5 SiO 1 .5 units and 10 mole % of (CH 3 ).sub. 2 SiO units and having 4.7% of residual hydroxy groups directly bonded to the silicon atoms in the amounts indicated in Table IV together with 20% of clay, 1% of calcium stearate and 20% of titanium dioxide, all based on the total amount of the silicone resin and the phenolic prepolymer, 0.3% of each triethylenediamine and phthalic acid based on the amount of the silicone resin and 12% of hexamethylenetetramine based on the amount of the phenolic prepolymer.
Glass rovings (ER-2310, Asahi Glass Fiber Co., Japan) were dipped in the dispersion prepared above and dried at 150°C to remove the solvent with subsequent cutting in 6 mm lengths into a molding composition. The solid pick up of the rovings was 45%. The molding composition was fabricated by compression molding at 170°C under pressure of 350 kg/cm 2 for 7 minutes. The properties of the fabricated articles are shown in Table IV.
Table IV______________________________________Sample No. 13 14 15 16* 17*______________________________________Silicone resin,parts 100 100 100 100 0Phenolic prepolymer,parts 50 150 250 0 100Flexural strength,determined at roomtemperature, kg/mm.sup.2 Initially 15.9 22.3 25.1 11.3 26.3 After aging of: 24 hrs. at 300°C 14.8 20.2 21.7 10.7 10.1 48 hrs. at 300°C 14.1 19.7 19.7 10.5 5.2Dielectric strength,× 10.sup..sup.-3 6.5 8.5 10 2.8 15Anti-arc resistance,sec. 240 230 210 250 180Anti-solventresistance, % 80 90 95 75 100______________________________________ *Control sample.
Example 5
To 100 parts of the same silicone resin as used in Example 1 were added 100 parts of a phenolic prepolymer expressed by the formula ##SPC8##
prepared in the presence of a Friedel-Crafts catalyst, 1 part of lead carbonate, 1 part of benzoic acid, 11 parts of hexamethylenetetramine, 2 parts of calcium stearate, 200 parts of quartz powder. The resulting mixture (Sample 18) was kneaded on a hot roller mill at 90°C for 10 minutes, and then cooled and crushed to produce a molding composition. This molding composition was fabricated by compression molding at 180°C under the pressure of 100 kg/cm 2 for 5 minutes with subsequent postcuring at 200°C for 2 hours. The thus fabricated article was tested to determine the various properties, the results of which are set out in Table V.
Table V______________________________________Sample 18______________________________________Flexural strength,determined at roomtemperature, kg/mm.sup.2 : Initially 8.8 After aging of: 2 hrs. at 200°C 8.7 48 hrs. at 300°C 7.8Dielectric strength,× 10.sup..sup.-3 9.2Anti-arc resistance,sec. 240Anti-solventresistance, % 95______________________________________
Example 6
A mixture (Sample 19) was prepared by the same procedure as set forth in Example 5 except the phenolic prepolymer was a compound having the following formula: ##SPC9##
From the above mixture was formed a molding composition, and from this molding composition was produced a fabricated article in accordance with the same procedure as indicated in Example 5. The fabricated article exhibited the various properties as set out in Table VI.
Table VI______________________________________Sample 19______________________________________Flexural strength,determined at roomtemperature, kg/mm.sup.2 : Initially 7.8 After aging of: 2 hrs. at 200°C 7.5 48 hrs. at 300°C 7.0Dielectric strength,× 10.sup..sup.-3 9.0Anti-arc resistance,sec. 210Anti-solventresistance, % 90______________________________________
Example 7
A mixture (Sample 20) was prepared by the same procedure as set forth in Example 5 except that the phenolic prepolymer was a compound having a higher polymerization degree and expressed by the following formula: ##SPC10##
From the above mixture was formed a molding composition, and from this molding composition was produced a fabricated article in accordance with the same procedure as indicated in Example 5. The fabricated article exhibited the various properties as set out in Table VII.
Table VII______________________________________Sample 20______________________________________Flexural strength,determined at roomtemperature, kg/mm.sup.2 : Initially 8.8 After aging of: 2 hrs. at 200°C 8.4 48 hrs. at 300°C 8.2Dielectric strength,× 10.sup..sup.-3 8.5Anti-arc resistance,sec. 240Anti-solventresistance, % 95______________________________________
Example 8
A dispersion in ethyl "Cellosolve", having a 55% solid content (Sample 21) was prepared by dispersing 100 parts each of the same silicone resin and phenolic prepolymer as used in Example 4 together with 40 parts of clay, 40 parts of titanium dioxide, 0.09 part of choline (beta-hydroxyethyl-trimethylammonium hydroxide), 0.1 part of 2-ethylhexanoic acid, 12 parts of hexamethylenetetramine and 2 parts of calcium stearic acid. Into this dispersion was dipped the same glass rovings as used in Example 4 so that the solid pick up of the rovings became 45%. The rovings thus treated were heated to 150°C. so that the ethyl "Cellosolve" contained therein evaporated, and then cut into pieces 6 mm long, which were then subjected to fabrication by compression molding at 180°C under a pressure of 350 kg/cm 2 for 7 minutes. The properties of the fabricated article are shown in Table VIII.
Table VIII______________________________________Sample 21______________________________________Flexural strength,determined at roomtemperature, kg/mm.sup.2 : Initially 20.7 After aging of: 24 hrs. at 300°C 19.2 48 hrs. at 300°C 18.5Dielectric strength,× 10.sup..sup.-3 7.2Anti-arc resistance,sec. 230______________________________________
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The resin composition comprises (a) 100 parts by weight of a silicone resin, (b) from 5 to 300 parts by weight of a phenolic prepolymer constructed by repeated xylylene units and phenylene units having phenolic hydroxy groups, (c) a silanol-condensation catalyst, and (d) a curing catalyst for phenol resins. These compositions have a very good processability for fabrication by molding, laminating or by other means, and the fabricated articles can enjoy the excellent properties inherent in silicone resins with respect to thermal stability and electric properties, and in phenolic resins with respect to mechanical strengths and anti-solvent resistance.
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BACKGROUND
The present exemplary embodiment relates to electrical switching mechanisms. It finds particular application in conjunction with medium voltage earthing switches, and will be described with particular reference thereto. However, it is to be appreciated that the present exemplary embodiment is also amenable to other like applications.
It is common to provide protection to technicians servicing an electrical component enclosure through the provision of an earthing switch. A typical earthing switch includes one or more blade contacts mounted on a rotatable shaft. An actuating mechanism rotates the shaft to move the blade contacts between an open position and a closed position in contact with a grounding electrode. The earthing switch is typically installed between a distribution bus and a circuit breaker connecting the distribution bus to a main line. The earthing switch, when closed, grounds the distribution bus.
Prior to earthing the line or bus terminals, it is typical to disconnect the upstream source of electrical power. In certain situations, however, the circuit may inadvertently be live during grounding. In other situations, the upstream source of electrical power may be inadvertently reenergized before performing closing of the switch. In still other situations, there could be back feed of electricity to the distribution bus such as, for example, in the case of a spinning electric motor producing current that back feeds to the distribution bus. Thus, even when the circuit breaker connecting the distribution bus to the main bus is open, current may exist in the distribution bus. In each of the foregoing situations, a properly operating earthing switch can protect technicians and equipment from harm.
Arcing can occur when an earthing switch is closed on a fault. The arcing, in turn, can cause melting of the contact material which can result in welding of the contacts. If the contacts are not opened while the metal is still fluid, a rough surface is produced. The voltage concentrations caused by the spikes on the now rough surface result in an even earlier striking of the arc the next time and can lead to permanent welding of the contacts.
To minimize arcing, many conventional earthing switches include coil springs configured to rapidly close the switch when actuated. Such coil springs are often supported adjacent to the rotatable shaft and operatively coupled to the shaft by a crank arm or other mechanism. When the switch is actuated to close, the spring is configured to act on the crank arm to rapidly rotate the shaft and thereby quickly close the switch.
Current earthing switch designs relying on coil springs are generally bulky since the coil springs and associated mechanisms are supported adjacent the rotating shaft and blade contacts. Further, such prior art earthing switches are not easily scalable to various applications, since most often the blade contacts are welded or otherwise permanently secured to the rotatable shaft. Thus, separate shaft/blade assemblies typically need to be manufactured for different applications.
BRIEF DESCRIPTION
The present disclosure provides a scalable earthing switch that incorporates a torsion spring to effect rapid closure of the switch. The torsion spring is supported coaxially about a rotatable shaft on which contact blades are mounted resulting in a more compact design. The blade contacts are separated axially along the length of the shaft by one or more spacers. By using difference size spacers the distance between adjacent blade contacts can be changed and, thus, the earthing switch can be easily scaled for different applications. A latching (detent) mechanism is provided for latching the switch in an open position.
In accordance with one aspect, an earthing switch for a connecting a power source to ground comprises an actuating mechanism, a rotatable shaft adapted to be rotated by the actuating mechanism, at least one moveable contact secured to the rotatable shaft for movement therewith between an open position and a closed position, a torsion spring for biasing the at least one moveable contact towards the closed position, and a detent mechanism for latching the at least one moveable contact in the open position.
The switch can further include a plurality of moveable contacts secured to the rotatable shaft for movement therewith, the moveable contacts being axially spaced apart along the shaft by at least one spacer. The at least one spacer can be coaxially received over the rotatable shaft, and may be conductive. The at least one moveable contact can include a pair of spaced apart blades adapted to receive a stab therebetween when in the closed position. The at least one moveable contact can include a non-circular bore adapted to be received on a non-circular section of the shaft for fixing the contact for rotation therewith. The actuating mechanism can include a rotary actuating mechanism for rotating the shaft.
The earthing switch can further comprise a mounting bracket, wherein the rotatable shaft is supported on the mounting bracket for rotation, and wherein a coil of the torsion spring is received coaxially over the rotatable shaft, a first end of the torsion spring being engaged with said mounted bracket, and a second end of the torsion spring being operatively connected to the movable contact, whereby rotation of the rotatable shaft in a first direction is opposed by the torsion spring while rotation of the rotatable shaft in the second direction is assisted by the torsion spring.
The detent mechanism can include at least one pawl adapted to engage a surface of a hub associated with the actuating mechanism for latching the switch in an open position. The at least one pawl can be pivotally mounted to a housing of the actuating mechanism for movement between a radially outer position and a radially inner position relative to the hub whereat the pawl is received in a recess in the hub thereby latching the switch open. A cam member can be provided for radially displacing the at least one pawl from its radially inner position, and the hub and cam can be mounted coaxially on an input shaft of the actuating mechanism whereby rotation of the input shaft from a position corresponding to a latched position of the switch towards a position corresponding to a closed position of the switch causes the cam to radially outwardly displace the at least one pawl from the recess and allow the switch to close.
In accordance with another aspect, a modular earthing switch assembly comprises a support member, a rotatable shaft having a non-circular cross-section supported for rotation on said support member, a moveable contact mountable on the rotatable shaft in a plurality of positions, the moveable contact having a bore with a non-circular cross-section for telescoping over the non-circular cross-section of the rotatable shaft thereby fixing the movable contact for rotation with the rotatable shaft, and at least one spacer received coaxially on the rotatable shaft and located adjacent the moveable contact, the at least one spacer axially locating the moveable contact along the rotatable shaft.
The switch can further include a torsion spring for biasing the movable contact towards a closed position. A mounting bracket can be provided, wherein the rotatable shaft is supported on the mounting bracket for rotation, and wherein a coil of the torsion spring is received coaxially over the rotatable shaft, a first end of the torsion spring being engaged with said mounted bracket, and a second end of the torsion spring being operatively connected to the movable contact, whereby rotation of the rotatable shaft in a first direction is opposed by the torsion spring while rotation of the rotatable shaft in the second direction is assisted by the torsion spring. The at least one moveable contact can include a pair of spaced apart blades adapted to receive a stab therebetween when in the closed position.
The switch can also include an actuating mechanism for rotating the shaft to effect movement of the at least one movable member between an open position and a closed position. A detent mechanism can be provided including at least one pawl adapted to engage a surface of a hub associated with the actuating mechanism for latching the switch in an open position. The at least one pawl can be pivotally mounted to a housing of the actuating mechanism for movement between a radially outer position and a radially inner position relative to the hub whereat the pawl is received in a recess in the hub for latching the switch open. A cam member can be provided for radially displacing the at least one pawl from its radially inner position, and the hub and cam can be mounted coaxially on an input shaft of the actuating mechanism whereby rotation of the input shaft from a position corresponding to a latched position of the switch towards a position corresponding to a closed position of the switch causes the cam to radially outwardly displace the at least one pawl from the recess and allow the switch to close.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an exemplary earthing switch in accordance with the disclosure;
FIG. 2 is an exploded view of the exemplary earthing switch of FIG. 1 ;
FIG. 3 is an enlarged view of the exemplary earthing switch of FIG. 1 showing details of the torsion spring;
FIG. 4 is an side elevational view of the exemplary earthing switch showing the torsion spring and set screw for adjusting torsion spring tension;
FIG. 5 is a perspective view of a latching mechanism of the exemplary earthing switch in a first position;
FIG. 6 is a front elevational view of the earthing switch in the position shown in FIG. 5 ;
FIG. 7 is a perspective view of the exemplary earthing switch in a second position;
FIG. 8 is a front elevational view of the earthing switch in the position shown in FIG. 7 .
DETAILED DESCRIPTION
With reference to FIG. 1 , an exemplary earthing switch 10 in accordance with the disclosure is illustrated. The earthing switch 10 generally includes a rotatable actuating shaft 14 on which a plurality of blade contacts 18 are mounted for rotation therewith between an open position and a closed position wherein said contacts 18 engage respective line/load stabs. An actuating mechanism, including an input shaft 22 and gearbox 26 , is connected to the actuating shaft 14 for moving the blade contacts 18 between the open and closed positions. Unlike prior art earthing switches that utilize coil-over springs, the earthing switch 10 utilizes a torsion spring 30 arranged coaxially with the actuating shaft 14 for biasing the blade contacts 18 towards the closed position. This results in a compact design that can be easily scaled for various applications. All of the components are supported on a mounting bracket 34 that can be mounted to a desired surface, such as within an electrical cabinet or the like.
With additional reference to FIG. 2 , the details of the exemplary earthing switch 10 will be described. The mounting bracket 34 includes a base plate 36 , a gear box end plate 38 secured to the base plate 36 , and a shaft end plate 38 also secured to the base plate 36 . The mounting bracket 34 includes a plurality of holes for securing the same to a desired surface using one or more suitable fasteners. The gear box 26 is secured to the base plate 36 and end plate 38 via a plurality of bolts 44 . A first end of the actuating shaft 14 is received through an opening 46 in the gear box 26 and supported therein for rotation. A second end of the actuating shaft 14 is supported for rotation by a bearing 48 secured to the shaft end plate 38 by bolts 50 .
The actuating shaft 14 includes a non-circular portion 54 thereof on which the plurality of blade contacts 18 are mounted. In the illustrated embodiment, the non-circular portion 54 of the actuating shaft 14 has a hexagonal cross-section, but other non-circular shapes could be used. Each blade contact 18 comprises a pair of individual blades 56 , each having an opening 58 in an end thereof having a cross-sectional shape corresponding to the cross-sectional shape of the non-circular portion 54 of the actuating shaft 14 . When received on the non-circular portion 54 , each blade 56 is fixed for rotation with the actuating shaft 14 .
The axially outer blade contacts 18 are mounted to the actuating shaft 14 with a ground spacer 60 disposed between each respective blade 56 at its point of attachment to the actuating shaft 14 . Like each blade 56 , each ground spacer 60 is keyed to the actuating shaft for rotation therewith. To this end, each ground spacer 60 has a central bore 62 having a cross-sectional shape that corresponds to the non-circular portion 54 of the actuating shaft. As will be described in more detail below, each ground spacer 60 also includes first and second radially extending ears 64 having stop surfaces 66 for limiting the extent of rotation of the actuating shaft 14 . The stop surfaces 66 make contact with the baseplate 36 when the actuating shaft 14 is rotated a predetermined amount in either direction. Accordingly, the ground spacers 60 act as limiters to prevent over-rotation of the shaft 14 .
Each ground spacer 60 further includes a bore 68 provided for connecting each ground spacer 60 to a grounding strap (not shown). The middle blade contact 18 has a spacer 69 between respective blades 56 . The spacer 69 is not a ground spacer (e.g., it does not have a tab for connection to a ground strap), although a ground spacer could be utilized in that position as well if desired.
A pair of tubular spacers 70 are provided for locating and/or spacing the blade contacts 18 axially along the actuating shaft 14 . The tubular spacers 70 also support the torsion spring 30 and, as such, can have an outer circumference that is closer in size to an inner circumference of the torsion spring 30 than is the outer circumference of the actuating shaft 14 . Together, the actuating shaft and blade contact assembly including ground spacers 60 , spacer 69 , and spacers 70 , define a conductive ground path from the blade contacts 18 to ground.
Opposite tails 74 of the dual coil torsion spring 30 are received in spring holes 76 that secure the spring 30 to respective blade contacts 18 . With reference to FIGS. 3 and 4 , a central portion 78 of the spring 30 between respective coils includes tab 79 . Tab 79 is a generally u-shape extension of the spring 30 that is configured to engage a set screw 80 mounted to the bracket 30 to thereby restrict rotation of the tab 79 relative to the bracket. Set screw 80 can be adjusted to adjust the tension (preload) of the torsion spring 30 . For example, the set screw can be unscrewed from the position shown in FIGS. 3 and 4 thereby displacing the tab 79 upward and increasing the spring preload. In contrast, if the set screw is screwed in further from the position shown, the preload of the spring will be reduced.
All of the components mounted on the actuating shaft 14 are secured thereon between hex nut portion 81 at a first end of the shaft 14 , and a hex nut 82 and washer 83 secured to the opposite end of the shaft 14 . As will be appreciated, the actuating shaft and blade contact assembly can be configured using components of differing sizes to produce a switch having a desired size and/or rating. For example, the spacing between the individual blades 56 of the blade contacts 18 can be changed by utilizing ground spacers 60 having a desired thickness. Also, the orientation of the blade contacts 18 can be changed by locating each blade in a desired angular position on the non-circular portion 54 of the actuating shaft 14 . Further, the spacing between each respective blade contact 18 can be altered by using spacers 70 of a desired length. In some cases, a given actuating shaft 14 can be used to support a plurality of configurations of the blade contacts 18 , etc., thereon. In other instances, an actuating shaft having a longer or shorter axial length may be provided instead of the illustrated actuating shaft 14 to accommodate larger or smaller contact assemblies.
As noted, a first end of the actuating shaft 14 is received in the gear box 26 and supported therein for rotation. In this regard, a miter gear 84 is keyed to the end of the actuating shaft via a key 86 received in a keyway of the miter gear 84 . In the illustrated embodiment, the miter gear is secured on the end of the actuating shaft 14 via a e-type circlip 90 , but could be secured to the shaft 14 in any suitable manner.
Miter gear 84 is engaged with a corresponding miter gear 92 that is secured to an end of the input shaft 22 and supported for rotation on a bearing 94 that is secured to the base plate 36 . As will be appreciated, rotation of the input shaft 22 results in rotation of the actuating shaft 14 and corresponding movement of the blade contacts 18 , for example, between their open and closed positions. In order to maintain the switch in an open position against the bias of the torsion spring 30 , miter gear 92 includes a contoured hub 93 that is part of a latching mechanism 96 designed to hold the switch in the open position.
The latching mechanism 96 (also referred to as a detent mechanism) includes a pair of roller pawls 98 adapted to engage and follow respective outer hub surfaces 99 of the contoured hub 93 in a manner that restricts rotation of the gear 92 from a position associated with the contacts 18 being in their open position. In other words, the latching mechanism 96 operates to latch the switch in the open position against the force applied by the torsion spring 30 . Once dislodged from the open position, the latching mechanism 96 allows the torsion spring 30 to rotate the switch contacts 18 unimpeded to the closed position.
Referring now to FIGS. 5 and 6 , the latching mechanism 96 is shown in an unlatched position with the blade contacts 18 being in a closed or partially open position (e.g., not open). The outer hub surfaces 99 of the hub 93 extend from the gear box 26 , with the miter gear 92 itself generally enclosed within the gear box 26 . Each roller pawl 98 is pivotally mounted to the gear box 26 by a bolt 100 , and is biased against the hub 93 via a pawl torsion spring 101 ( FIG. 2 ). Rollers 102 of each roller pawl 98 engage respective hub surfaces 99 of the hub 93 at diametrically opposed positions.
As will be appreciated, the hub surfaces 99 are discontinuous and also diametrically opposed. Each hub surface 99 extends approximately ¼ of the circumference of the hub 93 . In between the hub surfaces 99 are a pair of diametrically opposed recesses 106 in which the respective roller pawls 98 are adapted to reside when the switch is locked in the open position.
With reference to FIGS. 7 and 8 , it will be understood that the pawl torsion springs 101 (only shown in FIG. 2 ) bias the pawls 98 against the hub surfaces 99 such that, when input shaft 22 is rotated and the pawls 99 become aligned with the recesses 106 , the pawls 98 will pivot radially inwardly into the recesses 106 and secure the switch in the open position against the bias of the torsion spring 30 . Once in the position of FIGS. 7 and 8 , the rollers 102 engage end surfaces 110 of the hub 93 and restrict rotation of the hub 93 and by extension the input shaft 24 and actuating shaft 14 . In this position, the pawls 98 are in an “over-center” position with respect to their point of attachment to the housing 26 such that as the torsion spring 30 acts upon the actuating shaft 14 and thereby the hub 93 , the pawls are further driven radially inwardly thereby preventing rotation of the hub 93 and latching the switch open.
To release the latching mechanism 96 , a cam 112 is provided on the input shaft 22 and mounted for rotation therewith. Cam 112 has a pair of diametrically opposed cam lobes 116 adapted to urge the pawls 98 radially outwardly when the input shaft 22 is rotated from the position shown in FIGS. 7 and 8 (e.g., the switch open and latched position) towards a switch closed position (e.g., as shown in FIGS. 5 and 6 ). The cam lobes 116 are positioned radially about the input shaft 22 in a position such that they immediately engage and urge radially outwardly a surface of the pawls 98 , for example the rollers 102 , when the input shaft 22 is rotated from the open and latched position. As the shaft 22 is rotated, the cam lobes 116 radially displace the pawls 98 until the rollers 102 clear the end surfaces 110 at which point the pawls 98 no longer restrict rotation of the hub 93 , and by extension the input shaft 24 and actuating shaft 14 . Accordingly, the torsion spring 30 then can act to rapidly transition the switch to a closed position.
As will now be appreciated, the latching mechanism 96 enables the switch to be maintained in the open position against the force of the torsion spring 30 and then to quickly become unlatched and allow the full force of the torsion spring 30 to act upon the actuating shaft 14 to close the switch. This results in a rapid closure to avoid or minimize arcing issues that can sometimes occur when closing the switch against a fault.
The exemplary embodiment has been described with reference to the preferred embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the exemplary embodiment be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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A scalable earthing switch that incorporates a torsion spring to effect rapid closure of the switch. The torsion spring is supported coaxially about a rotatable shaft on which contact blades are mounted resulting in compact design. The blade contacts are separated axially along the length of the shaft by one or more spacers. By using difference size spacers the distance between adjacent blade contacts can be changed and, thus, the earthing switch can be easily scaled for different applications. A latching (detent) mechanism is provided for latching the switch in an open position.
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BACKGROUND OF THE INVENTION
Various types of plasma reactors employed in the manufacture of semiconductor microelectronic circuits require a large RF electrode at the reactor chamber ceiling that overlies the semiconductor workpiece. Typically, the workpiece is a semiconductor wafer supported on a conductive pedestal. RF power is applied to the support pedestal, and the ceiling or overhead electrode is a counter electrode. In some reactors, the RF power applied to the support pedestal is the plasma source power (determining plasma ion density) and is also the plasma bias power (determining ion energy at the wafer surface). In other reactors, an RF power applicator other than the wafer pedestal furnishes the plasma source power, while the RF power applied to the wafer pedestal serves only as plasma RF bias power. For example, the plasma source power may be applied by an inductive antenna or may be applied by the ceiling electrode. Thus, the ceiling electrode may either be a grounded counter electrode for the RF power applied to the wafer support pedestal or it may be connected to an independent RF power generator and function as an independent RF power applicator. In either case, the most uniform distribution of process gas is obtained by introducing the process gas through the ceiling. This requires that the ceiling electrode be a gas distribution plate.
There is a continuing need to improve the uniformity of process gas distribution across the wafer surface in a plasma reactor, particularly in a plasma reactor used for semiconductor etch processes as well as other semiconductor processes. This need arises from the ever-decreasing device geometries of microelectronic circuits and minimum feature sizes, some approaching 0.15 microns. Such small device geometries are dictated in most cases by the desire for higher microprocessor clock speeds, and require corresponding improvements in etch rates, etch uniformity across the wafer surface and damage-free etching. Previously, with devices having relatively large feature sizes, a single gas inlet in the plasma reactor overhead ceiling electrode/gas distribution plate provided adequate process gas distribution uniformity. A single inlet would necessarily be of a large size in order to meet the requisite gas flow requirements.
One problem with such a large inlet is that it is more susceptible to plasma entering the inlet and causing arcing or plasma light-up within the inlet. Such arcing damages the plate and/or enlarges the inlet and consumes power. Sputtering of the plate material around the inlet can also contaminate the plasma with by-products of the sputtering. With a large hole, the maximum electric field occurs near the center of the hole, and this is the likliest location for plasma light-up or arcing to begin. One solution proposed for reactors having a single gas inlet was to juxtapose a disk or puck in the center of the hole to keep gases away from the intense electric field at the hole center (U.S. Pat. No. 6,885,358 by Dan Maydan). However, with current device geometries incorporating very small feature sizes, much better process gas distribution uniformity across. the wafer surface is required. As a result, a single gas distribution inlet or orifice in the ceiling gas distribution plate is inadequate to provide the requisite gas distribution uniformity. Thus, an overhead gas distribution plate is currently made by drilling thousands of fine holes or orifices through the plate. The spatial distribution of such a large number of orifices improves gas distribution uniformity across the wafer surface. The smaller size makes each hole less susceptible to plasma entering the hole.
Unfortunately, it has not been practical to place or hold an individual puck in the center of each one of the thousands of holes to ward the gas away from the high intensity electric fields near the hole centers. Thus, in order to reduce plasma arcing, the gas inlet holes must be of minimal diameter and within a small dimensional hole-to-hole tolerance to ensure uniform gas distribution. Drilling such a large number of holes is costly. This is because the holes must have such a high aspect ratio, must be drilled through very hard material (such as silicon carbide) and sharp hole edges must be avoided. Moreover, the very need for such accurately sized holes means that performance is easily degraded as hole sizes are enlarged by plasma sputtering of the hole edges. Depending upon plasma ion density distribution across the ceiling surface, some holes will be widened at a greater rate than other holes, so that a gas distribution plate initially having highly uniform gas distribution across the wafer surface eventually fails to provide the requisite uniformity.
Another problem is that the need for greater etch rate has dictated a smaller wafer-to-ceiling gap in order to obtain denser plasma. The small gas orifices produce very high velocity gas streams. The high velocity gas streams thus produced can be so narrowly collimated within the narrow wafer-to-ceiling gap that the hole-to-hole spacing in the gas distribution plate produces corresponding peaks and valleys in gas density at the wafer surface and corresponding non-uniformities in etch rate across the wafer surface.
As a result, there is a need for an overhead gas distribution plate that functions as an electrode or counter electrode, and that is not susceptible to plasma arcing in the gas injection passages, that does not have high gas injection velocities and in which the gas distribution uniformity and velocity are not affected by enlargement of the gas injection passages.
SUMMARY OF THE DISCLOSURE
The invention is embodied in a plasma reactor for processing a semiconductor wafer, the reactor having a gas distribution plate including a front plate in the chamber and a back plate on an external side of the front plate, the gas distribution plate comprising a gas manifold adjacent the back plate, the back and front plates bonded together and forming an assembly. The assembly includes an array of holes through the front plate and communicating with the chamber, at least one gas flow-controlling orifice through the back plate and communicating between the manifold and at least one of the holes, the orifice having a diameter that determines gas flow rate to the at least one hole. In addition, an array of pucks is at least generally congruent with the array of holes and disposed within respective ones of the holes to define annular gas passages for gas flow through the front plate into the chamber, each of the annular gas passages being non-aligned with the orifice.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified cut-away cross-sectional side view of a plasma reactor embodying the present invention.
FIG. 2A is a partially exploded cross-sectional side view of a gas distribution plate of the plasma reactor of FIG. 1 in accordance with a first embodiment.
FIG. 2B is a side view of an assembled gas distribution plate of the plasma reactor corresponding to FIG. 2 A.
FIG. 3A is a plan view of one implementation of the front plate of the gas distribution plate of FIG. 2 B.
FIG. 3B is a plan view of the front plate of FIG. 3A bonded to the back plate in accordance with this implementation.
FIG. 4 is a cross-sectional side view of the assembly of FIG. 3B corresponding to lines 4 — 4 of FIG. 3 B.
FIG. 5 is a cross-sectional side view of a gas distribution plate of the plasma reactor of FIG. 1 in accordance with a second embodiment.
FIG. 6 is a cut-away partially exploded perspective view of a gas distribution plate of the plasma reactor of FIG. 1 in accordance with a third embodiment.
FIG. 7 is a cross-sectional view corresponding to lines 7 — 7 of FIG. 6 .
FIGS. 8A, 8 B, 8 C and 8 D are sequential cut-away partial side views of one portion of a gas distribution plate of FIG. 6, illustrating a first process for fabricating the gas distribution plate of FIG. 6 .
FIGS. 9A, 9 B, 9 C and 9 D are sequential cut-away partial side views of one portion of a gas distribution plate of FIG. 6, illustrating a second process for fabricating the gas distribution plate of FIG. 6 .
FIG. 10 is a cross-sectional side view of a gas distribution plate of the plasma reactor of FIG. 1 in accordance with a third embodiment.
FIG. 11 is a cross-sectional side view of an alternate gas distribution plate as shown in FIG. 10 .
DETAILED DESCRIPTION
Referring to FIG. 1, a plasma reactor includes a vacuum chamber 100 bounded by a reactor chamber cylindrical side wall 105 , a ceiling 110 and floor 115 . A vacuum pump 120 maintains a vacuum within the chamber at a desired chamber pressure. A wafer support pedestal 125 for supporting a semiconductor wafer or workpiece 130 is disposed at the bottom of the chamber 100 so that the wafer 130 faces the ceiling 110 . The wafer support pedestal 125 has conductive elements so that the pedestal 125 can serve as an electrode or RF power applicator. For this purpose, an RF generator 135 is connected to the pedestal 125 through an RF impedance match circuit 140 . The ceiling 110 is conductive in the illustrated embodiment and is connected to the RF return terminal of the RF generator 135 so that the ceiling 110 serves as a counter electrode for the wafer pedestal 125 . In some types of reactors, another RF generator 145 may be connected to the ceiling 110 through an RF impedance match circuit 150 , so that the ceiling 110 also serves as another RF power applicator. In this case, the frequencies of the two RF generators 135 , 145 are very different so that the two RF generators 135 , 145 function independently.
Process gas is introduced so as to provide maximum gas distribution uniformity across the top surface of the wafer 130 by injecting it through many uniformly spaced gas injection inlets 160 in the ceiling 110 . The ceiling 110 is thus a gas distribution plate. A gas source or supply 165 is coupled to a gas manifold 170 in the ceiling/gas distribution plate 110 , and the gas manifold 170 feeds each of the inlets 160 . As shown in FIGS. 2A and 2B, the inlets 160 of the gas distribution plate 110 are formed by two parallel planar plates, namely a back plate 205 and a front plate 210 which are manufactured separately (FIG. 2A) and then bonded together (FIG. 2 B). The back plate 205 is on top and the front plate 210 is on the bottom and faces the plasma in the interior of the chamber 100 . The back plate 205 consists of an array of relatively large cylindrical openings 215 in its bottom surface while the front plate 210 consists of an array of cylindrical pucks 220 matching the array of openings 215 . As shown in FIG. 2B, the pucks 220 of the front plate 210 fit within the openings 215 of the back plate 205 , the clearance between each opening 215 and matching puck 220 forming an annular gap therebetween, the annular gap being the gas inlet 160 . Gas feed orifices 230 in the back plate 205 are sized to provide the precise gas flow desired extend vertically from the gas manifold 170 overlying the back plate 205 to the annular gas inlets 160 . Since the gas distribution plate 110 consists of an array of hundreds or thousands of annular inlets 160 to achieve spatially uniform gas distribution across the entire wafer surface, the inlets 160 would in most cases allow too much gas flow. Therefore, the finely-sized orifices 230 provide the requisite flow control.
Significantly, each orifice 230 faces a horizontal gap 235 between the respective puck 220 and the back plate 205 , so that the gas is forced to make an abrupt turn to enter the gap 235 and another abrupt turn to enter the annular inlet 160 . It is difficult if not impossible for plasma in the chamber travelling upward in the annular inlets 160 to make both of these turns without being extinguished by collisions with the gas distribution plate surfaces within the annular inlet 160 and the horizontal gap 235 . A result is that the precisely sized orifices 230 are protected from plasma sputtering. This leaves only the annular inlets 160 subject to distortion in size from plasma sputtering or attack. However, the area of each annular inlet 160 is so large that plasma sputtering introduces only a small fractional difference in area from inlet to inlet, so that gas distribution uniformity across the wafer surface is virtually immune to such changes. Moreover, in the embodiment of FIGS. 2A and 2B, gas flow uniformity is determined by the uniformity of the orifices 230 only, so that changes in the sizes of the various annular inlets 160 have virtually no affect on gas flow uniformity. Thus, performance of the gas distribution plate 110 is virtually immune to changes induced by plasma sputtering or attack, a significant advantage.
In one embodiment, the back plate 205 and front plate 210 are formed of silicon carbide and are bonded together using existing techniques in silicon carbide manufacturing. One advantage of using silicon carbide as the material of the gas distribution plate 110 is that such material is practically impervious to attack by certain process gases and plasma species, such as halogen-containing process gases and plasma species. Also, silicon carbide is relatively compatible with silicon semiconductor wafer processing, so that contamination from plasma sputtering of such material is not as harmful as are other materials such as aluminum.
Another advantage of the annular-shaped gas inlets 160 is that each puck 220 keeps the plasma ions and gases away from the center of each opening 215 where electric fields are maximum. This feature helps prevent arcing or plasma light-up. The two-plate structure 205 , 210 of the gas distribution plate 110 enables cost-effective manufacture of hundreds or thousands of holes 215 and pucks 220 centered in each of the holes. The invention thus provides an economical gas distribution plate with sufficient uniformity of gas distribution to process extremely fine device features (e.g., 0.15 microns) on a very large wafer (10 inch to 20 inch diameter) with minimal plasma arcing while being impervious to long-term wear from plasma sputtering.
Another advantage is that the relatively large annular openings 160 provide a much lower gas injection velocity. Although each finely sized orifice 230 produces a very high velocity gas stream into the respective horizontal gap 235 , passage through the horizontal gap 235 and through the large annular inlet 160 dissipates its velocity. As a result, the gas flow from the bottom of the front plate 210 is much more uniform and free from high velocity narrow gas streams and plasma plumes. Therefore, a small wafer-to-ceiling gap does not lead to spatial non-uniformities in the gas distribution at the wafer surface using the gas distribution plate 110 , a significant advantage.
Many of the advantages enumerated above are pertinent to problems encountered in high power plasma reactors capable of high plasma ion densities. One of these problems is that high plasma ion density over the wafer surface is achieved in some reactors by a small wafer-to-ceiling gap to better confine the plasma. As noted above, the gas distribution plate 110 provides uniform gas distribution within such a small gap because of the large size of the annular inlets 160 . Another one of these problems is that high plasma ion density is achieved in some reactors by applying plasma source power to the ceiling or overhead gas distribution plate, which leads to arcing in the gas inlets. As noted above, the gas distribution plate 110 includes the pucks 220 that confine the gas closer to the periphery of each hole 215 where electric fields are minimum so as to suppress or prevent arcing. Thus, the gas distribution plate 110 is inherently suitable for use in high density plasma reactors.
FIGS. 3A, 3 B and 4 illustrate one implementation of the embodiment of FIGS. 2A and 2B. FIG. 3A shows that the front plate 210 having the array of pucks 220 consists of a web of longitudinal arms 310 and lateral arms 315 formed with the pucks 220 and holding them in the fixed array. Referring to FIGS. 3B and 4, the back plate 205 has longitudinal channels 320 and lateral channels 325 that receive the longitudinal and lateral arms 310 , 315 when the plates 205 , 210 are joined together. The pucks 220 are centered in the respective holes 215 and spaced apart from the back plate 205 by the horizontal gaps 235 and the annular inlets 160 and therefore do not contact the back plate 205 . Contact between the back plate 205 and the front plate 210 is along the longitudinal and lateral arms 310 , 315 that fit snuggly within the corresponding longitudinal and lateral channels 320 , 325 . It is along these contacting surfaces that the two plates 205 , 210 are bonded together. As noted previously above, if the two plates are silicon carbide material, then the bonding is carried out using standard silicon carbide bonding techniques.
FIG. 5 illustrates an embodiment in which a single orifice 235 a feeds a group of neighboring annular gas inlets 160 a , 160 b , 160 c . The single orifice 235 a feed the middle annular gas inlet 160 b directly via the horizontal gap 235 b , and feeds the adjacent annular inlets 160 a, 160 c through internal channels 505 , 510 connecting the adjacent annular inlets 160 a , 160 c with the middle annular inlet 160 b . One advantage of this embodiment is that the number of finely sized orifices 235 that must be drilled in the back plate 205 is greatly reduced.
FIG. 6 illustrates an embodiment in which a back plate 600 has parallel lateral slots 605 and a front plate 610 has an array of holes 615 and pucks 620 . The circular holes 615 and the cylindrical pucks 620 are concentrically arranged so that they define corresponding annular gas ports 616 . The slots 605 are aligned with respective rows of the holes 615 and pucks 620 . The width of each slot 605 is less than the diameter of each hole 615 (e.g., less than half). The plates 600 , 610 are joined together so that each slot 610 is centered with a respective row of the array of holes 615 . Referring to the cross-sectional view of FIG. 7, the resulting gas passage aligned with each hole 615 consists of a pair of arcuate slots 630 a , 630 b which appear in FIG. 7 in solid line. Process gas is fed into each slot 605 by a single fine orifice 635 through the back plate 600 . The diameter of the orifice 635 is selected to provide the requisite gas flow rate.
The embodiment of FIGS. 6 and 7 is simpler to form because there is no horizontal gap (e.g., the horizontal gap 235 of FIG. 2) between the puck 620 and the back plate 600 . Instead, the bond between the plates 600 , 610 is formed along the entirety of their adjoining surfaces. The pucks 620 are similarly bonded across the entirety of their top surfaces to the bottom surface of the plate 600 . The only areas of the top surfaces of the pucks 620 not thus bonded are the areas facing the narrow slots 605 .
In the foregoing embodiments, the pucks 620 function as flow diversion elements for transforming gas flow between the front and beck plates 610 , 600 from stream patterns in the back plate 600 to annular flow patterns in the front plate 610 . The stream patterns correspond to a first radius (i.e., the radius of the top orifices 635 ) and the annular patterns correspond to a second radius (i.e., the radius of each annular opening 660 ) which is larger than the first radius. The flow diversion elements 620 induce a rapid change of gas flow (a) from a vertical flow of the stream pattern in each orifice 635 (b) to a horizontal flow from the first radius (of each orifice 635 ) to the second radius (of the corresponding annular opening 660 ) and (c) to a vertical flow in each corresponding annular opening 660 .
FIGS. 8A-8D illustrate one method for fabricating the gas distribution plate of FIGS. 6 and 7 as a monolithic silicon carbide piece. In FIG. 8A, the back plate 600 is formed of sintered silicon carbide and the slots 605 are milled in the plate 600 . In FIG. 8B, graphite inserts 805 are placed in the slots 605 . In FIG. 8C, the front plate 610 is formed by chemical vapor deposition of silicon carbide on the bottom surface 600 a of the back plate 600 . Then, the graphite inserts are all removed by heating the entire assembly until the graphite material burns away, leaving the slots 605 empty, as shown in FIG. 8 D. In FIG. 8D, an array of annular openings 660 are milled completely through the entire thickness of the front plate 610 , corresponding to the holes 615 and pucks 620 illustrated in FIG. 6 . FIG. 8D also depicts the orifice 635 , which may be milled during one of the foregoing steps.
FIGS. 9A-9D illustrate another method for fabricating the gas distribution plate of FIGS. 6 and 7 as a monolithic silicon carbide piece. In FIG. 9A, the back plate 600 is formed of sintered silicon carbide and the slots 605 are milled in the plate 600 . In addition, a wide shallow channel 810 is formed in the back plate 600 centered along and parallel to each slot 605 . In FIG. 8B, silicon carbide inserts 815 are placed in the wide shallow slots 810 . In FIG. 8C, the front plate 610 is formed by chemical vapor deposition of silicon carbide on the bottom surface 600 a of the back plate 600 . In FIG. 8D, an array of annular openings 660 are milled completely through the combined thicknesses of the front plate 610 and the silicon carbide inserts 815 , corresponding to the holes 615 and pucks 620 illustrated in FIG. 6 .
FIG. 10 illustrates yet another embodiment in which the back plate 600 and the front plate 610 are both formed of anodized aluminum. The anodization produces an alumina thin film 600 - 1 on the back plate 600 and an alumina thin film 610 - 1 on the front plate 610 . The anodization layer protects the aluminum plates from the plasma.
While the invention has been described with reference to embodiments in which the ceiling gas distribution plate must function as an electrode (and therefore comprise conductive material), the gas distribution plate of the invention is also well suited to applications in which the gas distribution plate does not function as an electrode.
In those embodiments in which the ceiling gas distribution plate functions as an overhead electrode, it may consist of silicon carbide, as described above. If it is desired that the gas distribution plate have a resistivity less than that of silicon carbide (0.005-1.0 Ohm-cm), then each of the silicon carbide plates 600 , 610 may be fabricated in such a manner as to have a thin highly conductive graphite layers 910 , 920 running through the center of the plates and co-planar with the respective plate, as illustrated in FIG. 11 . This is accomplished by forming each plate 600 , 610 as a graphite plate. Each graphite plate is machined to form the structural features described above with reference to FIGS. 6 and 7. Then, each graphite plate 600 , 610 is siliconized using conventional techniques. However, the siliconization process is carried out only partially so as to siliconize the graphite plates to a limited depth beyond the external surface of the graphite. This leaves an interior portion of the graphite un-siliconized, corresponding to the graphite layers 910 , 920 enclosed within the silicon carbide plates 600 , 610 . The graphite layers 910 , 920 have a resistivity about one order of magnitude less than that of silicon carbide. Since the graphite layers 910 , 920 are completely enclosed in silicon carbide, they are protected from the plasma.
While the gas distribution plate of FIGS. 2A and 2B has been described as being formed of silicon carbide, it may, instead, be formed of silicin.
While the invention has been described in detail with reference to preferred embodiments, it is understood that variations and modifications thereof may be made without departing from the true spirit and scope of the invention.
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The invention is embodied in a plasma reactor for processing a semiconductor wafer, the reactor having a gas distribution plate including a front plate in the chamber and a back plate on an external side of the front plate, the gas distribution plate comprising a gas manifold adjacent the back plate, the back and front plates bonded together and forming an assembly. The assembly includes an array of holes through the front plate and communicating with the chamber, at least one gas flow-controlling orifice through the back plate and communicating between the manifold and at least one of the holes, the orifice having a diameter that determines gas flow rate to the at least one hole. In addition, an array of pucks is at least generally congruent with the array of holes and disposed within respective ones of the holes to define annular gas passages for gas flow through the front plate into the chamber, each of the annular gas passages being non-aligned with the orifice.
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BACKGROUND OF THE INVENTION
[0001] This invention relates to restoration of service in a telecommunications network.
[0002] With the advent of SONET rings, customer expectation of rapid network restoration has taken a substantial leap. Prior to the optical transport era, failed network connectivity due to a cable cut typically took four to six hours for manual repair. In 1989, AT&T introduced FASTAR™ in which a central operations system (called “RAPID”) oversees network connectivity with the aid of a team of monitors strategically placed throughout the network. When a failure occurs at a network element or a facility, alarms from the monitors with a view of the failure are sent to RAPID for root cause analysis. RAPID correlates the failed component to the disabled services, generates a list of service-bearing facilities to be restored, and proceeds with restoration based on a priority ordering of the service facilities. Restoration is effected using dedicated spare capacities that are strategically distributed throughout the network, in amounts averaging about 30% of the service capacity. Typically, the Time-To-Restore metric ranges from three minutes for the first channel restored on up to ten or twenty minutes for the last few channels in large scale failure events. This was a major improvement over the performance of prior restoration paradigms.
[0003] Still, FASTAR has certain limitations rooted in its central control architecture. For example, central collection of alarms creates a bottleneck at the central processor. In a large scale failure event, many alarm messages, perhaps from several monitors, need to be sent to the central processor. The central processor must stretch its event window in order to have reasonable assurrance of receiving all messages and obtaining a complete view of the failure. Also, the problem of planning restoration paths for many disparate routes is mathematically complex and quite difficult to solve, leading to restoration reroute solutions that are typically sub-optimal.
[0004] In 1995, network elements and transport facilities conforming to the SONET standards were introduced into AT&T transport network. The SONET standards introduced two new topographical configurations, namely, linear chain and closed ring, and in the latter the new restoration paradigm of ring switching. SONET linear chains and rings employ stand-by capacities on a one-for-one basis. That is, for every service channel, there is a dedicated, co-terminated protection channel. As in the older technologies, when a failure occurs on the service line of a span in either a linear chain or a closed ring, the SONET Add/Drop Multiplexers (ADMs) adjacent to the failed span execute a coordinated switch to divert traffic from the failed service channel to the co-terminated protection channel. When both the service and protection lines of a span have failed, however, a SONET ring provides the further capability to switch traffic on the failed span instead to the concatenated protection channels on surviving spans completing a path the opposite way around the ring. The ADMs at the two ends of the failed span each loop the affected traffic back onto the protection channels of the adjacent spans, whence the remaining ADMs around the ring cooperate by completing through connection of the protection channels the entire way around the ring. Since failure detection and protection switching are done automatically by the ADMs, restoration is typically fast and can routinely take less than 200 ms. In short, by setting aside a 100% capacity overhead in the standby mode and configuring facilities in closed rings, SONET standards make possible a three orders of magnitude improvement in restoration time over FASTAR. The challenge has thus shifted to designing a network that is restorable with SONET ring-like performance but without the high penalty in required overhead capacity,
SUMMARY OF THE INVENTION
[0005] An advance in the art is achieved with an arrangement that employs the notion of a failure at any point in the network can be quickly remedied by rerouting traffic at the failed point though network elements in close topological proximity to the failed point. This is accomplished by algorithmically and distributively assigning the responsibility for recovery from all failures to different network nodes. In one illustrative embodiment, each failure is assigned to one primary control node, and to a secondary, backup, node.
[0006] Each node maintains an awareness of the spare resources in its neighborhood and pre-plans re-route plans for each of the failures for which it is responsible. It maintains the created re-route plans and, upon detection of a failure, transmits a re-route plan to particular nodes that participate in the re-routing recovery planned for such a failure. Alternatively, it transmits re-route plans to the nodes that need them, and upon detection of a failure, the network node broadcasts an ID of the re-route plan that needs to be executed. Nodes that receive a plan ID that corresponds to a plan that they possess execute the relevant plan.
[0007] Whenever the spare resources change in a manner that suggests that a re-route plan needs to be revisited, the network node initiates a new re-route preplanning process.
BRIEF DESCRIPTION OF THE DRAWING
[0008] FIG. 1 depicts a network and illustrates the concept of a neighborhood;
[0009] FIG. 2 illustrates a path and the nodes involved in rerouting to circumvent a failure on span 23 -A; and
[0010] FIG. 3 presents a block diagram of that portion of a node that participates in the methods disclosed herein.
DETAILED DESCRIPTION
[0011] A distributed control system potentially is faster, more efficient and more robust than a central control system. Therefore the failure restoration management system disclosed herein centers on the use of a distributed restoration management of local failure. In accordance with the principles disclosed herein, the concept of a neighborhood is employed, based on the fact that the most efficient restoration routes are highly likely to pass through a small collection of nodes within close topological proximity to the failure site. FIG. 1 presents a view of a network in which the principles disclosed herein may be applied. For ease of understanding, the depicted network is of a very simple and regular topology (hexagonal) but, of course, that is not a requirement of this invention.
[0012] To better understand the description that follows, it is useful to review some of the nomenclature employed herein.
[0013] In the context of this disclosure, a path corresponds to the route over which communication is passed from an originating point in the network to a terminating point. Typically, a customer's terminal is connected to the originating point, another customer's terminal is connected to the terminating point, and the path provides a connection between the two.
[0014] The path is made up of links that are coupled to each other by means of nodes. Typically an adjacent pair of nodes will be joined by a large bundle of links. The link bundle may comprise the wavelengths in a multi-wavelength transport medium, or the channels in a channelized broadband transport medium, or any combination of similar means of bundling. A node is an element that routes signals of an incoming link to one of a number of outgoing links. Physically, this element is implemented with a switch or cross-connect (in circuit-switched applications), or a router (in packet-switched applications). Each link connects to a particular port on the nodal element at each of its ends.
[0015] The physical connection between nodes can be a cable (optical fibers, coax, etc.) or a collection of cables, each bearing one or more link bundles. A collection of cables leaving a particular node (say, node A) can be connected to a branch point (say, T) where the collection is split. Some of the cables are connected to cables that go to a node B while the others of the cables are connected to cables that go to a node C. Similarly, the collections from T to B and from T to C may contain ables that connect B to C. Because the branch point has no switching or routing capabilities, it is not termed a “node.” The collection of cables that span between two points (be it two nodes, two branch points, or one node and one branch point) is called a span. Thus, a link is a logical connection between ports on two nodes, that physically can pass through one or more spans.
[0016] The collection of link bundles, each traversing one or more of the spans in a configuration like the one just described, is called a shared risk link group. Any two link bundles belong to the same shared risk link group if both traverse the same span, or each separately has a span-sharing association with a third link bundle, or (in extreme examples) the two are related through an unbroken chain of span-sharing associations.
[0017] A neighborhood is node-centric. It is a collection of nodes that are reachable from the subject node through a preset number of link hops, n. FIG. 1 shows an example of the neighborhood of a node 10 , where n=2, delineated by hexagon 100 . As arranged in FIG. 1 , a neighborhood of a node (e.g., 40) comprises 18 nodes that surround the subject node and the links that connect them. To simplify this description, the FIG. 1 arrangement comprises no branch points, resulting in each link bundle traversing just one span, and in the entire network being free of shared risk link groups.
[0018] In accordance with the principles disclosed herein, each node maintains information about its neighborhood. Specifically, each node is informed of the identity of the nodes and the links that are within its neighborhood, the node port assignments at the two ends of each link, plus which of the links are cross-connected and to what other links (therefore in-use in paths) and which are not cross-connected (therefore idle and available as spare). This information is stored in memory of the node. The way that a node maintains this knowledge current is quite simple. When a node is equipped with a new port, it immediately attempts a hand-shake exchange with whatever node may be connected at the far end. One means of hand-shake is for the node to begin immediately to transmit a “keep-alive” idle-channel signal outbound from the port, bearing its own node ID and the identity of the particular port. At the same time it begins to monitor the receive side of the port for arrival of a like signal from the opposite node. Upon receiving such a signal, it proceeds to enter the new connectivity to its database, marking the new link as “available spare”. Then, and whenever thereafter it detects any other change in its connectivity, it broadcasts a message to all immediately adjacent nodes. The change may correspond to increased spare capacity because of installation of a new link as just described, or because of released links when a path is taken down, or it may correspond to reduced spare capacity because of new path provisioning or link failures, etc. The node updates its own information based on those changes and also broadcasts the information to its neighbors.
[0019] The broadcast is over all of the link bundles emanating from the node. In addition to details of the incremental change, the message includes a rebroadcast index set to 0 to indicate that it is the first node to broadcast the message. A node that receives this message updates its own information, increments the rebroadcast index by 1, and if that index is less than n, rebroadcasts the received information to the far end nodes of all of the link bundles emanating from it, other than the one from which it originally received the information.
[0020] With the very simple broadcast approach described above, a node might receive the same broadcast message a number of times. However, it is relatively easy to have the nodes recognize and ignore subsequent receptions of an earlier message, unless the rebroadcast index is less than that of the initial reception (in which case the node must handle the later reception as if it were the first in order to assure the message will propagate to the desired neighborhood boundary).
[0021] Through this updating protocol, all nodes in the neighborhood of node 10 keep node 10 up to date almost instantaneously about changes both in service path provisioning and spare capacity availability in the neighborhood of node 10 . The actual communication protocol that is used between nodes is not critical to this invention. An example of an acceptable protocol is any member of the TCP/IP protocol suite. The message channels may be either in-band on one of the links in each bundle, or out-of-band using an administrative data network.
[0022] In accordance with the principles of this invention, in addition to each node having its own neighborhood, each link bundle that connects two nodes has one of the nodes designated the command node (CN), while the other node is designated the backup command node (BCN). The designations can be arbitrary, but an algorithmic approach is preferred. One algorithmic approach is to select the node that is the higher of the two in an alpha-numerical ordering of node IDs. (Another might be to choose the western-most with ties going to the southern-most, if each node includes its Lattitude and Longtitude as part of its ID.) Whenever the first link in a new link bundle is added to the network, whether to a new node or between existing nodes, the two end nodes can negotiate the control designation accordingly. Thereafter, the one chosen must remain the CN for all links in the same bundle.
[0023] Normally, in accordance with the principles disclosed herein, the role of the CN for a given link bundle is a dual one: first, to carry out a restoration pre-planning process for the bundle, and second, to trigger execution of the pre-plan upon detecting failure of any link or links in the bundle. In the case where the bundle belongs to a shared risk link group, however, one and only one of the CNs for all link bundles in the group must be designated as the planning node (PN) for the entire group. This is necessary in order that the pre-plans be coordinated and not conflict regardless which span creating the shared risk might fail. The roles of the other CNs are then limited to triggering execution of the plans for failures of the links they command. Since nodes do not otherwise have access to span data and cannot auto-discover shared risk link groups the way they auto-discover links, designation of the planning node must be made by a central authority such as a Network Administrator, who must also arrange for downloading of the shared risk link group topology to the designated PN.
[0024] The restoration plan for a link bundle is the same for a failure in any of the spans it traverses, and provides a separate plan for each link in the bundle, coordinated such that there will be no contention should the entire bundle fail. Any one node may be the CN for a numbr of link bundles. For example (absent any shared risk spans), in accordance with a west-most CN assignment rule, node 10 carries out the pre-planning process for possible failure of the bundles borne on each of spans 23 , 24 , and 25 . For purposes of this disclosure, only single bundle failures are considered, but it should be apparent to any skilled artisan that the principles of this invention extend both to failures of shared-risk spans and to multiple near-simultaneous span failures.
[0025] The restoration pre-planning process is undertaken automatically upon detection of any path provisioning or other change in available spare capacity within the command node's neighborhood. The restoration plan that is created is a partial path restoration. That is, it covers only that portion of an affected path that begins and ends within the command node's neighborhood. In creating a restoration plan, the CN (or other designated PN) considers all links in the bundle. The CN constructs a plan for rerouting each and all of them, on available spare links through nodes in its neighborhood, to get around the failed span. In generating the plan, the CN is cognizant of the available spare links between node pairs in its neighborhood as well as the intra-neighborhood segments of all service paths using links in the particular target bundle.
[0026] The minimum spare capacity required for restoration in the network is pre-computed and pre-allocated (i.e., dedicated for restoration). This capacity pool is augmented by capacity allocated for service path provisioning but currently idle. The pre-planning problem is essentially a multi-commodity flow problem that can be solved by conventional linear programming techniques. Basically, it is a classic resource allocation problem that can be represented by a set of equations which need to be solved simultaneously. Numerous techniques are known in the art for solving a set of simultaneous equations. Once the pre-plan process is complete, the CN considers each restoration action, and develops for that action the messages which will need to be delivered to each node that will participate in the restoration action. The message instructs each such node to establish connections within the node's switch or router so that paths can be created to route traffic around the failed span.
[0027] A particular node in the neighborhood of the CN responsible for a link bundle may be a participant in the restoration plan of several links in that bundle. As such, it may be the recipient of a composite message. The restoration plan messages can be sent to the nodes that participate in the various restoration plans at the time a failure occurs, except that the restoration plans are send immediately to the backup node. Alternatively, the backup plans may be tagged with a Plan ID and sent in advance (whenever a new or revised plan is complete) for local storage at the target node. The speed-of-recovery is somewhat higher in embodiments where the messages are sent to the participating nodes as soon as the plan is complete. This stems from the fact that a call for executing a particular plan (identified by its ID—which, effectively, is a pointer) requires less information transfer (and could use the broadcast mechanism) and, hence, is faster. Advantageously, each node that receives a restoration message performs sanity checks on these before committing them to storage. The messages are kept in storage pending notification by the appropriate CN to execute the pre-planned cross connects.
[0028] There are many possible alternative formats for the message that a CN would send to a participating node to instruct it to execute a particular plan. The message might be ID.nn, where the ID specifies the particular link bundle, and the nn specifies the restoration plan for the path using link nn in that bundle. The ID, for example, may have the form xx.yy, which specifies the command node and the backup command node, hence also the particular bundle. As indicated above, the instruction that a node will need to execute is to establish a connection within the switch or the router, from a first specified port, i, to a second specified port, j, so that path segments can be created to reroute traffic of the blocked link. The two port indices, i,j are sufficient for all rerouting nodes other than the Upstream Transfer Node (UTN) and downstream Transfer Node (DTN). The UTN is the node in the failed path where the payload traffic is to be diverted from its original path onto the restoration route. The DTN is the point in the restored path where the payload traffic rejoins the original path. Note that for bidirectional restoration of bidirectional paths, the same node that serves as UTN for one signal direction serves as DTN for the opposite direction, and conversely. Regardless, at both the UTN and the DTN the required path transfer operations entail three ports. The three indices involved with the UTN correspond to the transfer from an i→j connection to an i→k connection, and if the restoration strategy so dictates, this will be implemented via bridging the i→k connection onto the i←j connection without deleting the latter. In any case, the three indices involved with the DTN transfer operation correspond to a switch (commonly termed a “roll”) from an i←j connection to an i←k connection
[0029] A node detects a link failure through the appearance of a failed-signal condition at its receive port, or due to electronic malfunction in the port itself. Some examples of failed-signal conditions to which the node must react include AIS-L (Alarm Indication Signal-Link), LOS (Loss of Signal), and LOF (Loss of Frame) or LOP (Loss of Pointer). A node detecting any such condition must insert a locally generated signal such as AIS-P (Alarm Indication Signal-Path) that is distinct from any of the possible link failure signal conditions, so that nodes further downstream of the failed link will recognize the failure as one to which they must not autonomously respond.
[0030] A typical failure scenario is depicted in FIG. 2 , where a particular path happens to exist between nodes 60 and 50 , traversing nodes 17 , 12 , 10 , 14 , and 18 . In this illustrative example, span 23 has traffic flowing in both directions (designates 23 -A and 23 -B), and the fiber that carries traffic from node 10 to 14 (span 23 -B) is failed, possibly due to a partial cable cut. When node 14 detects the signal failure condition, it immediately sends out an AIS-P or equivalent signal downstream along the failed path (and all simultaneously failed paths), as previously noted.
[0031] Particularly if node 14 is not the command node, it must also send a signal to node 10 to alert it to the failure, in case the failure in fact proves to be one directional. This signal may be out-of-band on an administrative link network, in which case it must enumerate all failed links, or most advantageously it may be in-band on each failed link in the form of a “Far End Receive Failure-Link” (FERF-L) or equivalent signal. Similarly as in the case of AIS-L, a node receiving FERF-L must either substitute FERF-P, or in this case (since the FERF-L would appear in the overhead of an otherwise normal service signal) simply remove it from the signal propagating further downstream.
[0032] Since both nodes 10 and 14 know of the failure, the command node for the link bundle on span 23 takes control (e.g., node 10 ). The backup command node (node 14 ) sends an inquiry to the control node, such as ping of the Internet Protocol (IP), to determine that the control node is in good operating order. When the BCN receives an affirmative response, the BCN keeps “hands off”, and the restoration continues under the control of the CN. Otherwise, the BCN assumes the role of CN and takes responsibility for restoring the failed link.
[0033] The CN consults its database and retrieves the restoration plan that it pre-planned for this failure. If the relevant part of the plan has already been sent to the participating nodes, the CN advantageously needs to merely broadcast a trigger message containing the plan ID to its immediate neighbors. The immediate neighbors cooperate by propagating the message deeper into the neighborhood, using the same rebroadcast index as for connectivity changes, until it reaches the limit of the CN's neighborhood. Each node receiving the trigger message checks its own database to determine whether it is a participant in the identified plan, and if so, proceeds to execute its part. If the relevant part of the plan has not already been sent to the participating nodes, the CN identifies the participating nodes and proceeds to download the relevant part to each participant in an IP message addressed to it. In this latter case it should be noted that the participant nodes might receive their orders in a somewhat random order depending on the IP routing scheme deployed. Since each node is to execute its task autonomously, the order of message arrival does not have an adverse effect.
[0034] It might be that the restoration plan for restoring a failure in fiber cable span 23 calls for nodes 17 and 14 each assigned the role of transfer node (both UTN and DTN assuming bidirectional restoration), and node 13 assuming the role of a cut-through node. After the restoration orders have been received, the participant nodes ( 17 , 13 , and 14 ) independently retrieve the relevant plan and execute their assigned tasks.
[0035] At the time of restoration execution, node 17 in its role as UTN starts from the state where, for the normal service path connection, the receive side of port i is connected to the transmit side of port j (and conversely for bidirectional service), port j being the port closest to the failure. Port k is the designated termination of the pre-planned restoration path. Assuming the network follows the generally recommended bridge-and-roll restoration strategy, the UTN task is to bridge the received service signal at port i to the transmit side of port k. Concurrently, node 14 in its UTN role sets up a similar bridge connection of the service signal in the opposite transmission direction to the port terminating its end of the restoration path. Each of the two nodes then, in their roles as DTN, monitor the receive side of the restoration path port (port k at node 17 ) for onset of normal service signal replacing the distinctive keep-alive idle signal otherwise received at its end before the bridge connection at the opposite end and all intermediate cross-connects have been completed. Immediately upon detecting the onset of normal service signals, each independently completes the roll of service to the restoration path. The roll constitutes (for example, at node 17 ) a switch of the normal service connection (receive side of port j connected to the transmit side of port l) to the restoration path connection (receive side of port k to transmit side of port l. Upon successfully completing this roll operation, each transfer node reports its success to the CN, or if the operation cannot be successfully completed before a preset timeout, it instead reports the failed attempt to the CN. Of course, the CN itself may be one of the two transfer nodes, in which case it needs to receive a completion message from the opposite transfer node only.
[0036] The task of each node between the two transfer nodes is quite simple. When any such node receives a restoration trigger message, it simply accesses its database, identifies the connection that it needs to establish, proceeds to do so, then reports successful completion (or a failed attempt) to the CN.
[0037] In embodiments that do not employ the bridge-and-roll approach, the transfer nodes each simply switch to the restoration path. At node 17 , for example, this constitutes a switch from the l-j connection to the l-k connection. However, this embodiment is less robust (hence not recommended) in that the inclusion of service verification in the DTN role may be more difficult if it requires monitoring for normal service signal onset at a receive port that is already cross-connected rather than still open.
[0038] In the above discussion, the state of the cross connect fabrics of the participant nodes is assumed to remain unchanged between the time the pre-plan message arrives and the time of actual restoration execution. In fact, this may not be true if a node is asked to execute a first restoration plan and, before another pre-planning session is complete, it is asked to execute a second restoration plan that calls upon the same spare resources. Even with just one plan in progress, it may simply happen that one or more of the pre-planned restoration channels fails before the next pre-planning session is complete.
[0039] If the control node receives a message of restoration failure from either transfer node, or link unavailability from one of the other participating nodes, restoration for that link is declared “failed”. The control node then sends a message to the participating nodes to reverse the failed restoration plan for the particular path, and triggers backup restoration heuristics. The control node then waits for the next cycle of pre-planning to launch a new effort to restore that still failed link.
[0040] When a report of successful restoration of a path is received from all participating nodes, the control node records the executed pre-plan for that path as part of the record of current routing for the underlying end-to-end service. The bypassed partial path (between transfer nodes) is kept as the record for later normalization upon repair of the failed link.
[0041] FIG. 3 presents a general block diagram of a node. It includes a communication module 200 , for sending and receiving messages from the various transmission mediums that are connected to the node, a processing module 210 , a database 220 , and a cross connect fabric 230 . Processing module 210 interacts with database 220 and with communication module 200 and processes information in connection with the messages that flow through module 200 . Among the processing that module 210 performs is:
determination of whether it is a control node with respect to a particular link that emanates from the node, ascertainment of what facilities exist in its neighborhood availability of those facilities, the restoration pre-planning disclosed above; in connection with each link for which the node is a control node, analysis of failure conditions in the spans between the node and immediately adjacent nodes, analysis of failure messages, analysis of restoration condition messages, requests to execute restoration plans, carrying out of received requests to execute a restoration plan, communicating with adjacent nodes about their operating status for which it is a backup control node, and communicating with adjacent nodes about its operating status with respect to which it is a control node.
[0052] Of course, it is not very difficult to include the functions of communication module 200 in processing module 210 . Database 220 maintains information, inter alia, about:
the links for which it is a control node, the node's own restoration plans, which other nodes the node is a backup control node, information about those nodes' restoration plans, and information about restoration tasks that other nodes may expect it to execute.
[0058] Cross connect fabric 230 carries out the inherent routing function of the node, as well as the routing functions that particular restoration plans may require.
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A network that is architectured to distributively be responsible for remedying failures achieves advantageous operation. This is accomplished by algorithmically and distributively assigning the responsibility for recovery from all failures to different network nodes and by re-routing traffic at the failed point though network elements in close topological proximity to the failed point. Each node maintains an awareness of the spare resources in its neighborhood and pre-plans re-route plans for each of the failures for which it is responsible. It maintains the created re-route plans and, upon detection of a failure, transmits a re-route plan to particular nodes that participate in the re-routing recovery planned for such a failure. Alternatively, it transmits re-route plans to the nodes that need them, and upon detection of a failure, the network node broadcasts an ID of the re-route plan that needs to be executed. Nodes that receive a plan ID that corresponds to a plan that they possess execute the relevant plan. Whenever the spare resources change in a manner that suggests that a re-route plan needs to be revisited, the network node initiates a new re-route preplanning process.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority of provisional patent Application Ser. No. 60/026,339 filed Sep. 19, 1996.
FIELD OF THE INVENTION
This invention relates to lawn and garden tools, and more particularly to a detachable broom head that can be removably mounted to most commonly used lawn and garden rakes.
BACKGROUND
Lawn and garden tools that include a combination of a rake and broom are known in the art. Horkey, U.S. Pat. No. 3,668,850 and Lutz, U.S. Pat., No. 3,885,765, for example disclose lawn and garden tools that can be used as both a rake and a broom. While disclosing the general idea of broom and rake combinations, these prior art lawn and garden tools are unnecessarily cumbersome to use as a result of their relatively complicated designs.
Horkey discloses a rake fastened to a broom by a slidable shaft. However, in order to convert between the raking and brooming features of the tool, it is first necessary to move a latch located within the tool handle. This design, therefore, is not very efficient for a gardener requiring both features of this tool. For example, in order to switch between the raking and brooming features of this lawn and garden tool, a gardener would first have to stop raking, move the latch into the brooming position, and then begin to use the broom. In order to return to raking, the same process would have to be completed in reverse. Moreover, the broom bristles in Horkey's lawn and garden tool are not sufficiently angled away from the rake tines. This aspect of the design would require the gardener to hold the tool in such a way that it is substantially perpendicular to the ground to avoid interference with the bristles when using the rake. In short, the design of this broom and rake combination sacrifices the true functionality of both the broom and the rake.
Lutz also discloses a relatively complicated lawn and garden tool which can be converted between a wide and narrow rake. Although referred to as a broom, the narrow rake simply does not have the soft, dense bristles necessary to adequately function as a broom. The narrow rake, for example, would not be able to satisfactorily sweep fine debris such as dirt and small leaves. Furthermore, like the tool disclosed by Horkey, this design also requires the gardener to stop using the tool in order to convert between the wide and narrow settings, resulting in an inefficient loss of time.
Consequently, there exists a need for a simple, efficient, easy to use lawn and garden tool that can function both as a rake and as a broom.
SUMMARY OF THE INVENTION
The present invention, therefore, provides a detachable broom head that can easily be removably mounted to most commonly used lawn and garden rakes. The detachable broom head allows a gardener to use a single lawn and garden tool for tasks that require both raking and brooming. The unique, yet simple, design of the detachable broom head makes it possible to switch between raking and brooming by merely rotating the rake handle 1800. The broom head is attached to the upper face of the rake frame in such a manner that a dual purpose lawn and garden tool is created. In one orientation, the tool functions as an ordinary rake. By merely flipping the tool over so that the broom bristles face the ground, the same tool can function effectively as a broom. Moreover, unlike the prior art, when the brooming feature is no longer required, the broom head can be detached from the rake and conveniently stored until needed.
The broom head may be quickly and easily attached and detached from the rake. In one embodiment, the attachment means comprise a pair of flexible attachment clips. The attachment clips help grip the rake frame. The attachment clips contain a rib-engaging recess corresponding to a rib located on the upper face of the frame of the rake. In the presently preferred embodiment, the profile of the broom head is generally contoured to help assist in engaging the rake frame. Therefore, the broom head easily slides over the rake frame, and is locked into place when the rib on the upper surface of the rake frame is engaged. Additionally, finger tabs are provided on the attachment clips to help disengage the recesses from the rib in order to remove the broom head from the rake.
In another embodiment, the attachment means comprise a coupler that can be attached to the rake, for receiving the broom head. Preferably, the coupler includes a spring and an axle section. The lower surface of the broom head is contoured to engage the coupler. A plurality of flanges extending outwardly from the lower surface of the broom head engage the spring and axle sections of the coupling device, locking the broom head on the rake.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features and advantages of the present invention will be appreciated as the same become better understood by reference to the following Detailed Description of the Invention when considered in connection with the accompanying drawings, wherein:
FIG. 1 is a perspective view of a broom head according to the present invention attached to a lawn and garden rake;
FIG. 2 is a side view of the broom head of FIG. 1;
FIG. 3 is a top view of the broom head of FIG. 2;
FIG. 4 is a top view of the attachment clips of the broom head of FIG. 2.
FIG. 5 is a top view of the upper surface of the broom head of FIG. 2.
FIG. 6 is a side view of an alternative embodiment of a broom head according to the present invention attached to a lawn and garden rake;
FIG. 7 is a top view of the broom head of FIG. 6 attached to a lawn and garden rake;
FIG. 8 is a back view of a lawn and garden rake with the broom head of FIG. 6 attached, with a portion of the rake removed;
FIG. 9 is a side of the broom head of FIG. 6 without the coupling;
FIG. 10 is a top view of the upper surface of the broom head of FIG. 6.
DETAILED DESCRIPTION OF THE INVENTION
The improved lawn and garden tool according to the present invention comprises a detachable broom head that can be removably mounted to most commonly used lawn and garden rakes.
In one embodiment of the invention shown in FIG. 1, the detachable broom head 10 is designed to easily slide onto various lawn and garden rakes 12, such as the gardening rake sold by Cal-Flex Flexrake Corp under the mark FLEXRAKE®. The rake has a set of flexible tines 14 extending outwardly from the frame 16 of the rake. The frame has an upper face (not shown and a lower face 20. The tines 14 are angled toward the lower face 20 of the frame. A rib 22, extending the width of the frame, is present on both the upper and lower 20 faces, adjacent to the tines.
The broom head 10 comprises a frame 21 having an upper surface 24 and lower surface 25, a plurality of bristles 26 attached to, and extending outwardly from, the upper surface 24, and a means for attaching the broom head 10 to the rake 12. In the embodiment shown in FIGS. 1-5 the means for attaching the broom head 10 to the rake 12 includes a pair of flexible attachment clips 28 that grip the lower face 18 of the frame of the rake, securing the broom head onto the rake. The attachment clips 28 are integrally formed with the frame 21 of the broom head, and extend downwardly from the upper surface 24 at such an angle that the profile of the broom head is essentially an inverted `V` or `U` shape. The attachment clips are contoured for a snug fit over the rake frame. To assist in gripping the upper face of the frame of the rake, a rib-engaging recess 30 extends across the width of each attachment clip for cooperatively engaging the rib 22 on the lower face 20 of the rake frame. If desired, a similar recess 32 may be added to the upper surface 24 of the broom head to engage the rib 22 on the upper face 20 of the rake frame, thereby further securing the broom head to the rake.
To aid in removal of the broom head from the rake frame, each attachment clip further includes an angled finger tab 34 extending outwardly from the bottom of the clip. The finger tabs 34 preferably contain curved indentations and are of a width adapted to allow a user to easily pull on the finger tabs, disengaging the recesses from the rib on the lower face of the rake frame as is necessary to remove the broom head. Once the rib has been disengaged, the broom head will easily slide off the rake frame.
In addition, a hook or U-shaped handle 36 may be provided on the broom head, centered along the width of the frame 21 of the broom head, directed opposite the attachment clips. The handle 36 may be used for various purposes, such as pulling the broom head away from the rake frame during detachment, hanging the broom head during storage (e.g. in a garage or storage shed; on a gardener's person when not currently needed, etc.), or as an additional means for attaching the broom head to the rake frame, via a handle clip (not shown) on the rake shaft, or like means.
The attachment means is made out of plastic, or some other material that is rigid, yet flexible enough to snugly attach to the rake frame. Except for the bristles, the entire broom head may be integrally formed. The bristles may be attached to broom head by fasteners or any other means well known in the art.
The distribution of the broom bristles 26 is such that the width of the broom bristles corresponds to that of the rake tines 18 for easy sweeping of gutters and the like. The bristles 26 are also designed to have a length that extends past the bend in the rake tines, but as can be seen in FIG. 2, at such an angle that the bristles and tines will not interfere with one another during either raking or sweeping operations, respectively. FIG. 2 also illustrates the use of a step 38 near the bottom of the upper surface 24 of the broom head to further ensure that the bristles do not interfere with the rake tines, both during use of the tool and during attachment and detachment of the broom head. It should be understood that a variety of different types of bristles as well known in the art can be used with the present invention. The bristles can be fine, coarse, or a combination of both depending on the particular surface or debris being swept.
This design allows for simple and easy attachment and detachment of the broom head to the rake frame. In order to attach the broom head to the rake, the broom head is simply slid over the rake frame until the rib on the lower face 20 of the rake frame engages the recesses in the attachment clips 28. In order to keep the bristles away from the tines, it is important to make sure that the attachment clips are placed on the lower face of the rake frame, and not the upper face. Due to the profile of the broom head, the attachment process if essentially self-guiding. In order to detach the broom head from the rake, it is simply necessary to pull outwardly on the finger tabs 34 (i.e. away from the rake). This will disengage the rib from the recesses and allow the broom head to be separated from the rake frame by pulling on the U-shaped handle.
While this embodiment was illustrated using a FLEXRAKE® brand rake, the broom head attachment clips can be readily adapted to a variety of different rakes based on the particular design and location of the rib on the frame of the rake. Likewise, while a rib was used to illustrate the means of attachment to the rake, it should be understood that this embodiment can be adapted to accommodate any rib-like member. Moreover, it should be readily apparent that the recess in the attachment clips could be replaced by a rib or rib-like member to engage a recess present on the rake frame.
An alternate embodiment of the present invention is shown in FIGS. 6-10. Where the attachment means of the previous embodiment depended primarily on the presence of a rib or rib-like member on the rake frame, this embodiment provides a means of attaching the broom head to the rake that can be employed with most commonly used lawn and garden rakes, whether or not the frame contains a rib for attachment.
The broom head 112 comprises a frame 121 having an upper 124 and lower 125 surface, a plurality of bristles 126 attached to, and extending outwardly from, the upper surface 124, and a means for attaching the broom head to the rake. In this embodiment, the means for attaching the broom head to the rake includes a coupling device 127 that can be attached to the upper face 118 of the rake frame. While lawn and garden rakes come in different shapes and sizes, the use of the coupling device will allow the broom head according to the present invention to be attached to most any design.
The coupling device 127 comprises a hollow dumbbell shaped component, formed of a hollow axle 129 and a pair of rollers 131 having a hollow center for receiving the axle. One roller is attached to each end of the axle 129, thereby creating the dumbbell shape. A spring 133 is passed through the axle and rollers. Clips 135 are positioned in the outermost slots of rake 110 in order to attach the coupler 127 to the rake 110. The ends of the spring 133 are attached to clips 135 through holes in the end of the clips, positioning the coupler 127 on the upper face 118 of the rake as show in FIG. 7.
As illustrated, it is preferred that clips 135 contain multiple holes along the width of the clip so that the coupler may be positioned at various heights along the upper face of the rake, as dictated by the design of the rake. This allows the broom head to be positioned at various heights along the upper face of the rake, so that variations in design would not affect the functionality of the broom head. Moreover, for some rake designs, particularly metal garden rakes, it may not be necessary to use the clips as the ends of the spring could be attached directly to the frame of the rake.
Likewise, although a spring 133 is described to attach the coupler to the rake, it is to be understood that other materials may also be used without affecting the functionality of the broom head. For example, a rubber or bungi-type material could be used in place of the spring if safety concerns dictate. Likewise, any material with sufficient elasticity may be used. Moreover, other coupling devices could be used to attach the broom head to the rake, without departing from the inventive concepts disclosed herein.
The lower surface 125 of the broom head frame, as shown in FIG. 8, is designed to receive and engage the coupler 127. This is accomplished primarily by the presence of three flanges, or protrusions, extending outwardly from the lower surface 135 of the broom head frame.
A center flange 141, is located near the center of the lower surface of the broom head frame, protruding outwardly and at an angle, in the direction opposite the bristles 126. The center flange engages the axle 129 of the coupler during operation, and therefore the inside surface of the center flange may be shaped to form a groove for receiving the axle. Similarly, a pair of grooves may be formed in the lower surface 125 of the broom head frame, adjacent the center flange, for receiving the rollers of the coupler. The width of the center flange 141 is preferably slightly less than the width of the axle 129, and the length of the center flange is preferably to prevent the coupler 127 from accidentally disengaging from the rake during use.
Two side flanges 143 are also located on the lower surface 125 of the frame, one on each side of the broom head, protruding toward the center of the broom head. The side flanges engage the spring 133 during operation, and therefore the inner surfaces of the side flanges may be grooved to receive the spring. The length of the side flanges 143 is preferably such that when attached, a portion of the spring 133 extends over the top of each side flange. Due to the position of the spring during attachment, the upper portion of the side flanges preferably extends out farther than the lower portion, in order to secure the broom head to the rake.
In addition, a recess 145 may be provided in the upper surface of the broom head to act as a hand grip during attachment and detachment of the broom head. It is recommended that while attaching and detaching the broom head, the rake be held vertically so that the ground may be used for leverage.
In order to attach the broom head 112 to the rake 110, it is recommended that the coupler 127 first be attached to the rake. The coupler 127 can be attached to the rake as previously described using clips 135. Once the coupler has been attached to the rake, it is possible to attach the broom head to the coupler. The broom head is positioned over the coupler so that the shaft 129 is located between the center flange 141 and the lower surface 125 of the broom head frame. Then the broom head is pulled down, using hand grip 145, so that the spring is placed in tension. The broom head is be pulled down until both side flanges 143 clear the spring 133. Once the side flanges clear the spring, the hand grip 145 may be slowly released. The tension in the spring tends to pull the broom head up to a position where the combination of the flanges and the tension in the spring secure the broom handle to the rake, as shown in FIG. 12.
When desired, it is possible to detach the broom head from the rake. To detach the broom head it is recommended to first pull the broom head down away from the tines of the rake, again using the hand grip 145. While pulling down, the broom head is preferably slowly rotated so that the bristles 126 begin to move away from the rake tines 114. Rotating the broom head will help disengage the spring 133 from the side flanges 143. Once the springs have been disengaged from the side flanges, the broom head can be easily removed from the rake by lifting the broom head off of the coupler 127. Then, the coupler can be removed from the rake. Alternately, if desired, the coupler can remain on the rake as it does not interfere with the operation. This will allow the broom head to be quickly attached to the rake when needed again.
As described in connection with the previous embodiment, if desired, a hook or U-shaped handle 136 may be attached to the broom head to assist storage of the broom head.
Both embodiments described provide a simple, efficient, and easy to use detachable broom head that can transform an ordinary lawn and garden rake into a tool that can function both as a rake and as a broom. Once the broom head has been attached, the user can quickly and easily switch between the raking and brooming features of the tool, as each task requires. The tool can be used as an ordinary rake, since the bristles of the broom head do not interfere with the rake tines. When the brooming feature is needed, the rake handle can be rotated 180° so that the bristles are ready to use, for example, in sweeping up dirt or fine debris. Moreover, when the brooming feature is no longer required, the broom head can be removed and conveniently stored until needed again.
While various embodiments of this invention have been shown and described, it would be apparent to those skilled in the art that many more modifications are possible without departing from the inventive concepts herein. It is, therefore, to be understood that within the scope of the appended claims, this invention may be practiced otherwise than as specifically described.
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A detachable broom head is provided for quick and easy attachment to a lawn and garden rake. The broom head is adapted to be removably mounted on the rake such that a dual purpose lawn and garden tool is created. In one orientation the tool functions as an ordinary lawn and garden rake. In a second orientation the tool functions as a broom. Therefore, it is possible to use a single lawn and garden tool for tasks that require both raking and brooming. Additionally, the broom head may be attached to the rake so that the bristles of the broom do not interfere with the normal operation of the rake. In one embodiment, a pair of attachment clips are provided on the broom head to grip the rake frame. In another embodiment, a coupler is provided to attach the broom head to the rake.
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[0001] This application claims the benefit of U.S. provisional application No. 60/620,353, filed Oct. 21, 2004, which is incorporated herein by reference.
BACKGROUND
[0002] This invention relates to weapons defense, in particular to defense against low-flying projectiles, such as rocket propelled grenades and shrapnel.
[0003] Protective arrangements have been devised to limit the destructive effect of exploding weaponry. For example, the 1943 patent to Wesseler (U.S. Pat. No. 2,326,713) discloses knitted wire shielding fabric “for minimizing the destructive effects of bombs, torpedoes and similar elements of warfare.” One form of Wesseler's shielding fabric is described as having “missile deflecting capacity.” Deflection systems also are disclosed by Corrado (U.S. Pat. No. 1,204,547) (torpedoes); Fitch (U.S. Pat. No. 4,625,668) (missiles); Feitosa (U.S. Pat. No. 2,100,211) (aerial bombs); Zuckermann (U.S. Pat. No. 2,347,653) (aerial bombs); Hume (U.S. Pat. No. 2,348,387) (aerial bombs); and Schwab (U.S. Pat. No. 2,351,297) (aerial bombs).
[0004] Nowadays armed conflict in various parts of the world often involves the use of manually portable launchers that fire rocket propelled grenades (“RPGs”) or similar warheads that are designed to explode upon impact. Such “low-flying” warheads travel at relatively. low velocity (as compared to bullets, for example) and typically approach a ground-based target at a relatively low angle of elevation (as compared to aerial bombs, for example, which are dropped from aircraft). Detonation of such low-flying warheads typically is effected by impact pressure on a fuze. Some have a back-up time delay system that detonates the warhead after a preset period of time.
[0005] Often it is necessary to protect personnel and/or materiel at particular locations from the threat posed by RPGs and other low-flying projectiles, which could include non-explosive projectiles as well as explosive warheads. The need for such protection is acute in open terrain and shipboard situations, where there are no natural or man-made barriers (e.g., berms or walls) that would otherwise afford protection. This invention is designed to provide an effective protection system against low-flying projectiles.
SUMMARY OF THE INVENTION
[0006] As RPGs and other low-flying warheads are designed to explode upon impact, the present invention aims to inhibit the likelihood of such explosions preferably by preventing the detonating impact. To prevent the impact, the warhead is “caught” in flight or deflected by a net-like barrier that gradually decelerates the warhead so that it remains intact. If the warhead does explode upon impacting the barrier or after it drops to the ground, substantial blast protection is afforded by the barrier itself, which preferably is deployed at a safe distance from personnel and materiel, thus considerably reducing or eliminating the destructive effect of the blast.
[0007] The projectile is caught or deflected by a barrier that has a net suspended on a ground- or floor-supported frame, which also restrains the bottom margin of the net. Either or both of the top and bottom margins may be resiliently restrained. The side margins of the net preferably are unrestrained, and the net preferably is wider than the frame. Depending on the angle and/or the velocity of the projectile, kinetic energy of the projectile is absorbed by means of net flexion, frame flexion, and/or action of any resilient net restraint. After the projectile is arrested or deflected, the barrier substantially returns to its original position to afford continued protection. The frame preferably has a clear space behind the net to accommodate rearward net deflection by the projectile substantially without interference by the frame. The frame optionally can be adjustable so as to enable adjustment of the angle of the net relative to the vertical in order to tailor the installation to surrounding circumstances for optimum protection, i.e., to minimize the likelihood that warheads fired from particular locations will ride up and over the top of the net.
[0008] The term “net” as used herein is defined as an expanse of any flexible material, e.g., fabric or screening or the like, having sufficient strength and small enough mesh size to at least arrest or deflect (i.e., prevent passage of) an unexploded, low-flying warhead. For optimal protection, the net optionally and preferably should have the properties of a blast curtain, i.e., sufficient strength and small enough mesh size to resist the force of a localized warhead explosion and substantially prevent the passage of small fragments of shrapnel.
[0009] The barrier is modular and is readily portable so that it can be easily transported to and deployed in potentially hostile locations, either on land or on the deck of a ship. Users can erect the barrier system's modular units as needed, e.g., side-by-side to create a wide line of defense or a continuous barrier for perimeter protection around a potential target area, preferably with the nets of adjacent barrier units overlapping. Barrier height can be customized to suit any application. If desired, the barrier units can be anchored to the ground or floor, or to the deck of a ship, and adjacent units can be connected to one another.
[0010] The above and other features, aspects and advantages of the invention will become more apparent from the following detailed description of exemplary embodiments shown in the accompanying drawing figures.
BRIEF DESCRIPTION OF THE DRAWING
[0011] FIG. 1A is a perspective view of a first embodiment of a barrier unit according to the invention for protection against low-flying projectiles.
[0012] FIG. 1B is a perspective view of the barrier unit shown in FIG. 1A , illustrating flexure of the frame and the net as a low-flying projectile is intercepted.
[0013] FIG. 2A is perspective view of a second embodiment of a barrier unit according to the invention.
[0014] FIG. 2B is a perspective view of the barrier unit shown in FIG. 2A , illustrating flexure of the frame and the net as a low-flying projectile is intercepted.
[0015] FIG. 3A is perspective view of a third embodiment of a barrier unit according to the invention.
[0016] FIG. 3B is a perspective view of the barrier unit shown in FIG. 3A , illustrating flexure of the frame and the net as a low-flying projectile is intercepted.
[0017] FIG. 4 is a perspective view of a fourth embodiment of a barrier unit according to the invention.
[0018] FIG. 5 is a perspective view of a fifth embodiment of a barrier unit according to the invention.
[0019] FIG. 6 is a perspective view of a sixth embodiment of a barrier unit according to the invention.
[0020] FIG. 7 is a perspective view of a seventh embodiment of a barrier unit according to the invention.
[0021] FIG. 8 is a perspective view of a plurality of barrier units of the type shown in FIG. 6 , arranged to form a barrier system along a line of defense.
[0022] FIG. 9 is a top plan view of the arrangement of FIG. 8 .
[0023] FIG. 10 is a side elevational view of an adjustable frame portion that enables angular adjustment of the net.
DETAILED DESCRIPTION
[0024] The same reference numbers are used throughout the drawing figures to refer to the same or like parts in the different embodiments. In the figures the net is illustrated as being “see-through,” i.e., as translucent or transparent. This is done merely to be able to depict structure that is behind the net without having to eliminate or break away substantial portions of the net. The actual light-transmitting characteristics of the net will depend, of course, on the color, mesh size and chemical makeup of the net material.
[0025] A first embodiment of a barrier system unit for protection against low-flying projectiles is shown in FIGS. 1A and 1B . The barrier unit 100 includes a frame 102 and a net 104 . The frame 102 includes a plurality of base members 106 , 108 , 110 , 112 in the form of flexible rods that are interconnected by means of brackets 113 . Specifically, there are front 106 and rear 108 base members and left 110 and right 112 side base members. These base members 106 , 108 , 110 , 112 fit into appropriately sized hollow sockets 115 carried by the brackets 113 .
[0026] Stabilizers 114 project rearwardly from sockets 115 on the two rear brackets 113 . Stabilizers 114 are designed to keep the barrier unit 100 from tipping backwards or flipping over when impacted by a low-flying projectile 130 . The underside of each bracket 113 may be provided with a rubbery coating or pad to minimize sliding on hard surfaces, and/or cleats to minimize sliding on sand or soil. At least one hole may be provided in each bracket 113 through which a spike may be driven in order to anchor the barrier unit to the ground. Sandbags may be placed on brackets 113 for stability, irrespective of whether spikes are used.
[0027] Flexible side arch members 116 , 118 of the frame 102 project upwardly and forwardly from the rear brackets 113 . The upper ends of the arch members 116 , 118 support hollow axles 117 , each of which carries a pair of pulleys 124 . A crossbar 120 interconnects axles 117 . As later described, the side-facing sockets 115 on brackets 113 , and the hollow axles 117 , make this a modular system so that a plurality of barrier units 100 can be interconnected or otherwise juxtaposed to form a wider line of defense.
[0028] The pulleys 124 guide cables 126 that are resiliently extensible by means of elongated coil springs 128 , which exert a retractive force on the cables. Each spring 128 can be located intermediate the ends of the cable, or at its lower (rear) end, as shown. The lower end of each spring 128 (or lower end of each cable 126 ) may be connected to a respective rear base member 108 as shown, or to a rear bracket 113 , or to a stabilizer 114 . The other (upper) end of each cable 126 is connected to a net bar 122 . Net 104 is anchored along its top margin to net bar 122 , which acts as a stiffener for the top margin of the net, and is anchored along its bottom margin to front base member 106 .
[0029] In the ready state ( FIG. 1A ), the net bar 122 is disposed substantially above the front base member 106 . In an activate state (i.e., when a low-flying projectile 130 impacts the barrier unit 100 —see FIG. 1B ), the load applied to the net results in a downward and rearward pull on net bar 122 and, accordingly, a pull on cables 126 and a stretching of springs 128 . This causes side arch members 116 , 118 to bend downwardly, which moves axles 117 , pulleys 124 and crossbar 120 downwardly and forwardly. The result is that net bar 122 , although lowered, remains positioned generally above the front base member 106 . The projectile thus is kept from riding up and over the top of the net.
[0030] Several mechanisms act to absorb the kinetic energy of the projectile 130 and gradually reduce its velocity until it is arrested so as to reduce the likelihood of an impact-triggered detonation. These include flexion of the net 104 , downward motion of net bar 122 , bending of the arch members 116 , 118 , and extension of the springs 128 . When the projectile 130 is arrested, it drops to the ground in front of the net 104 with insufficient force to trigger detonation. The barrier unit 100 returns substantially to its ready state by virtue of the restorative nature of the net 104 , the flexible arch members 116 , 118 and the springs 128 .
[0031] In the case of a projectile that has a back-up time delay system, the arrested warhead would be expected to explode after it drops to the ground in front of the net. However, the barrier system still would afford a good measure of protection for personnel and materiel behind the net because the net would act as a blast curtain, and forestall the blast at a reasonably safe distance from the assets to be protected.
[0032] The various components of the barrier unit may be made of a variety of suitable materials, and in suitable sizes, as follows. The net 104 preferably is made of a blast-resistant material, preferably of a mesh size small enough to block the passage of flying fragments from an exploding warhead. Examples include but are not limited to polyethylene or aramid fiber, which may be uncoated, or may be coated with polyvinyl chloride; and polyethylene-wrapped stainless steel cord. A commercial example is that disclosed in U.S. Pat. No. 5,915,449, which is incorporated herein by reference. The net preferably is about 10 to 30 ft. wide by about 10 to 30 ft. high. Brackets 113 are plate-like in form and cover an area about 1.0 ft 2 to 3.0 ft 2 . They preferably are made of steel or aluminum. Base members 106 , 108 , 110 , 112 ; crossbar 120 ; net bar 122 ; arch members 116 , 118 ; sockets 115 ; and axles 117 are about 1½ to 2½ in. in diameter, and are made of any suitably strong and flexible material, such as steel, aluminum, fiberglass, or carbon fiber. Spring rates are chosen to allow a desired degree of net deflection for the anticipated threat, and will depend on net material, net size, and frame flexion, as will be understood by those skilled in the art. For wider nets one or more intermediate cable and pulley sets could be added to provide added support.
[0033] FIGS. 2A and 2B show an alternative embodiment of barrier unit 200 in which hanging weights 228 on the rear (lower) ends of the cables 226 are used in lieu of the springs 128 used in the first embodiment. In this embodiment, the arch members 216 , 218 are provided with intermediate stub axles 217 that support secondary pulleys 224 . The primary pulleys 124 (on axles 117 ) and the secondary pulleys 224 guide the cables 226 that extend between the net bar 122 and the weights 228 . The weights preferably are in the range of 5 to 75 lbs., and may take any form (e.g., sandbags) that can be conveniently attached to cables 226 .
[0034] The operation of this barrier unit 200 is similar to the previously described unit 100 . Specifically, in the ready state, the net bar 122 is disposed substantially above the front base member 106 . In an activate state (i.e., when a low-flying projectile 130 impacts the barrier unit 200 ), the load applied to the net results in a downward and rearward pull on net bar 122 and, accordingly, a pull on cables 126 and a tendency to raise weights 228 . This causes side arch members 216 , 218 to bend downwardly, which moves axles 117 , pulleys 124 and crossbar 120 downwardly and forwardly. The result is that net bar 122 , although lowered, remains positioned generally above the front base member 106 —again to keep the projectile from riding up and over the top of the net.
[0035] In this embodiment, the kinetic energy of the projectile 130 is absorbed by means of flexion of the net 104 , downward motion of net bar 122 , bending of the arch members 216 , 218 , and elevation of the weights 228 . When the projectile 130 is arrested, it drops to the ground in front of the net 104 with insufficient force to trigger detonation. The barrier unit 200 returns substantially to its ready state by virtue of the restorative nature of the net 104 , the flexible arch members 116 , 118 and the weights 228 . Weight size is chosen to allow a desired degree of net deflection for the anticipated threat, and will depend on net material, net size, and frame flexion, as will be understood by those skilled in the art.
[0036] FIGS. 3A and 3B show another alternative embodiment of barrier unit 300 in which spring-loaded spools 324 are carried on axles 117 . The spools 324 have internal torsion springs 328 (not shown), which are substitutes for the springs 128 of the first embodiment, and for the weights 228 of the second embodiment. These internal torsion springs 328 apply a retractive force to cables 326 , which are wound in or on spools 324 and support the net bar 22 so that the net 104 is held generally upright. Each torsion spring may be in the form of a spiral (i.e., clock-type), but any form of torsion spring may be used. The torsion spring may be supplemented with a damper to help dissipate energy during active use. Commercially available dampers that are suitable include those that employ friction disks, and those that employ a fluid forced through one or more orifices or past a series of vanes.
[0037] The operation of this barrier unit 300 is similar to the previously described barrier units 100 , 200 . Specifically, in the ready state, the net bar 122 is disposed substantially above the front base member 106 . In an active state (i.e., when a low-flying projectile 130 impacts the barrier unit 200 ), the load applied to the net results in a downward and rearward pull on net bar 122 and, accordingly, a pull on cables 326 . As cables 326 pay out from spools 324 , torsion springs 328 tighten. This causes side arch members 116 , 118 to bend downwardly, which moves axles 117 , spools 324 and crossbar 120 downwardly and forwardly. The result is that net bar 122 , although lowered, remains positioned generally above the front base member 106 —again to keep the projectile from riding up and over the top of the net.
[0038] In this embodiment, the kinetic energy of the projectile 130 is absorbed by means of flexion of the net 104 , downward motion of net bar 122 , bending of the arch members 116 , 118 , and tightening of the torsion springs 328 as the cables 326 pay out. If the spools 324 are equipped with dampers as described above, the dampers serve to dissipate additional energy. When the projectile 130 is arrested, it drops to the ground in front of the net 104 with insufficient force to trigger detonation. The barrier unit 300 returns substantially to its ready state by virtue of the restorative nature of the net 104 , the flexible arch members 116 , 118 and the torsion springs 328 . Torsion spring rates are chosen to allow a desired degree of net deflection for the anticipated threat, and will depend on net material, net size, frame flexion, and the effect of dampers, if present, as will be understood by those skilled in the art.
[0039] Any of the above embodiments can be modified so that the bottom margin of the net, instead of being firmly anchored to the frame, is resiliently restrained, e.g., by cables with springs in the manner of the embodiments of FIGS. 4-7 . With such an arrangement, the top margin of the net can be resiliently restrained as disclosed above; alternatively the net can be suspended from the frame with its top margin firmly anchored to the frame.
[0040] As noted earlier, the barrier system of the invention is modular so that multiple units can be interconnected to form a wider line of defense. To facilitate this, each of the brackets 113 has a side-facing socket 115 that is designed to be connected to a corresponding element of an adjacent barrier unit. Similarly, the side-facing portion of each axle 117 is designed to be connected to a corresponding element of an adjacent barrier unit. As a result, multiple barrier units 100 , 200 , 300 can be joined side-by-side. A degree of flexibility in the base members 106 , 108 and the crossbar 120 , and in their connections to sockets 115 and 117 , respectively, allows a series of interconnected barrier units to arc around an area so as to form a partial or full protective perimeter. Preferably, angled or other types of connectors (not shown) could be used to couple adjacent barrier units together.
[0041] It is possible to stitch or otherwise attach filler nets (not shown) to the adjacent nets of the joined barrier units in order to reduce the likelihood of projectile penetration at the lateral margins of the nets. However, it is preferred to use nets and net bars that are wider than those illustrated and described in the above embodiments. In that case, the cables 126 , 226 , 326 of the respective embodiments could be guided by the outer pair of pulleys 124 or the outer pair of spools 324 ; alternatively, the outer pair of pulleys or spools could be dispensed with and the net bar and net would extend laterally outwardly further from the supporting cables. Adjacent barrier units would be staggered so that the nets overlap in a manner similar to that shown in FIGS. 8 and 9 and described below in connection with the embodiments of FIGS. 6 and 7 .
[0042] Further embodiments of the invention are illustrated in FIGS. 4-8 . These embodiments use a net material as disclosed above, but employ a more robust frame than the previously described embodiments, the frame thus being more suitable for supporting a larger net and/or standing up to harsher conditions.
[0043] The barrier unit 400 depicted in FIG. 4 has a net 402 with a top margin 404 , a bottom margin 406 , and side margins 408 . The top margin 404 is secured to a top net bar 410 . The bottom margin 406 is secured to a bottom net bar 412 . The net bars 410 , 412 are similar in construction to net bar 122 above ( FIG. 1A ), and serve to stiffen the top and bottom margins 404 , 406 . The net 402 with its net bars 410 , 412 is suspended from a frame 420 by means of three cables 450 that are attached to top net bar 410 . The bottom margin of the net is restrained by the frame by means of three cables 470 .
[0044] Frame 420 may be made of any of the materials mentioned above in connection with the previously described embodiments. The frame components could be designed to have a degree of flexibility that enables them to be a meaningful factor in energy absorption, but preferably they are more rigid than those of the previously described embodiments. The frame components may be welded or otherwise secured together, but preferably most or all of them they are knock-down in design (bolted, clamped or otherwise removably connected) so that the unit can be transported compactly and easily and assembled on-site. Frame 420 has a ground- or floor-engaging base portion comprising three laterally spaced longitudinal bottom bars 422 interconnected by two lateral bottom ties 424 . Each bottom bar 422 has secured to it a front plate 426 , a center plate 428 and a rear plate 430 . These plates may have holes through which spikes may be driven in order to anchor the unit to the ground. Each of the front and rear plates 426 , 430 has three stabilizers 432 that extend forwardly and rearwardly, respectively, to enlarge the effective footprint of the unit.
[0045] Frame 420 also has an upper portion comprising three laterally spaced longitudinal top bars 434 interconnected by two lateral top ties 436 . The upper portion is supported on the base portion by means of three spaced upright portions, each comprising a front post 438 , an angled and bent rear strut 440 , and four stabilizer struts 442 . The front ends of top bars 434 are cantilevered and are disposed substantially forward of posts 438 and above front plates 426 so that net 402 hangs substantially vertically, with ample deflection space behind it.
[0046] Each cable 450 suspending top net bar 410 is guided by a frame-mounted front pulley 452 at or near the front end of top bar 434 , and a frame-mounted rear pulley 454 at or near the top of post 438 . Cable 450 is anchored to the frame via a coil spring 456 , which places the cable under initial tension and renders it resiliently extensible. Similarly, each cable 470 restraining the bottom net bar 412 is guided by a frame-mounted front pulley 472 at or near front plate 426 , and a frame-mounted rear pulley 474 on bottom bar 422 behind post 438 . Cable 470 is anchored to the frame via a coil spring 476 , which places the cable under initial tension and renders it resiliently extensible. Spring rates are chosen to allow a desired degree of net deflection for the anticipated threat, and will depend mostly on net material and net size (the frame flexion factor should be minimal given the robust nature of the frame). A suspended weight, a torsion or other type of spring, a gas spring, or any other element or unit that applies a restorative force (and optionally a damping force) to each cable may be substituted for the coil springs in this or any other embodiment.
[0047] The front ends of top bars 434 optionally may be made adjustable in length so as to adjust the fore/aft position of pulleys 452 and, hence, the fore/aft position of top margin 404 of the net, to vary the angle of the net relative to the vertical. This is illustrated by dashed lines and reference number 435 in FIG. 4 for just one of the top bars 434 , it being understood that a frame having this adjustment feature will necessarily require that all top bars 434 be adjustable in this manner. This adjustment feature may be incorporated into this or any other embodiment of the barrier unit. Adjustment of the fore/aft position can be accomplished by any suitable structure. For example, as illustrated in FIG. 10 , each top bar 434 may have a movable telescoping front portion 434 a that can be extended forwardly from the fixed portion 434 and be secured in a selected position by means of a shear pin or pins (not shown) placed in aligned holes 435 b in the fixed ( 434 ) and movable ( 434 a ) telescoping portions. Other examples of length-adjustable members are well-known to those skilled in the art, and include telescoping members with locking clutch collars; telescoping threaded members; and hinged, foldable extensions, to name just a few.
[0048] When a projectile impacts net 402 , the net will deflect rearwardly due to net flexion and the extension of springs 456 , 476 , all of which serve to absorb the kinetic energy of the projectile in a manner similar to the operation of the embodiment of FIGS. 1A , 2 A, arresting the projectile and causing it to drop to the ground in front of the net. However, by comparison much less kinetic energy would be absorbed through frame flexion due to the more robust construction of the frame of this embodiment.
[0049] This embodiment and those described below can be modified so that the net is suspended from the frame with its top margin firmly anchored to the frame. Alternatively, the bottom margin of the net can firmly anchored to the frame. In either case, the other margin of the net would be resiliently restrained as disclosed.
[0050] The embodiment of FIG. 5 is similar to that of FIG. 4 . The differences reside in the base portion of frame 500 , in which each bottom bar 522 has three depending legs 532 , which are intended to be buried in the ground to stabilize the unit. One or more apertured plates 528 also may be provided on each bottom bar 522 .
[0051] The embodiment of FIG. 6 is similar to that of FIG. 4 , but employs a modified net 602 that is wider than the frame 600 . Protrusion of the net laterally beyond the sides of the frame facilitates deployment of a more effective multi-unit barrier system because the nets of adjacent units can be overlapped. Top net bar 610 and bottom net bar 612 preferably are as wide as net 602 . Note that the lateral cables 650 , 670 are located inboard of the ends of the net bars 610 , 612 . It is possible for the unit to be configured so that only one side of the net projects beyond the frame, but the symmetrical arrangement illustrated in FIG. 6 provides more flexibility in terms of configuring an effective barrier system.
[0052] The embodiment of FIG. 7 has the combined attributes of the embodiments of FIGS. 5 and 6 . Depending legs 732 can be buried in the ground for stability, while a symmetrical net assembly 702 , 710 , 712 wider than the frame allows for net overlap in a barrier system.
[0053] FIGS. 8 and 9 depict a barrier system deployed with the nets 602 of adjacent units overlapping one another (units 600 according to the embodiment of FIG. 6 are used as an example). The units are shown in alternating positions, which defines a substantially straight barrier. The units could also be placed in stepped positions (each one slightly behind the preceding one) so that the net faces continuously recede. In either case the units can be angled so as to form a generally arcuate barrier. Adjacent units optionally can be joined together by suitable links 902 (only two are shown in FIG. 9 ) for added stability of the barrier system as a whole. Links 902 can be placed at ground level and/or above ground level. They can take any suitable form that will help keep adjacent units from separating or shifting. Examples include but are not limited to bars clamped or bolted to the frames, and cables or chains encircling or otherwise secured to frame members, to name just a few.
[0054] The invention is not limited to the above-described embodiments, and it will be understood by those skilled in the art that various modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
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A barrier system acts to gradually decelerate and arrest low-flying projectiles, such as RPGs, to reduce the likelihood of a fuze-detonating impact. The barrier system, which includes a frame-supported net and net suspension, preferably with energy absorbing characteristics, preferably is modular and portable so that similar barrier units can be arranged, and optionally joined together, to form a wider line of defense, such as a defensive perimeter around a potential target area.
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TECHNICAL FIELD
[0001] This invention relates generally to mobile communications devices and methods and, more specifically, relates to content delivery, web browsers and device software over the air delivery used with wireless communications terminals and appliances.
BACKGROUND
[0002] As the amount and complexity of software in mobile communications devices increases there is an increasing need for manufacturers, service providers and software developers to maintain the mobile device configuration and its software components after the manufacturing phase. For example, selling add-on applications or commercial content to users of mobile devices ideally requires compatibility checking and management of the interrelated dependencies of the software modules. While providing generic profile or model information of the device may be sufficient for relatively simple content delivery (e.g., such as a music download), for application installations and particularly for firmware updates it is essential to obtain detailed mobile device information in order to correctly select delivery versions and download packages. In many cases, however, these important details are not known to the user, and/or are not visible to the user through the user interface.
[0003] The Open Mobile Alliance (OMA) has standardized a set of service enablers to fulfill the needs of device management and downloads of digital products. However, many of the standards are quite tightly focused on the mobile domain, and thus integrating them as architectural components into a more generic digital delivery system entity is not straightforward.
[0004] In many cases the use of digital delivery for mobile devices is e-commerce oriented. As such, in addition to technical level device management tasks there are several user level aspects such as demand creation, menu browsing, selection, commitment and payment.
[0005] A natural technology choice, and the current defacto method for implementing the user interface, is through web technologies, particularly HTTP browsing and web applications. Thus, any attempt to address the problems discussed above should ideally be compatible and inter-operate with existing and future web-related technologies, including web browsers.
[0006] General reference with respect to updating a user can be made to the following U.S. Patents, all by Richard R. Reisman: U.S. Pat. No. 5,694,546, “System for Automatic Unattended Electronic Information Transport Between a Server and a Client by a Vendor Provided Transport Software with a Manifest List”; U.S. Pat. No. 6,125,388, “System for Transporting Information Objects Between a User Station and Multiple Remote Sources Based upon User Modifiable Object Manifest Stored in the User Station”; U.S. Pat. No. 6,594,692 B1, “Methods for Transacting Electronic Commerce”; and U.S. Pat. No. 6,658,464 B2, “User Station Software that Controls Transport, Storage, and Presentation of Content from a Remote Source”.
SUMMARY OF THE PREFERRED EMBODIMENTS
[0007] The foregoing and other problems are overcome, and other advantages are realized, in accordance with the presently preferred embodiments of these teachings.
[0008] In one aspect this invention provides both a method and a system to automate a device session in combination with a user's interaction with a server. The method includes, in response to receiving a certain type of HTTP request message from the device during a browsing session, sending a HTTP response message to the device. The HTTP response message includes a dedicated MIME-type for indicating that a device management session is being initiated, and the device management session is identified by an identifier that forms part of the HTTP response message. The device replies to the HTTP response message with a device management session reply that comprises device details and the identifier. Using the device details, the system develops a list containing at least one download option that is compatible with the device and sends the list to the user. In response to a user selecting the at least one download option from the list, the system delivers the selected at least one download option to the device during a device management session.
[0009] In another aspect this invention provides a method to operate a device to download information via a wireless network, and a device having a controller that operates in accordance with the method. The method includes, during a wireless HTTP session, making an inquiry with the device with regard to downloadable information; in response to the inquiry, initiating a secure device management wireless dialog with the device to obtain device-specific parameters descriptive of at least certain capabilities of the device; generating a list and sending the list to the device, the list comprising at least one entry that is descriptive of downloadable information that is compatible with the device capabilities; and during a wireless HTTP session, selecting at least one entry from the list to be downloaded to the device.
[0010] In a further aspect of this invention there is provided a device management server that is operable with a device to download information via a wireless network to the device. The device management server includes a first interface for coupling to the device, a second interface for coupling to a workflow manager and a controller that operates with a program to perform operations that are initiated in response to the device, during a wireless HTTP session, making an inquiry with regard to downloadable information. The device management server is further responsive to the workflow manager initiating a secure device management wireless session with the device to obtain device-specific parameters descriptive of at least certain capabilities of the device; to cooperate with the workflow manager via the second interface to generate a list and to send the list towards the device via the first interface, where the list contains at least one entry that is descriptive of downloadable information that is compatible with the device capabilities; and during a wireless HTTP session, to download information to the device corresponding to at least one entry from the list selected by a user of the device.
[0011] In a still further aspect of this invention there is provided a workflow manager operable with a device and with a device management server for downloading information via a wireless network to the device. The workflow manager includes a first interface for coupling to the device via a web site and to the device management server, a second interface for coupling to at least one back-end system, and a controller that operates with a program to perform operations initiated in response to the device, during a wireless HTTP session, making an inquiry to the web site with regard to downloadable information. The workflow manager initiates a secure device management wireless session with the device to obtain device-specific parameters descriptive of at least certain capabilities of the device; and cooperates with the device management server via the first interface and with the at least one back-end system via the second interface to generate the list that is descriptive of downloadable information that is compatible with the device capabilities. The workflow manager further operates to send the list towards the device via the first interface and via the web server.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The foregoing and other aspects of the teachings in accordance with this invention are made more evident in the following Detailed Description of the Preferred Embodiments, when read in conjunction with the attached Drawing Figures, wherein:
[0013] FIG. 1 is logical level sequence diagram of a typical sequence for digital delivery as part of an e-commerce oriented use case;
[0014] FIG. 2 is a message flow sequence diagram for the exemplary case of a firmware update that takes place with a device in accordance with preferred embodiments the invention;
[0015] FIG. 3 is a block diagram of a device suitable for use in the message flow sequence of FIG. 2 ;
[0016] FIG. 4 is a block diagram of a DM server suitable for use in the message flow sequence of FIG. 2 ;
[0017] FIG. 5 is a block diagram of a workflow manager suitable for use in the message flow sequence of FIG. 2 ;
[0018] FIG. 6 shows a non-limiting example of the structure of a HTTP Response message that carries a Device Management notification message in accordance with an aspect of the teachings of this invention; and
[0019] FIG. 7 shows a non-limiting example of the structure of the Device Management notification message that is carried by the HTTP Response message of FIG. 6 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] Examples of documents that are descriptive of current web-related technologies of interest to the presently preferred embodiments of this invention include: RFC 2616: Hypertext Transfer Protocol-HTTP1.1, IETF, June 1999; RFC 2109: HTTP State Management Mechanism; IETF, February 1997; and SyncML Device Management Protocol, Version 1.1.2 (OMA-SyncML-DMProtocol-V — 1 — 2-20030612-C), Open Mobile Alliance, June 2003.
[0021] In order to ensure a pleasant user experience during a digital delivery transaction, the inventors have realized that the detailed level device information gathering and management procedures should be automated and seamlessly integrated with the digital delivery transaction. In the preferred embodiments of this invention a model is used that utilizes OMA service enablers, preferably OMA Device Management and OMA Download, as integrated sub-components in a web browsing-based digital delivery transaction. The use of the presently preferred embodiments of this invention is particularly beneficial for the firmware update use case, but may be applied to benefit other digital delivery applications as well.
[0022] For the purposes of this invention “firmware” may be considered to comprise computer code written in a relatively low level language that is executable either directly or indirectly (e.g., after being run through a compiler or an interpreter) by a data processor that forms part of the device 10 . An example of firmware, or a firmware upgrade, could be a revision to, as non-limiting examples, an operating system module, an http protocol stack implementation, or an improvement to a wireless network access and/or scanning procedure necessitated by, or made optional in view of, a change to an underlying communications standard. In contradistinction, an “application” may be considered a higher level program that imparts a new, and possibly optional, functionality to the device 10 , such as an improved or different Internet browser, or a media player, or an image capture program that provides for archiving captured images (assuming that the device 10 includes a digital camera) to some network-provided image database. As can be appreciated, the specifics of the device 10 construction and operation, such as the revision level of its operating system software, the amount of installed memory, the type (e.g., model number) of its digital camera and other types of parameters can have a significant influence on the type and/or revision level of the firmware or application software that is downloaded to the device 10 . As but one example, the user may desire to download firmware or an application that is incompatible with the hardware of the device 10 , or that requires more memory than the device 10 has installed, or that assumes an operating system version that was released subsequent to the manufacture date of the device 10 . In any of these cases simply downloading the user-requested firmware or application could create significant problems for the user, and a less than optimum user experience with the web site 30 , which may be associated with the manufacturer of the device 10 , or with a network operator with whom the user 1 has a subscription. One motivating factor for this invention is to avoid such problems, and to do so with a minimal impact on the user. It is a desirable goal to provide the user with an optimal experience for both user-interactive and non-user-interactive (e.g., background) type of operations.
[0023] It should be appreciated at the outset that while the preferred and exemplary embodiments of this invention discussed below are presented in the OMA framework, this invention is not limited for use only with OMA-based enablers and technology.
[0024] By way of introduction, a typical sequence for digital delivery as part of an e-commerce-oriented use case is illustrated in FIG. 1 in the form of a logical level sequence diagram. FIG. 1 shows an end user 1 associated with a mobile station (MS) 10 , a DM server 20 and a web server 30 . A user session is assumed to exist between the end user 1 and the web server 30 , while a device session exists between the MS 10 and the DM server 20 . FIG. 1 is useful in explaining the problems that arise in a conventional digital delivery session to a MS 10 , and thus aids in providing an enhanced understanding of the improvements provided by the preferred embodiments of this invention.
[0025] It should be noted through that the teachings of this invention are applicable to a number of user interface technologies, are not limited to only web-interface technologies. As non-limiting examples, the teachings of this invention are also applicable to Wireless Application Protocol (WAP) technologies, and to JAVA™ based applications.
[0026] With regard to FIG. 1 , it may be assumed that as the successful result of successful marketing and according to web link information the user 1 has arrived at the web site 30 which has downloadable items available for mobile stations. This interaction is shown as the generic browsing 40 . To ensure that the alternatives presented to the user 1 are actually compatible with and functional in the user's MS 10 , the server-side system needs to know the capabilities of the MS 10 . A conventional manual procedure to accomplish this would be to restrict the spectrum of digital product variances according to a range of MS 10 models and, as a starting point for the user interaction, prompt the user 1 for the MS 10 model information. However, there are number of disadvantages inherent in this conventional approach. As a few examples, and first, this approach can result in a bad user experience, as the user 1 is prompted to perform a mundane data entry task. Further, unless the instructions to the user are perfectly clear, the user 1 may abandon the web server 30 and go elsewhere for the desired digital delivery. Second, the information reliability can be compromised by requiring the user 1 to enter the information. As may be appreciated, in some cases the correctness of the device information is very critical for a successful delivery (and particularly for a successful activation of a delivered application or firmware). Third, and related to the first two issues, the complexity of the information required may be such that the user 1 does not know the information, and may not be able to retrieve it using the conventional user interface of the MS 10 .
[0027] In addition to the user session 40 , a separate device session 42 is used to gather sufficient device information to create a menu of alternative downloadable items for the user 1 . This menu may shown in a web-based user session 44 , where user 1 can browse through the menu, read additional information, select and commit to a delivery. Finally, and according to the user 1 selection(s), the delivery and related device management tasks are completed through a second device session 46 .
[0028] The inventors have realized that a problem that arises in the exemplary scenario depicted in FIG. 1 is how to best combine the two different sessions (user session and device session) and transfer data between them. For example, after the user 1 has arrived at the web server 30 by using a web browser, and desires that a list of relevant items be shown, what is the best way to begin an OMA device management session to obtain the device (MS 10 ) capability and compatibility information? Further, and assuming that this automatic information gathering can be completed, what is the best technique to return the results in the web session to the user's browser? In other words, what is the most opportune manner in which to integrate or bootstrap an OMA DM session with the user's web browsing session?
[0029] In order to gain a fuller understanding of the underlying problems that are inherent in providing an integrated user browser and OMA DM session, a brief discussion is now provided of some pertinent basic fundamentals of web technologies (in the context of HTTP), and also OMA device management.
[0030] HTTP is the simple and powerful network protocol of the web. It is usually implemented on top of Transport Control Protocol/Internet Protocol (TCP/IP) sockets to transfer resources (files, application output) from a HTTP server (usually a web server) to a HTTP client (such as a web browser).
[0031] Originally, the concept of a web session did not exist in HTTP, as HTTP is a stateless protocol; i.e., it has two messages, request and response, and includes alternative methods: GET, POST and HEAD. In the original sense, a HTTP “session” starts when the request message is sent, and the HTTP session ends when the response message is received.
[0032] At first, the underlying TCP/IP session was closed after each pair of request-response messages. However, as web technology progressed and became more widely used the size and complexity of web pages increased dramatically, leading to the typical currently viewed web pages with tens or hundreds of separate HTTP resources (such as flashing GIF icons, blinking banners, and animated thumbnail advertisements). As a result of this increase in HTTP web page complexity the computing resource expense, at both the client and at the server, to open and close down a dedicated TCP/IP socket for each HTTP request became too great. In response, protocol specialists standardized (in HTTP 1.1) a technique to use a persistent TCP/IP connection. However, even with the persistent TCP/IP socket in place it is not possible for the server to send a response message towards the client without a preceding HTTP request message. Stated another way, a web server cannot push information to a browser (see RFC 2616: Hypertext Transfer Protocol-HTTP/1.1, IETF, June 1999).
[0033] Notwithstanding the stateless orientation of HTTP, the need for web sessions quickly became apparent as more web applications appeared. The HTTP state management mechanism (see RFC 2109: HTTP State Management Mechanism; IETF, February 1997) provides the web application developer with features on top of HTTP to combine several HTTP messages into one specific user session. An implementation includes cookies, which carry user and session related information in all of the messages from the client to the server. The server typically encrypts the cookie to prevent a fraudulent client from tampering with its content.
[0034] Turning now to OMA DM, and as the full name for OMA DM indicates, the SyncML Device Management Protocol utilizes SyncML in the device management domain. This is a client-server protocol for implementation in a DM client and in a DM server.
[0035] A DM client includes a management tree, which is a tree-formed data structure containing manageable objects. To carry out the required device management tasks a DM server uses commands such as Get, Replace and Exec that are targeted to the objects in the management tree.
[0036] OMA DM is optimized for interactions between a server and a device, such as the MS 10 of FIG. 1 . For user interactions there are simple commands to implement features such as notifications and user choices, but in general the user interface capabilities of OMA DM are very limited.
[0037] Prior to an OMA device management session being established a device should be “bootstrapped”. The SyncML Device Management Protocol standard defines two methods for bootstrapping:
(a) Customized bootstrap, where devices are loaded with SyncML DM bootstrap information at manufacture (also referred to as a factory bootstrap); and (b) Server initiated bootstrap, where a server sends out bootstrap information via some push mechanism, e.g. WAP Push or OBEX. In this method the server must be informed of the device address/phone number beforehand. During the bootstrapping procedure a number of parameters are set in the device, including the server address and identification, as well as both client and server-related authentication information. While the presently preferred embodiments of this invention prefer to use the factory bootstrap procedure, the server-initiated bootstrap procedure may be used as well.
[0040] Having thus described the HTTP and OMA DM environments that are most germane to the presently preferred (but non-limiting) embodiments of this invention, a description is now provided of the presently preferred embodiments of methods and apparatus in accordance with this invention.
[0041] Salient aspects of this invention include the use of a dedicated MIME-type in a HTTP response message to launch the OMA DM session and to send bootstrapping parameters to the device; the encryption with a secret key of the bootstrapping information in a client provisioning message (notification may be used in lieu of bootstrapping); and the use of an upper layer digital delivery session and its identification to combine a web session and device session(s) into one overall logical transaction. A further aspect of this invention relates to a procedure to return control to the web session after the device session by use of a queued HTTP request; an OMA DM Exec command to a web browser object with a predefined URL; and a user response to a previously sent activation prompt.
[0042] More specifically, what is implied by this further aspect of the invention is the following:
[0000] 1. A Queued HTTP Request
[0043] As a reaction to the HTTP response (message (g) of FIG. 2 , discussed below), and in addition to the DM session establishment (message (h) of FIG. 2 , discussed below), the device 10 creates an HTTP request to the web server 30 . The web server 30 queues the request until it receives a user options message (message (o) of FIG. 2 , discussed below), and then sends the response to the browser 10 B (message (p) in FIG. 2 , discussed below).
[0000] 2. OMA DM Exec
[0044] After creating the menu (activity (n) in FIG. 2 , discussed below), a workflow manager 50 requests the DM server 20 to send an Exec command to device 10 DM Client 10 A, and in this manner requests that the device's web browser 10 B become active and send an HTTP request to the web server 30 . The web server 30 responds to this HTTP request by sending the options (message (o) of FIG. 2 , discussed below) to web browser 10 B in the HTTP response (message (p) in FIG. 2 , discussed below).
[0000] 3. User Response to Activation Prompt.
[0045] As part of the HTTP response (message (g) in FIG. 2 , discussed below), there also exists user interface information to be presented in web browser 10 B. This user interface activity includes presenting a prompt for the user (e.g. “please wait, device information being gathered”) and a submit (e.g., “ok”) button. When the user accepts the information (e.g., by pressing the “ok” button) the web browser 10 B sends a HTTP request to web browser 30 . This request will then be handled as in alternative 1 (as a queued HTTP request).
[0046] In general, MIME was originally intended to extend the format of Internet mail to allow non-US-ASCII textual messages, non-textual messages, multi-part message bodies and non-US-ASCII information in message headers. The following RFCs define MIME: RFC 2045: MIME Part One: Format of Internet Message Bodies; RFC 2046: MIME Part Two: Media Types; RFC 2047: MIME Part Three: Message Header Extensions for Non-ASCII Text; RFC 2048: MIME Part Four: Registration Procedures; and RFC 2049: MIME Part Five: Conformance Criteria and Examples. Reference can also be had to RFC 1341 (June 1992), which was obsoleted by RFC 1521: MIME (Multipurpose Internet Mail Extensions) Part One: Mechanisms for Specifying and Describing the Format of Internet Message Bodies (September 1993); and RFC 1342: MIME (Multipurpose Internet Mail Extensions) Part Two: Message Header Extensions for Non-ASCII Text (September 1993).
[0047] A system description is now provided with respect to the embodiment of FIG. 2 , which shows the signal and message flow between the user 1 , the device, such as the MS 10 of FIG. 1 , the web site (or web server) 30 , the DM server 20 , the above-mentioned workflow manager 50 and one or more back-end systems 60 . The capabilities and responsibilities of these various components, which may also be referred to herein as actors, is described below, followed by a description of the usage sequence depicted in FIG. 2 .
[0048] It should be noted that in a presently preferred embodiment of this invention, but by no means as a limitation upon the practice of this invention, the link between the device 10 and the web site 30 is carried at least partially though a wireless link, such as a cellular RF link, or a Bluetooth link, or a wireless local area network (WLAN) link, or through an optical link, possibly via a network provider (e.g., via a cellular network operator, or a WLAN hotspot operator) of the device 10 .
[0049] For the purposes of the description of the presently preferred embodiments of this invention, and not as a limitation upon the practice of this invention, the user 1 is a human being that uses the device 10 . The user 1 may be interested in (possibly commercial) digital products available in the network, such as content, applications and/or firmware updates. Web browser is the preferred application to discover, select and commit to delivery of a digital product. The user 1 does not necessarily own the device 10 .
[0050] For the purposes of the description of the presently preferred embodiments of this invention, and not as a limitation upon the practice of this invention, the device 10 is or includes a mobile component having an instance of an OMA DM client application implementation 10 A and a HTTP 1.1 compliant web browser 10 B. For firmware updates the device 10 may have, as an exemplary and non-limiting example, OMA Firmware Over the Air (FOTA) capability. The device 10 may be, as exemplary and non-limiting embodiments, a cellular or a non-cellular telephone, or a computer having a wireless interface (RF and/or IR) with a local and/or a wide area network (LAN and/or WAN), or a personal digital assistant (PDA) having a wireless interface (RF and/or IR) with a LAN and/or a WAN, or any suitable Internet appliance enabling the user 1 to operate a browser to contact the web server or site 30 . This being the case, the device 10 will typically comprise a wireless (RF or optical) transceiver.
[0051] Reference is made to FIG. 3 for showing a non-limiting example of a block diagram of the device 10 that is suitable for use in the message flow sequence of FIG. 2 . Device 10 is assumed to include a controller 1 , such as a microprocessor, that is coupled to memory 12 that stores, in addition to an operating system and other typical software, software for implementing the OMA-DM client 10 A in accordance with this invention, as well as a web browser 10 B. Also found in the memory 12 may be a device table 10 C that stores device details (e.g., hardware capabilities, operating system version, memory capacity) that were loaded upon manufacture, or when the device was first activated. Also provided is a user interface (UI) 13 , or an interface to a suitable UI. In one non-limiting embodiment the UI 13 includes a user display (e.g., a LCD display) 13 A and a keyboard or keypad 13 B user data entry device. The controller 11 is also coupled to a suitable RF or optical transceiver 14 for communication with the website 30 and the DM Server 20 , typically via a wireless network/operator, such as a cellular telephone network operator, or a Wireless LAN network. Note that in a wired embodiment of the device 10 the transceiver 14 may be coupled to an electrical or optical cable or other wiring.
[0052] For the purposes of the description of the presently preferred embodiments of this invention, and not as a limitation upon the practice of this invention, the web site 30 contains or is linked to a HTTP 1.1-compliant web server that implements the user interface (HTML pages) towards the user 1 . The web site 30 preferably has an Application Program Interface (API) to implement web applications, and an interface towards other server side components (e.g., 20 , 50 , 60 ).
[0053] For the purposes of the description of the presently preferred embodiments of this invention, and not as a limitation upon the practice of this invention, the DM server 20 implements an OMA SyncML DM protocol stack, communicates with the DM client 10 A in the device 10 , and has interfaces to other server-side components ( 30 , 50 , 60 ). Reference with regard to SyncML can be had to, as examples, SyncML Device Management Protocol, Version 1.1.2 (OMA-SyncML-DMProtocol-V1 — 1 — 2-20030612-C, Open Mobile Alliance, June 2003, as well as to SyncML Device Information DTD, version 1.1, February 2002 (where DTD represents Document Type Definition)).
[0054] Reference is made to FIG. 4 for showing a non-limiting example of a block diagram of the DM server 20 that is suitable for use in the message flow sequence of FIG. 2 . DM server 20 is assumed to include a controller 21 , such as a microprocessor, that is coupled to a memory 21 A that stores, in addition to an operating system and other typical software (SW), software for implementing the OMA SyncML DM protocol stack and software for communicating with the OMA-DM client 10 A of the device 10 . The DM server 20 includes input and output interfaces (I/Os) 22 A and 22 B (which may be logical and/or physical I/Os) for communication with the device 10 and the workflow manager 50 . Note that both I/O interfaces 22 A, 22 B may be embodied as logical interfaces that communicate via TCP/IP over the Internet.
[0055] For the purposes of the description of the presently preferred embodiments of this invention, and not as a limitation upon the practice of this invention, the workflow manager 50 keeps track of the overall digital delivery process, e.g., a firmware update transaction. The workflow manager 50 creates a unique transaction identification (TID), uses the web server 30 and DM server 20 as interfaces to the user 1 and the device 10 , and combines the individual lower level sessions into one logical transaction. The workflow manager 50 preferably uses the services in the back-end systems 60 to complete certain specific tasks during the transaction with the device 10 .
[0056] Reference is made to FIG. 5 for showing a non-limiting example of a block diagram of the workflow manager 50 that is suitable for use in the message flow sequence of FIG. 2 . Workflow manager 50 is assumed to include a controller 51 , such as a microprocessor, that is coupled to a memory 51 A that stores, in addition to an operating system and other typical software (SW), software for generating the TID and for managing and correlating the various transactions with the device 10 and other system components. The workflow manager 50 I/Os 52 A and 52 B (which may be logical and/or physical I/Os) for communication with the web site 30 , the DM server 20 , and the back-end server(s) and system(s) 60 . As with the DM server 20 , both I/O interfaces 52 A, 52 B may be embodied as logical interfaces that communicate via TCP/IP over the Internet.
[0057] For the purposes of the description of the presently preferred embodiments of this invention, and not as a limitation upon the practice of this invention, the back-end server(s) and system(s) 60 provide services for the workflow manager 50 . The services may include, but are not restricted to, security services for authentications, encryptions and signatures, device 10 -related services such as legal and warranty status information, as well as detailed product management services, such as Product Data Management (PDM) information.
[0058] For the purposes of the description of the presently preferred embodiments of this invention, and not as a limitation upon the practice of this invention, the workflow manager 50 and the back-end system(s) 60 are controlled by the same entity that controls the web site 30 and the DM server 20 . However, this is not a limitation upon the practice of this invention, and one or both of these components may be under the control of third parties. For example, one of the back-end systems 60 may be a third party digital signature authenticator, or a third party digital payment facilitator.
[0059] Turning now to the exemplary sequence diagram shown in FIG. 2 , the following steps are executed in accordance with the embodiments of this invention. At (a) the user 1 browses through competing web sites and finds a desired vendor's firmware (FW) update pages. At (b) the user 1 clicks a link in a FW update page to determine which new FW update alternatives (if any) are available for the device 10 . At (c) the web site 30 sends a page to the user 1 , via the device 10 , and the HTTP response is used to inform the user 1 via the device 10 that automated device information gathering is about to start. A suitable message may be: “Wait while we retrieve the requested firmware for your phone”. At (d) the user 1 accepts, via the user interface of the device 10 , the automated device session establishment, which results in a HTTP request being sent from the browser 10 B to the web server 30 . At (e) the web server 30 informs the workflow manager 50 that there is a user request to start a firmware update transaction (FWupdTransaction) and to establish an OMA DM session. In response, the workflow manager 50 creates a new transaction with a unique TID. At (f), and with the assistance of the back-end services 60 , the workflow manager 50 creates a suitable OMA client provisioning (CP) message and signs it with the secret key. An INIT DM message is sent to the web site 30 with the encrypted CP. At (g), and as part of the HTTP response, the web site 10 sends the signed CP message, with a MIME-type dedicated to OMA device management, to the device 10 . The TID is embedded in the HTTP response message. Based on the MIME-type information and the signed CP message, at step (h) the device 10 checks the validity of the DM bootstrapping information, sets the parameters accordingly, and launches the OMA DM client application 10 A. At (i) the OMA DM client 10 A establishes an OMA DM session and sends device 10 information details to the DM server 20 . These device details may be stored in the table 10 C in the memory 12 of the device 10 , and may have been loaded upon manufacture, or when the device was first activated. In any case, the user 1 need not be aware of the device 10 information, as this step (i) preferably occurs automatically, and without involvement of the user 1 . The TID is preferably included as a part of this information that is sent back to the DM server 20 . At (j) the DM server sends the TID and the received device information to the workflow manager 50 , and at (k) the workflow manager 50 communicates with the back-end services 60 to determine whether the amount and level of details in device 10 information is sufficient to create a list of alternatives (a menu of firmware download options). If there is a need for more detailed and specific device 10 information, at (l) the workflow manager 50 requests the DM server 20 to fetch the relevant data from the device 10 . In this case at (m), and by using the OMA DM protocol, the DM server 20 obtains the additional device 10 information and sends it back to the workflow manager 50 . At (n) the workflow manager 50 creates (or uses one or more back-end services 60 to create) a list of available alternatives, i.e., a menu of firmware download options for the end user 1 . At (o) the workflow manager 50 sends the menu of firmware download options to the web site 30 , and at (p) the web site 30 returns the menu to the browser 10 B for the user 1 to select products or request more (web-formalized) information. This can be accomplished at (p) via at least three techniques: a previously queued HTTP request; an OMA DM exec to web object; or a user action in a previously sent web page. By whatever technique is used at (p), additional web browsing, involving HTTP requests and responses (user 1 via device 10 with the web site 30 ), and eventual delivery of the requested firmware and device management (device 10 and DM server 20 ), occurs at steps (q) and (r), respectively. Note that any suitable technology and mechanism can be used for the actual download of the firmware to the device 10 .
[0060] An aspect of combining a web session with an automated DM session, in accordance with embodiments of this invention, involves conveying the OMA DM notification message within an HTTP response message (message (g) in FIG. 2 ). Referring to FIG. 6 , the HTTP response message generally contains a Status Line field 102 , a General Headers field 104 , a Response Headers field 106 , an Entity Headers field 108 , a delimiter or separator, shown as a carriage return/line feed (CRLF) 109 , and a Message Body field 110 . Of most interest to the non-limiting embodiments of this invention is the Entity Headers field 108 , that contains a Content-Type field 108 A, a Content-Length field 108 B and a Last-Modified field 108 C. Of particular interest is the Content-Type field 108 A that conveys the above-mentioned predetermined MIME-type. As non-limiting examples, the predetermined MIME-type for a General Notification Initiated Session Alert message may be Content-type 108 A: “application/vnd.syncml.notification”, and the Content-Type code may be 0x44.
[0061] In a presently preferred, but non-limiting embodiment of the structure of the HTTP response message illustrated in FIG. 6 , the OMA DM notification is carried in the Message-Body field 110 .
[0062] An exemplary HTTP response message content may be as follows:
Response = Status-Line (102 in Fig. 6 ) *(( general-header (104 in Fig. 6 ) | response-header (106 in Fig. 6 ) | entity-header (108 in Fig. 6 ) ) CRLF) CRLF (109 in Fig. 6 ) [ message-body ] (110 in Fig. 6 ) status-line = HTTP/1.1 <Space> status-code+reason-phrase status-code+reason-phrase = 200 <Space> OK | 400 <Space> Bad Request | 404 <Space> Not Found | 500 <Space> Internal Server Error | 501 <Space> Not Implemented general-header = Date: <Space> date <CRLF> Connection: <Space> close <CRLF> response-header = Server: <Space> vendor-string <CRLF> entity-header = Content-Length: <Space> integer-greater-or-equal-0 <CRLF> Content-Type: <Space> text/html <CRLF> Last-Modified: <Space> date <CRLF> [ Cache-Control: <Space> no-cache <CRLF> ] // only for dynamic pages [ Expires: <Space> date <CRLF> ] // only for dynamic pages message-body = // the contents of the document requested by the client date = // date format according to RFC822 and RFC1123 vendor-string = // server identification // (freely definable by the server implementor)
[0063] The fields of an exemplary embodiment of the OMA DM notification message 120 are shown in FIG. 7 , where:
Field Description digest 122 MD5 Digest value trigger-hdr 124, containing: version 124A Device Management Version ui-mode 124B not-specified/user-interaction initiator 124C Server/User initiated (client/server) future-use 124D reserved for future DM use sessionid 124E Session identifier length-identifier 124F Server Identifier length server-identifier 124G Server Identifier trigger body 126 vendor-specific
[0064] One non-limiting example of a DM Device Details message (message (i) in FIG. 2 ) is shown below (reference may be had again to: SyncML Device Management Protocol, Version 1.1.2 (OMA-SyncML-DMProtocol-V — 1 — 2-20030612-C), Open Mobile Alliance, June 2003):
<SyncML xmlns=‘SYNCML:SYNCML1.1’> <SyncHdr> <VerDTD>1.1</VerDTD> <VerProto>DM/1.1</VerProto> <SessionID>1</SessionID> <MsgID>1</MsgID> <Target> <LocURI>http://XXXX/mgmt-server</LocURI> </Target> <Source> <LocURI>IMEI:XXXX</LocURI> </Source> <Cred> <!-- Client credentials --> <Meta> <Type xmlns=“syncml:metinf”>syncml:auth-basic</Type> <Format xmlns-‘syncml:metinf’>b64</Format> </Meta> <Data> <!—base64 formatting of userid:password --> </Data> </Cred> <Meta> <!-- Maximum message size for the client --> <MaxMsgSize xmlns=“syncml:metinf”>5000</MaxMsgSize> </Meta> </SyncHdr> <SyncBody> <Alert> <CmdID>1</CmdID> <Data>1200</Data> <! -- Server-initiated session --> <Item></Item> <Item> <Data>123 blah blah</Data> <! -- one example of sending TID --> </Item> </Alert> <Alert> <CmdID>XXX</CmdID> <Data>TIDXXXX 123 blah blah </Data> <! -- or alternative way of sending TID --> </Alert> <Replace> <CmdID>3</CmdID> <Item> <Source><LocURI>./DevInfo/DevId</LocURI></Source> <Meta> <Format xmlns=‘syncml:metinf’>chr</Format> <Type xmlns=‘syncml:metinf’>text/plain</Type> </Meta> <Data>abc blah blah 123 blah blah</Data> </Item> <Item> <Source><LocURI>./DevInfo/Man</LocURI></Source> <Meta> <Format xmlns=‘syncml:metinf’>chr</Format> <Type xmlns=‘syncml:metinf’>text/plain</Type> </Meta> <Data>BEST MANUFACTURER Inc.</Data> </Item> <Item> <Source><LocURI>./DevInfo/Mod</LocURI></Source> <Meta> <Format xmlns=‘syncml:metinf’>chr</Format> <Type xmlns=‘syncml:metinf’>text/plain</Type> </Meta> <Data>BEST PHONE 2004</Data> </Item> <Item> <Source><LocURI>./DevInfo/DmV</LocURI></Source> <Meta> <Format xmlns=‘syncml:metinf’>chr</Format> <Type xmlns=‘syncml:metinf’>text/plain</Type> </Meta> <Data>123 blah abc blah</Data> </Item> <Item> <Source><LocURI>./DevInfo/Lang</LocURI></Source> <Meta> <Format xmlns=‘syncml:metinf’>chr</Format> <Type xmlns=‘syncml:metinf’>text/plain</Type> </Meta> <Data>blah blah</Data> </Item> </Replace> <Final/> </SyncBody> </SyncML>
[0065] The foregoing description has provided by way of exemplary and non-limiting examples a full and informative description of the best method and apparatus presently contemplated by the inventors for carrying out the invention. However, various modifications and adaptations may become apparent to those skilled in the relevant arts in view of the foregoing description, when read in conjunction with the accompanying drawings and the appended claims. As but some examples, the use of other similar or equivalent download scenarios, application program and firmware download technologies (e.g., firmware downloads may use other than OMA FOTA technology), messaging types and device management protocols and methods may be attempted by those skilled in the art. However, all such and similar modifications of the teachings of this invention will still fall within the scope of this invention.
[0066] Furthermore, some of the features of the present invention could be used to advantage without the corresponding use of other features. As such, the foregoing description should be considered as merely illustrative of the principles of the present invention, and not in limitation thereof.
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A method includes, in response to receiving a certain type of HTTP request message from a device during a browsing session, sending a HTTP response message to the device. The HTTP response message includes a dedicated MIME-type for indicating that a device management session is being initiated, and the device management session is identified by an identifier that forms part of the HTTP response message. The device replies to the HTTP response message with a device management session reply that comprises device details and the identifier. Using the device details, the system develops a list containing at least one download option that is compatible with the device and sends the list to the device. In response to a user selecting the at least one download option from the list, the system delivers the selected at least one download option to the device during a device management session.
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SUMMARY OF THE INVENTION
This invention relates to an improved wind deflector which is mounted to the roof of a vehicle towing a trailer.
The wind deflector of this invention includes a planr sheet part having a leading edge which is directed toward the front of the towing vehicle and a trailing edge which is directed toward the rear of the vehicle. The sheet part of the deflector carries a baffle at its leading edge. The baffle is spaced from the roof of the towing vehicle and serves to displace and direct air first downwardly under the sheet part at its leading edge and then upwardly along the lower surface of the sheet part in laminar fashion in front of the towed trailer. In this manner air flow eddies which were usually produced between the deflector and trailer in prior art deflectors are substantially reduced, and an increased downward force upon the towing vehicle is created to improve ride, handling and stability of the towing vehicle.
Accordingly, it is an object of this invention to provide a wind deflector which improves the ride and stability of a vehicle towing a trailer.
Another object of this invention is to provide a wind deflector for use upon a vehicle, such as the tractor of a semi-truck, for the purpose of deflecting air over the front wall of a towed trailer.
And still another object of this invention is to provide a wind deflector which is for use upon a vehicle towing a trailer and which is of economical construction.
And still another object of this invention is to provide a wind deflector used with a tractor pulling a trailer for the purpose of improving the gas mileage of the tractor and its ride and stability.
Other objects of this invention will become apparent upon a reading of the invention's description.
BRIEF DESCRIPTION OF THE DRAWINGS
A preferred embodiment of this invention has been chosen for purposes of illustration and description wherein:
FIG. 1 is a view of a tractor and trailer as seen from the side having the air deflector of this invention mounted to the tractor.
FIG. 2 is a perspective view of the tractor and trailer of FIG. 1 showing the air deflector of this invention mounted to the roof of the tractor and having portions broken away for purposes of illustration.
FIG. 3 is a top plan view of the deflector of this invention mounted to the tractor and as seen from line 3--3 of FIG. 1.
FIG. 4 is a sectional view of the air deflector taken along line 4--4 of FIG. 3 with arrows illustrating the air flow about the deflector.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment illustrated is not intended to be exhaustive or to limit the invention to the precise form disclosed. It has been chosen and described in order to best explain the invention and its application and practical use to thereby enable others skilled in the art to best utilize the invention.
The towing vehicle 10 in FIG. 1 is depicted as a tractor having a trailer 12 coupled to it. Vehicle 10 includes a cab 14 having a roof 16. The forward wall 18 of trailer 12 extends above the level of vehicle roof 16. Wind deflector 20 is mounted to vehicle roof 16.
Deflector 20 includes a sheet part 22 having a leading edge 24 directed toward the front of vehicle 10 and a trailing edge 26 directed toward the rear of the towing vehicle and located above the level of leading edge 24. Sheet part 22 is planar and includes parallel side edges 28. An upturned deflector part 29 extends along the trailing edge 26 of sheet part 22.
A baffle, designated generally by the reference numeral 30, is carried at the lower surface 32 of sheet part 22 adjacent its leading edge 24. Baffle 30 includes a front surface part 34 and rear surface part 36. Baffle 30 extends from one side edge 28 to the other side edge 28 of sheet part 22. Front surface part 34 of the baffle joins sheet part leading edge 24 and extends rearwardly in a diverging direction from lower surface 32 of the sheet part. The junction of front surface part 34 and sheet part 22 at its leading edge 24 is of a generally abrupt V-shape. Rear surface part 36 of baffle 30 extends rearwardly and upwardly from the rear edge of front surface part 34 until it joins lower surface 32 of the sheet part between its leading edge 24 and trailing edge 26.
A fixed rudder 38 extends along each side edge 28 of sheet part 22. Rudders 38 extend above upper surface 40 of sheet part 22 and also below lower surface 32 of the sheet part. Baffle 30 and deflector part 29 both extend between rudders 38. Additionally, rudders 38 extend forwardly of leading edge 24 of sheet part 22.
Sheet part 22, baffle 30, deflector part 29 and rudders 38 may be formed of a light weight material, such as aluminum, with the baffle and deflector part not only regulating the direction of air flow about the deflector but also providing strength to the assembled components of the deflector.
Deflector 20 includes brackets 42 which mount sheet part 22 and the other assembled components of the deflector to roof 16 of vehicle cab 14. Brackets 42 position baffle 30 a substantial distance above the level of roof 16. In an actual working embodiment it was found that a spacing of four inches between the baffle and the roof of the towing vehicle provided the desired air flow about the deflector and around the following trailer. The rear pair of brackets 42 are adjustable to vary the angle of incline of sheet part 22 of the deflector, depending upon the distance the deflector is mounted from trailer 12 and the height of trailer forward wall 18. Additionally, the rear pair of brackets 42 may be constructed so as to allow sheet part 22 to be pivoted toward roof 16 at baffle 30 and placed in a collapsed or stored position when the deflector is not needed.
When the oncoming air contacts deflector 20 during movement of vehicle 10, baffle 30 acts as a displacement medium causing a portion of the air at the leading edge 24 of sheet part 22 to be diverted downwardly beneath the baffle along front surface part 34 and then upwardly along rear surface part 36 of the baffle and along lower surface 32 of sheet part 22, as illustrated by arrows 44. The remaining portion of the air contacting the deflector will pass over the leading edge 24 and along the upper surface 40 of sheet part 22, as illustrated by arrows 46. As the air indicated by arrows 44 passes around baffle 30, a substantial area of reduced or low pressure is created between sheet part 22 and roof 16 of vehicle 10 adjacently rearwardly of the baffle and generally laminar air flow is introduced along lower surface 32 of the sheet part. This reduces the formation of air flow eddies between the deflector and trailer forward wall 18 so as to reduce vibration transmitted by the deflector to the cab 14 of vehicle 10 and improves the flow of air around trailer 12. Additionally, the reduction in pressure beneath sheet part 22 and rearwardly of baffle 30 increases the downward force upon vehicle 10 created by the air striking the deflector so as to improve vehicle stability. The air flow passing about the upper surface 40 and lower surface 32 of sheet part 22 streams from trailing edge 26 of the sheet part and deflector part 29 in a laminar manner.
It is to be understood that the invention is not to be limited to the details above given, but may be modified within the scope of the appended claims.
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A wind deflector which is mounted spacedly above the roof of a vehicle towing a trailer and which includes a baffle at its leading edge to displace and direct air flow between the deflector and the vehicle roof for the purpose of improving the stability and ride of the vehicle and to reduce the formation of eddies in the air flow between the deflector and the trailer.
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CROSS REFERENCES TO RELATED APPLICATIONS
A related application, filed by Charles F. Lambert, Jr. on Oct. 13, 1976 under Ser. No. 731,552, now U.S. Pat. No. 4,085,520 discloses and claims the aforesaid Lambert Anti-Pollution Grain Drying Apparatus. Both applications are owned by a common assignee, the Clayton & Lambert Manufacturing Company of Buckner, KY 40010.
BACKGROUND OF THE INVENTION
1. Field Of The Invention
This invention relates to the art of drying wet grain, continuously or batchwise, and to the air pollution problem it creates.
2. Description Of The Prior Art
The Francis U.S. Pat. No. 3,449,840 and a Lambert, Jr. U.S. Pat. No. 3,755,917 both disclose a grain drying apparatus of the continuous (or batch) rotary sweep type. As a continuous drier, the lag side of the sweep continuously deposits wet grain as it rotates, say counter-clockwise (CCW), over a circular perforated floor, to form a circular layer of grain extending clockwise (CW) on the floor from the wet lag side of the sweep to the lead side thereof. This circular layer of grain dries progressively from the wet lag side to the dry lead side of the sweep as hot air is blown upwardly through the layer. As it dries, its thickness decreases; hence, its dry end is much thinner than its wet end. The dry lead side of the sweep continuously retrieves dried grain from the adjacent dry end of the circular layer. The moist or wet hot air, flowing from the entire layer, is contaminated with fugitive dust. It is discharged from the bin into the ambient atmosphere, thereby polluting the atmosphere.
SUMMARY OF THE INVENTION
Objects Of The Invention
The principal objects of the present invention are: to reduce the loss of heat passing through the dry grain and flowing into the suction system on the dry lead side of the sweep; to increase the recovery of fugitive dust created within the confines of the sweep as a whole; to reduce the emission of fugitive dust into the ambient atmosphere; and to improve the general design.
Statement Of The Invention
The aforesaid copending Lambert, Jr. application SN-731,552, now U.S. Pat. No. 4,085,520 which adds said anti-pollution system to the prior art grain driers, includes a suction canopy chamber embracing the fugitive dust created along the lead side of the sweep and a duct system leading to a high efficiency cyclone separator for separating and recovering that dust and discharging the clean air into the ambient atmosphere.
I have come to appreciate that, since the depth of the dry end portion of the grain layer decreases more or less progressively as it approaches the point of retrieval, there is, in said Lambert anti-pollution system, a progressive increase in the amount of unused hot air flowing from that progressively thinner layer of grain; hence, I propose to provide the lead side of the sweep with an overflow dam, which compels the grain in the dry end portion of the layer to build up to and remain at a desired thickness and then overflow into the dry grain retrieving or removal means. In this way, the resistance of the dry end portion of the layer to the flow of hot air is increased over what it would otherwise be with a consequent decrease in the amount and temperature of the hot air discharging from that portion and flowing into the suction system.
Moreover, I have found that fugitive dust is also created on the wet lag side of the sweep by the incoming wet grain as it falls toward the floor and that much of this wet-side dust, together with the dust created by the outgoing dry grain discharging into the center well, can be sucked through the suction canopy chamber into the anti-pollution duct system and thus prevented from escaping through the bin atmosphere to the outside ambient atmosphere.
Furthermore, in accordance with my invention, the clean air, discharging from the outlet of the high efficiency cyclone used in the anti-pollution system, may be directed back into the grain drying bin under its perforated floor so that the dust and heat content are once again subject to recapture. Preferably, the cyclone outlet air is recycled into the bin through one of its air heaters. Finally, I improve the design, particularly the inner end support of the rotary sweep.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is illustrated in the accompanying drawing wherein:
FIG. 1 is a top plan view of a grain bin installation embodying the present invention;
FIG. 2 is a partly broken side elevation of FIG. 1;
FIG. 3 is a somewhat schematic top plan view showing the positional relationship of important rotary sweep parts between the outer wall of the bin and the vertical axis thereof;
FIG. 4 is a section taken along line 4--4 of FIG. 3 to show the left or lag and right or lead sides of the sweep;
FIG. 5 is a partly broken vertical section taken along line 5--5 of FIG. 4;
FIG. 6 is a perspective view of the parti-cylindrical cap covering the outermost part of the top of the center cylinder;
FIG. 7 is a fragmentary perspective view of the innermost end of the canopy;
FIG. 8 is a horizontal section through the upper part of the center cylinder, this view, which looks downward, omits the funnel-mouthed grain inlet conduit and the inner ends of the upper and lower grain-handling augers;
FIG. 9 is an enlarged section along line 9--9 of FIG. 2 with the rotary sweep swung 90° CCW from its position in FIG. 2; and
FIG. 10 is a vertically exploded view of the center support means and grain trough.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The structure illustrated comprises: a Lambert-type of anti-pollution grain drying apparatus; and my improvement.
The Lambert Apparatus
The Lambert apparatus illustrated, which includes a grain drier of the type disclosed in the Francis and Lambert U.S. Pat. Nos. 3,449,840 and 3,775,917, and which also includes the Lambert anti-pollution apparatus of said copending application, conventionally comprises: a grain bin; grain drying means; wet grain feed means; dry grain discharge means; a rotary sweep; sweep drive means; sweep support means; and Lambert's anti-pollution means.
Grain Bin
The grain bin 10 has a bottom plenum chamber 11 under a perforated partition or floor 12 separating the plenum chamber 11 from an upper drying chamber 13, having one or more wall openings (not shown) for discharging the hot moisture-laden air into the ambient atmosphere. The top of the grain bin is covered by a conical roof 14.
Grain Drying Means
The grain drying means simply comprises a "hot air" blower 16 mounted to blow atmospheric air through a heater (not shown) into the bottom plenum chamber 11 to establish a continuous flow of hot drying air from the bottom plenum chamber successively through the floor 12, a grain layer on the floor 12, the drying chamber 13 and one or more air discharge openings in the bin wall.
Wet Grain Feed Means
The wet grain feed means includes: an inlet conduit 18, feeding grain to and downwardly through the center of the conical roof 14; a conical wet grain hopper 19, mounted on the interior bin walls to receive the incoming wet grain; and a funnel-mouthed conduit 20 centrally positioned not only to receive wet grain from the bottom of conical hopper 19 but also to feed that grain downwardly along the axis of the bin into the lag side of the rotary sweep. The vertical conduit terminates at its lower end in a horizontal sleeve 21 having an inner closed end and an outwardly projecting outer end.
Dry Grain Discharge Means
The dry grain discharge means comprises: a stationary trough 22 having an open top positioned adjacent the level of a centrally disposed opening in the bin floor, straight end walls and V-slanted side walls which terminate in a rounded or semi-cylindrical bottom wall 23; and a conveyor auger or screw 24 extending radially along the rounded bottom 23 of trough 22 and through a conveyor pipe 25 projecting, from an opening in one end wall of the trough, successively through the plenum chamber 11 and an outer wall of the bin to a desired discharge area outside of the bin.
Rotary Sweep
The rotary sweep 27 comprises: a rotary cylinder 28 concentric to the vertical axis of the sweep 27 and vertically arranged, at the floor level of the bin, to open downwardly into said V-shaped trough 22 with which it cooperates to form a vertical center well 29; a wet grain distributing conveyor 30 arranged on the lag side of the sweep with its inner end housed in sleeve 21; a dry grain retrieving conveyor 31 arranged on the lead side thereof with its inner end housed in choke sleeve 31A; a horizontally elongate vertical partition wall 32 projecting radially from the rotary cylinder 28 to separate the lag side of the sweep from the lead side thereof, and having horizontally offset upper and lower vertically straight portions and a rearwardly declining or slanted vertical mid-portion separating the upper lag-side wet grain distributing conveyor 30 from the lower underlying lead-side dry grain retrieving conveyor 31; and a radially-elongate leveling wall 33, on the lag side of the lag conveyor 30. The cylinder 28 is slotted on its auger side, its slot edges flanged and its slot closed by a shallow U-shaped channel 28A, through which the augers pass.
Rotary sweeps may be arranged to rotate horizontally in sweep fashion in either direction. For the sake of clarity, the sweep illustrated will be referred to throughout this application as moving counter-clockwise (CCW). It receives an incoming stream of wet grain from the wet grain feed means through conduit 20, 21 and drops it on the floor where it piles up, its lag side conveyor 30 distributes that pile of grain radially over the floor, its leveling wall 33 scrapes the distributed grain to maintain the wet end of the circular layer at a desired thickness, and its lead side conveyor 31 moves the dry end of the circular layer inwardly to the center well 29 where it drops into trough 22 of the dry grain discharge means.
A suitable seal 34 is interposed between the round bottom of rotary cylinder 28 and a round hole in a plate placed on the top of the stationary trough 22 to facilitate relative rotation therebetween. The seal 34 doesn't transmit weight.
Drive Means
The drive means requires only one outside electric motor 36 to drive the dry grain discharge and retrieving augers 24 and 31, the wet grain distributing auger 30 and the rotary sweep 27. To drive the dry grain discharge auger 24, motor 36 is connected to the outer end thereof. To drive the retrieving auger 31, the inner end of the bottom grain discharge auger 24 is connected to the retrieving auger 31 through a vertically spaced pair of intermediate and terminal gear boxes 37 and 38 in the center well. As seen in FIG. 5, the intermediate gear box 37 is located in the upper half of stationary trough 22 while the terminal gear box 38 is located in the lower half of rotary cylinder 28. To drive the distributing auger 30, the terminal gear box 38 is connected by chain 39 to the receiving end of the shaft of auger 30. As seen in FIG. 8, the rotary sweep 27 terminal gear box 38 is connected through chain 40 and tracking shaft 41 to a tracking gear 42 which, when rotated, tracks along stationary ring gear 43 carrying the outer end of the sweep with it.
Rotary Sweep Support Means
The rotary sweep is supported at its outer and inner ends. The outer end of the sweep is conventionally supported from rollers on the lower flanges of the stationary ring gear 43 and, since this type of support is in the form of a widely known and used outer roller-bracket assembly, it is not deemed necessary to illustrate or describe it.
The inner end of the Lambert rotary sweep was supported largely by an end-to-end vertical post arrangement, including a stationary lower center post and an upper rotatable post, wherein the center weight was transmitted downwardly through the floor level by a power transmitting shaft. My arrangement, which will be subsequently described, supports and transmits all of the center weight upon and through structural members.
The Anti-Pollution Means
The Lambert anti-pollution means, which is in the form of a suction system for removing and capturing airborne dust coming from the grain in the vicinity of the lead side of the sweep, comprises: a suction chamber 45 arranged on the front side of the partition wall 32 to extend over and above the lead side of the sweep, this suction chamber being composed of a canopy 46 forming the roof of the chamber and a depending curtain 47 extending from the periphery of the canopy's opposite end and front walls downwardly into contact with the underlying grain so as to form the vertical end walls and the front wall of the suction chamber; a pair of orbital conduits 48; a hollow donut casing 49; stationary conduit means 50; blower 51; and an outside dust separator 52.
The orbital conduits 48 connect outlets in the roof of the suction chamber canopy 46 to the interior of the donut casing 49 through an inlet in the casing's bottom wall, which is rotationally mounted on the casing's stationary side walls. The stationary conduit means 50 connects the interior of the donut casing 49, through an opening in a stationary wall thereof, to a blower 51 which suctions air from the suction chamber 45 successively through orbital conduits 48, donut casing 49 and the approaching portion of the conduit means 50 and then blows that air through dust separator 52 where the dust is separated from the air and the cleaned air discharged either to atmosphere or in accordance with my invention.
My Improvement
I propose: to improve the support means; to provide an overflow dam, which is useful in the grain drying apparatus whether or not it is equipped with anti-pollution means; and to improve the anti-pollution means.
Improved Support Means
My support means comprises: a lower stationary integrated support assembly; and an upper rotary integrated support assembly.
The lower assembly includes: a pair of trough supporting base brackets 55, one on each slanted outer side of the trough 22 to bridge the vertical space between that side and the bottom of the bin; a cross-bracket 56 arranged transversely within and mounted on the inner slanted faces of the walls of the trough adjacent the upper ends of the vertical brackets 55; a pair of horizontally-spaced upright brackets 57 mounted on cross-bracket 56, one located on each side of the vertical axis of the grain bin adjacent opposite sides of intermediate gear box 37; and an axisconcentric top plate 58 on the upper end of upright brackets 57, which terminate in the vicinity of the floor level. These stationary parts 55-58 and trough 22 are all rigidly connected together and remain stationary at all times.
The upper rotary assembly, which rests rotationally on the top plate 58, includes: a base plate 60 resting on, and in rotational face-to-face relation to, said top plate 58; an integrated three-sided vertical casing having two opposed side walls 61, 62 located at and connected to the opposite sides of terminal gear box 38; and a third or bight wall 63 extending transversely from one side wall 61 to the other side wall 62 and integrated with both. The side walls extend the full vertical length of cylinder 28. The bight wall 63 projects beyond the upper end of the cylinder 28.
The side walls 61, 62 incline for a short distance outwardly upward from the top of the terminal gear box 38 to widen the space therebetween sufficiently to receive the incoming wet feed sleeve 21 which houses the inner end portion of the distributing auger 31 within rotary cylinder 28. The side walls 61, 62 continue straight upwardly along opposite sides of the upper distributing auger 30 and terminate at or near the top of rotary cylinder 28. Bight wall 63 is in the form of a straight plate vertically arranged within the cylinder 28 between the bin axis and the distributing auger 30 and tracking shaft 41 drive chains 39, 40. It extends upwardly beyond the top of rotary cylinder 28 sufficiently to receive and support the inner end of the tracking shaft 41 and terminates near the bottom level of the funnel-mouth of the wet grain receiving conduit 20.
The inner end of dry auger 31 is supported by the housing of terminal gear box 38. The inner end of wet auger 30 is supported on the bight wall 63 of the integrated casing 61-63. Likewise, the inner end of the tracking shaft 41 is supported on the upper end portion of the bight wall 63. Thus the weight of the apparatus at the inner ends of wet and dry augers 30, 31 and of track shaft 41 is transmitted through the integrated casing 61-63, and associated structural parts, directly to base plates 60 of the upper assembly 60-63, thence to the top plate 58 of the lower assembly 55-58.
The innermost roof truss 65 of the canopy rests upon the upper end of the side walls of the integrated casing 61-63. The rotary cylinder 28 is supported on casing 61-63 by means including a T-bracket 66 connecting two points on the inner wall of the cylinder to the casing through the cross bar of bracket 66 and a 3rd point of the cylinder to the casing through the stem of bracket 66. The casing also supports the funnel-mouthed conduit 20, its sleeve 21 and air-locking choke sleeve 31A of retrieving auger 31. The roof of canopy 46 covers a small portion of the open top of rotary cylinder 28. The remainder of the open top of cylinder 28 is covered by a parti-cylindrical cap 68, i.e. a partial band-shaped or ring-shaped cap, having a closed top and an open bottom. The top of cap 68 is on a level slightly above the uppermost level of canopy 46. Suitable walls (not shown) close any vertical openings resulting from this difference in levels.
Overflow Dam
In accordance with a particular feature of my invention, an overflow dam is arranged on but near to the lead side of the lead auger 31 so that, as the rotary sweep 27 sweeps forwardly, it piles up the dry grain in front of it until the dry grain layer thickness exceeds the vertical height of the dam whereupon the dry grain begins to overflow the dam.
The dam is in the form of an elongate metal plate 70 which is slightly longer than the horizontal space between the bin wall and the outer end of the air-locking sleeve 31A of dry auger 31. The plate 70 is supported from the lead side of partition wall 32 by two or more horizontally spaced vertical bars 71 and from the truss system of the canopy 46 by two or more slanted bars 72 which may be lengthened or shortened by turnbuckles 73 or other suitable adjustable means. The overflow feature is useful in continuous batch driers of the type illustrated with or without any anti-pollution means.
Improved Anti-Pollution Means
The anti-pollution means is improved, in accordance with my invention, by extending the canopy 46 rearwardly over the lag side of the rotary sweep so as to extend over the lag space 75, which extends on all sides of lag auger 30 between partition wall 32 and leveling wall 33. The lag space 75 communicates with the space extending under the canopy between the roof trusses of the canopy 46. As a consequence, space 75 is also subject to the suction exerted through orbital conduits 48 connecting the suction chamber 45 to the donut casing 49.
Again, in accordance with my invention, the suction chamber 45 is extended to the center well 29 of rotary cylinder 28. Suction from the orbital conduits 48 causes air to flow from the center well 29 of the rotary cylinder 28 upwardly into and obliquely through the suction space 76 lying under the canopy 46 between the innermost truss 65 and the adjacent canopy-supporting member of its truss system.
My invention contemplates either the conventional discharge of the cleaned air from the high efficiency cyclone separator 52 directly into the ambient atmosphere or the unconventional discharge of that air back into the plenum chamber 11 so that its dust and heat contents are once again subject to recapture. The cyclone air outlet is recycled into the plenum chamber 11 through outlet pipe 78, which, preferably, is connected to the intake of one of the hot air blowers 16.
Both the partition wall 32 and the leveling board 33 are conventionally provided with yieldable sealing means (not shown) which scrape the wall of the bin.
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An improved grain drying apparatus of the type having a bin with a perforated floor through which hot air is blown upward for grain drying purposes, and a rotary sweep assembly employing a wet grain distributing auger on its lag side and a dried grain retrieving auger on its lead side. One improvement includes an inclined elongate plate forming an overflow dam which extends along the floor on the lead side of the retrieving auger and which is connected to the sweep assembly for rotation therewith so as to build up the thickness of dried grain on the floor ahead of the retrieving auger to increase the resistance of the dried grain to the upward flow of hot air on the lead side such that a greater proportion of hot air will flow upwardly through the floor on the lag side through the wet grain being deposited thereon. Additional features include provision for connecting the suction system of the apparatus to the wet lag side of the bin as well as to a central well into which the retrieving auger deposits dried grain for removal from the bin, and a system for recycling air suctioned from the bin through an external cyclone dust separator back into a plenum chamber under the perforated floor.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part application based on U.S. Ser. No. 11/500,317 filed on Aug. 8, 2006 entitled “Intracoronary Injection of a Mixture of Autologous Bone Marrow Derived Mononuclear Cells and Autologous Bone Marrow Derived Mesenchymal Stem Cells for Utilization and Rescue of Infarcted Myocardium.
BACKGROUND OF THE INVENTION
Technical Field
[0002] There are several methods to deliver cells to the heart, among them: intracoronary (by the use of a catheter), intracardiac (directly into the heart during the intraoperative procedure of coronary artery bypass grafting, CABG or by transendocardial delivery), and intravenously (direct injection into a main blood vessel in the arm, leg, etc).
[0003] Myocardial dysfunction resulting from atherosclerosis related myocardial infarction (MI) is a widespread and important cause of morbidity in the USA and mortality amongst adults. Due to scar- and ischemia-related post infarction events, clinical manifestations are enormous and heterogeneous. The damaged left ventricle undergoes progressive ‘remodeling’ and chamber dilation, with myocyte slippage and fibroblast proliferation. These events reflect an apparent lack of effective intrinsic mechanisms for myocardial repair and regeneration. Unless, deep (and still unknown) modifications are introduced in the area proximate to the damage to force proliferation of resident myocytes (Beltrami, 2001), all restorative therapies for MI must consider the use of an exogenous source of cardiomyocyte progenitors.
[0004] A main issue in the decision to be taken has been the source and nature of cells to utilize. According to preclinical studies, the choice has ranged from resident differentiated but quiescent cardiomyocytes to stem cells or cardiomyocyte progenitors (Warejcka, 1996; Wang, 2000; Siminiak, 2003). Since, a cardiac monopotential stem cell has not yet been identified, the clinical options are narrowed to the use of a multipotential stem cell exhibiting a potential to differentiate into the cardiomyocyte lineage. From this point of view, marrow-located stem cells display the required biological properties for a cell therapy approach to treat patients with myocardial infarction (Wulf, 2001; Wagers, 2002; Herzog, 2003). Using animal models, it has been reported a near-normalization of ventricular function after treatment of acute infarcted myocardium with locally-injected bone marrow-derived precursor cells (Jackson, 2001; Orlic, 2001, for a recent review, see Husnain, 2005). However, it was not clear whether the beneficial effect produced by the graft was elicited by hematopoietic stem cells, precursors for cardiomyocytes and/or endothelial cells, stem cell plasticity or just contamination with other marrow cells (Wagers, 2002). On the other hand, the transplantation of unfractionated sheep bone marrow into chronically infarcted myocardium did not result in any beneficial effect (Bel, 2003).
[0005] In addition, several studies have utilized mesenchymal stem cells (MSC) as a cell archetype for regenerative purposes after myocardial infarction. In vitro studies have shown that MSC have the potential to differentiate into spontaneous beating myotube-like structures, which express natriuretic peptides, myosin, desmin, and actinin and exhibit sinus node-like and ventricular cell-like action potentials (Makino, 1999; Bittira, 2002). In vivo studies have shown that when MSC are implanted into myocardium they undergo a milieu-dependent (microenvironment) cardiomyogenic differentiation and develop into myofibers containing striated sarcomeric myosin heavy chain and cell to cell junctions (Wang, 2000; Barbash, 2003). The xenogeneic or syngeneic transplantation of MSC have shown that infused cells were signaled and recruited to the normal and/or injured heart (Allers, 2004; Bittira, 2002), where they undergo differentiation and participate in the pathophysiology of post-infarct remodeling, angiogenesis and maturation of the scar (Bittira, 2003; Pittenger, 2005; Minguell, 2006). Furthermore, recent pig studies have shown that MSC infusion improves left ventricular function following myocardial infarction with no detectable immune or other toxicity (Min, 2002; Shake, 2002).
[0006] Thus, the results of experimental studies showing that the implant of bone marrow-derived progenitor cells improves heart function after myocardial infarction have prompted several groups to test this notion in people. In the last 3 years, various clinical studies have assessed the effect of transplantation of autologous bone marrow in myocardial regeneration after acute myocardial infarction. In all these studies, the source of “repairing” cells has been the bone marrow mononuclear cell fraction (BM-MNC), which contains B, T and NK lymphocytes, early myeloid cells, endothelial progenitors and a very low number of hematopoietic and/or mesenchymal stem cells. In these studies, bone marrow was aspirated (40-250 ml) from patients, the BM-MNC prepared and the resulting cells (10.sup.6 to 10.sup.7) implanted into the infarcted ischemic myocardium, by using either a direct or a catheter-mediated injection. Results showed that the autologous implantation procedure is safe, feasible and seems to be effective under clinical conditions (Assmus, 2002; Perin, 2003; Sekiya, 2002; Stamm, 2003; Strauer, 2002; Tse, 2003). In all cases, the observed therapeutic effect was attributed to bone marrow progenitors-associated neovascularization (angiogenesis, Rafii, 2003), thus improving perfusion of infarcted myocardium.
[0007] Based on preclinical and clinical studies, the rationale of the present clinical study is the following: every clinical attempt for myocardial regeneration might consider the implant of autologous progenitor cells, with the potential to differentiate and mature into cardiomyocytes, thus contributing to the recovery of local contractility. However, a comprehensive therapy should also consider the revascularization of the ischemic tissue by the implant of endothelial progenitor cells.
BRIEF SUMMARY OF INVENTION
[0008] Consequently, we propose that the combined infusion of autologous purified and expanded marrow-derived mesenchymal stem cells (a source of cardiomyocyte progenitor) and autologous bone marrow mononuclear cells (a primary source of endothelial progenitors) represents an effective and enduring myocardial replacement therapy. The above presupposes that the pair of implanted autologous progenitors will express their respective biological programs after interacting with proper microenvironment locus of the receptor tissue (Minguell, 2001; Wagers, 2002; Rafii, 2003).
DETAILED DESCRIPTION OF THE INVENTION
[0009] Results of experimental studies have shown that intramyocardial implantation of autologous mononuclear bone marrow cells induces neovascularisation, but not a robust improvement in heart function, after myocardial infarction. We propose that the above therapy in conjunction with one that provides a source of cardiomyocytes will represent a substantial promise as a cellular agent for cardiovascular therapy.
[0010] As a source of cardiomyocyte progenitors and based on in vitro, ex vivo and in vivo studies, we propose the use of autologous ex vivo expanded bone marrow-derived mesenchymal stem cells (MSC). Encouraging preliminary efficacy data in large animal models of myocardial infarction (Minguell, 2006) and accumulating safety data from human studies of MSCs in non-cardiovascular applications is encouraging.
[0011] In detail, our invention is the intracoronary injection (implant via catheter or direct injection) of a mixture of autologous bone marrow-derived mesenchymal stem cells (BM-MSCs) (cells that have the potential to differentiate and mature into mature cardiomyocytes) and autologous bone marrow-derived mononuclear cells (BM-MNCs) (cells that contain endothelial progenitors) that have the potential to differentiate and mature into cardiomyocytes and endothelial cells, representing an effective and enduring myocardial replacement therapy. See procedure below.
[0012] Primary bone marrow aspirations from the iliac crest will be performed in patients twenty-five.+−.five days before receiving the cell infusion for preparation and expansion of BM-MSC. A secondary (25.+−. 5 days from primary aspiration) bone marrow aspiration from the iliac crest for preparation of BN-MNC will be performed within 5 hours of the intracoronary cell infusion to patients. For cell infusion, aliquots of autologous expanded BM-MSC and BM-MNC are taken and mixed together for a final volume of infusion medium.
[0013] For a better understanding of procedures and schedule, please refer to the following Table.
[0000]
TABLE 1
DIAGRAM OF PROCEDURES AND SCHEDULE
Days to
Type of sample
infusion
Step
to be taken
Type of test to be performed
−25
1 st Bone marrow aspirate
cell suspension
differential cell count;
for preparation of MSC
microbiological
cells
−25
Mononuclear cell fraction
cell suspension
differential cell count
−20
Passage #0 (Primary BM-
growth medium &
cell number, viability,
MSC culture)
cell suspension
microbiological
−16
Passage #1
cell suspension
cell number, viability
−12
Passage #2
cell suspension
cell number, viability
−8
Passage #3
cell suspension
cell number, viability
−4
Passage #4 (Expanded
growth medium &
cell number, viability,
MSC)
cell suspension
microbiological, mycoplasma
0
Final preparation of BM-
BM-MSC
cell number, viability
MSC
suspension
microbiological, mycoplasma,
Gram stain,
immunotypification,
differentiation potential
0
2 nd Bone marrow aspirate
BM-MSC
cell number, viability
for preparation of MNC
suspension
microbiological, Gram stain,
cells
immunotypification
0
Cell product for infusion
BM-MSC plus
cell number, viability
(final mixture of autogous
BM-MNC
microbiological, Gram stain,
BM-MSC and BM-MNC)
suspension
endotoxin
BM-MNC: bone marrow-derived mononuclear cell fraction
BM-MSC: bone marrow-derived mesenchymal stem cells
[0014] Cell infusion (transplantation) may be done in patients intraoperatively in conjunction with coronary artery bypass grafting by direct injection following the circumference of the infarct border or via intracoronary percutaneous balloon catheter designed for angioplasty. Subjects may include patients who fit criteria for acute myocardial infarction or patients with a defined region of myocardial dysfunction related to a previous myocardial infarction.
[0015] Wall motion and left ventricular ejection fraction is evaluated by MRI and echocardiography. SPECT is used to assess viability and myocardial perfusion.
[0016] A method for myocardial replacement therapy for a patient is disclosed. It involves acquiring two types of bone marrow-derived cells, a source of a therapeutically effective amount of mesenchymal stem cells that give rise to cardiomyocytes and a source of endothelial precursor cells either from mononuclear cells as such or after purification, that may give rise to new fine blood vessels. The therapeutically effective amount of mesenchymal stem cells and said mononuclear cells into an injection medium is combined. Such is injected into the patient. This method may be used wherein the step of acquiring a source of a therapeutically effective amount of mesenchymal stem cells that give rise to cardiomyocytes comprises performing a first bone marrow aspiration on said patient and producing a therapeutically effective amount of expanded bone marrow-derived mesenchymal stem cells. This method of myocardial replacement therapy may also include producing said therapeutically effective amount of autologous expanded bone marrow-derived mesenchymal stem cells, wherein the first bone marrow aspiration comprises performing said first bone marrow aspiration at least 20 days before the patient receives said injection medium, wherein said first bone marrow aspiration allows for expansion of a therapeutically effective amount of autologous expanded bone marrow-derived mesenchymal stem cells and where the performing of said first bone marrow aspiration from the patient's iliac crest.
[0017] Further, the above method for myocardial replacement therapy for the patient may include acquiring a source of a therapeutically effective amount of the autologous expanded bone marrow-derived mononuclear as a source of endothelial precursor cells and comprises performing said second bone marrow aspiration from the patient's iliac crest.
[0018] As an alternate, the method for myocardial replacement therapy for the patient of the last paragraph above may be accomplished to obtain said therapeutically effective amount of mesenchymal stem cells that give rise to cardiomyocytes and said therapeutically effective amount of endothelial precursors cells in mononuclear cells, by combining a therapeutically effective amount of aliquots of said therapeutically effective amount of autologous expanded bone marrow-derived mesenchymal stem cells and said therapeutically effective amount of endothelial precursors in mononuclear cells for a final volume of said injection medium.
[0019] As another alternate, the method for myocardial replacement therapy for the patient of the paragraphs above may be accomplished by injecting said injection medium by intraoperatively injecting said therapeutically combination of cells in injection medium comprises directly to the heart in conjunction with coronary artery bypass grafting or by any other transendocardial delivery system similar to the circumference of the infarct border.
[0020] As another alternate, the method for myocardial replacement therapy for the patient of the paragraphs above may be accomplished by injecting said injection medium by injection via intracoronary catheter.
[0021] As another alternate, the method of the paragraphs above may be accomplished by said injection medium being said therapeutically effective amount of autologous expanded bone marrow-derived mesenchymal stem cells combined with said therapeutically effective amount of endothelial precursors cells in mononuclear cells.
[0022] As another alternate, the method of the paragraphs above may be accomplished by the number of mesenchymal cells being increased in a first aspiration of bone marrow by ex vivo expansion.
[0023] As another alternate, the method of the paragraphs above may be accomplished by the second aspiration being performed only to prepare the mononuclear cells.
[0024] As another alternate, the method of the paragraphs above may be accomplished by the second aspiration occurring on the day when the amount of mesenchymal stem cells is sufficient to produce the therapeutically effective amount.
REFERENCES
[0000]
Allers C, Sierralta W D, Neubauer S, Rivera F, Minguell J J, Conget P A. Dynamic of distribution of human bone marrow-derived mesenchymal stem cells after transplantation into adult unconditioned mice. Transplantation 78, 503, 2004
Assmus B, Schachinger V, Teupe C, Britten M, Lehmann R, Dobert N, Grunwald F, Aicher A, Urbich C, Martin H, Hoelzer D, Dimmeler S, Zeiher A M. Transplantation of Progenitor Cells and Regeneration Enhancement in Acute Myocardial Infarction (TOPCARE-AMI). Circulation 2002; 06: 3009-3017.
Barbash I M, Chouraqui P, Baron J et al. Systemic delivery of bone marrow-derived mesenchymal stem cells to the infarcted myocardium. Circulation. 2003; 108: 863.
Beltrami A P, Urbanek K, Kajstura J, Yan S M, Finato N, Bussani R, Nadal-Ginard B, Silvestri F, Leri A, Beltrami C A, Anversa P. Evidence that human cardiac myocytes divide after myocardial infarction. N Engl J. Med. 2001; 344:1750-1757.
Bittira B, Kuang J Q, Al-Khaldi A, Shum-Tim D, Chiu R C. In vitro pre-programming of marrow stromal cells for myocardial regeneration. Ann Thorac Surg. 2002; 74: 1154-1159.
Bittira B, Shum-Tim D, Al-Khaldi A, Chiu R C. Mobilization and homing of bone marrow stromal cells in myocardial infarction. Eur J Cardiothorac Surg. 2003; 24: 393-398.
Herzog E L, Chai L, Krause D S. Plasticity of marrow-derived stem cells. Blood 2003; 102: 3483-3493.
Husnain H K, Ashraf M. Bone marrow stem cell transplantation for cardiac repair. Am J Physiol Heart Circ Physiol 2005; 288: H2557-H2567.
Jackson K A, Majka S M, Wang H, Pocius J, Hartley C J, Majesky M W, Entman M L, Michael L H, Hirshi K K, Godell M A. Regeneration of ischemic cardiac muscle and vascular endothelium by adult stem cells. J Clin Invest 2001; 107: 1395-1402
Makino S, Fukuda K, Miyoshi S, Konishi F, et al. Cardiomyocytes can be generated from marrow stromal cells in vitro. J Clin Invest. 1999; 103: 697-705.
Minguell J J, Erices A, Conget P. Mesenchymal stem cells. Exp. Biol. Med. 2001; 226, 507-517.
Minguell J J, Erices, A. Mesenchymal Stem Cells and the Treatment of Cardiac Disease. Experimental Biology and Medicine (in press) January issue, 2006.
Min J Y, Sullivan M F, Yang Y, Zhang J P, Converso K L, Morgan J P, Xiao Y F. Significant improvement of heart function by cotransplantation of human mesenchymal stem cells and fetal cardiomyocytes in postinfarcted pigs. Ann Thorac Surg. 2002, 74: 1568-1575.
Orlic D et al. Bone marrow cells regenerate infracted myocardium. Nature 2001; 410, 701-705.
Perin E C, Dohmann H F, Borojevic R, Silva S A, Sousa A L, et al. Transendocardial, autologous bone marrow cell transplantation for severe, chronic ischemic heart failure. Circulation. 2003; 107:2294-2302
Pittenger M F, Martin B J. Mesenchymal stem cells and their potential as cardiac therapeutics. Circ Res. 2004; 95:9-20.
Rafii S, Lyden D. Therapeutic stem and progenitor cell transplantation for organ vascularization and regeneration. Nat. Med. 2003; 9: 702-712.
Sekiya, 2002 I, Larson B L, Smith J R, Pochampally R, Cui J G, Prockop D J. Expansion of human adult stem cells from bone marrow stroma: conditions that maximize the yields of early progenitors and evaluate their quality. Stem Cells, 2002; 20: 530-541.
Shake J G, Gruber P J, Baumgartner W A, Senechal G, Meyers J, Redmond J M, Pittenger M F, Martin B J. Mesenchymal stem cell implantation in a swine myocardial infarct model: engraftment and functional effects. Ann Thorac Surg. 2002; 73: 1919-1925.
Siminiak T, Kurpisz M. Myocardial replacement therapy. Circulation 2003; 108:1167-1171
Stamm C, Westphal B, Kleine H D et al. Autologous bone-marrowtem-cell transplantation for myocardial regeneration. Lancet, 2003; 361: 45-46
Strauer B E, Brehm M, Zeus T et al. Repair of infarcted myocardium by autologous intracoronary mononuclear bone marrow cell transplantation in humans. Circulation 2002; 106: 1913-1918
Tse H F, Kwong Y L, Chan J K, Lo G, Ho C L, Lau C P. Angiogenesis in ischaemic myocardium by intramyocardial autologous bone marrow mononuclear cell implantation. Lancet. 2003; 361: 47-49.
Wagers A J, Christensen J L, Weissman I L. Cell fate determination from stem cells. Gene Therapy 2002; 9:606-612.
Wang J S, Shum-Tim D, Galipeau J, Chedrawy E, Eliopoulos N, Chiu R C. Marrow stromal cells for cellular cardiomyoplasty: feasibility and potential clinical advantages. J Thorac Cardiovasc Surg. 2000; 20: 999-1005.
Warejcka D J, Harvey R, Taylor B J, Young H E, Lucas P A. A population of cells isolated from rat heart capable of differentiating into several mesodermal phenotypes. J Surg Res 1996; 62:233-242.
Wulf G G, Jackson K A, Goodell M A. Somatic stem cell plasticity: current evidence and emerging concepts. Exp. Hematol. 2001; 29: 1361-1370
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The present invention is a method for improving cardiac function and myocardial regeneration in living subjects after the occurrence of myocardial infarction. The method is a combination stem cell therapy involving a mixture of bone marrow-derived mesenchymal stem cells and bone marrow derived mononuclear cells surgically implanted by using either a direct or catheter-mediated injection into damaged myocardium. Studies have shown that the implant improves heart function and myocardial regeneration and echocardiographic measurements.
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CLAIM OF PRIORITY
[0001] This patent application claims priority under 35 USC 119 (e) (1) from U.S. Provisional Patent Application Ser. No. 61/974,328 filed Apr. 2, 2014, of common inventorship herewith entitled, “Gated Bath Ring,” which is incorporated herein by reference as though the same were set forth in its entirety.
FIELD OF THE INVENTION
[0002] The present invention pertains to the field of bathtubs, and more specifically to the field of safety accessories in bathing children.
BACKGROUND OF THE INVENTION
[0003] The prior art has put forth several designs for safety accessories in bathing children. Among these are:
[0004] U.S. Pat. No. 5,687,433 to Michael S. Garner, Craig S. Scherer and Michael C. Thuma describes a bath seat usable in a tub for infants and small children that includes a seat portion with a curved back support mounted thereto. The base includes at least one deformable tub gripping element for removably affixing the seat to a bath tub. The seat includes first and second spaced apart, elongated members which are attached to regions of the back support and extend therefrom. A removable tray is adapted to slidably engage the elongated members. A releasable latch, carried in part on the tray and in part on at least one of the elongated members, locks the tray to the one elongated member in one of a plurality of linearly displaced positions. The seat includes a strut extending between the base and the tray to lockingly engage and support the tray. The strut prevents a child from slipping under the tray and maintains the child in the seat during the bath.
[0005] U.S. Pat. No. 5,010,606 to Michael S. Bernstein, David W. Crossley and Michael I. Lerner describes a simple circular bath seat which provides back support and is positionable rotationally in a bath tub where a person bathing a child is enabled to reposition the child and secure the relative position of the seat in order to more easily bath the child.
[0006] None of these prior art references describe the present invention.
SUMMARY OF THE INVENTION
[0007] It is an object of the present invention to provide an assistive bath ring which is easily adjustable or expandable to accommodate needs of a growing child or a special need's child.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is an illustrative prototypical top down diagonal view showing one embodiment of the present invention with telescoping legs, showing the device in the closed position. This embodiment has the post mounted to the gate and is designed to be opened at the back.
[0009] FIG. 2 is an illustrative prototypical top down diagonal view showing the embodiment of the present invention of FIG. 1 in the open position.
[0010] FIG. 3 is an illustrative prototypical top down diagonal view showing an alternative embodiment of the present invention with telescoping legs, showing the device in the closed position. This embodiment has the post mounted to the seat and is designed to open at the front.
[0011] FIG. 4 is an illustrative prototypical top down diagonal view showing the embodiment of the present invention of FIG. 3 in the open position.
DETAILED DESCRIPTION OF THE INVENTION
[0012] For infants and small children, bath time often is associated with free spirited play as splashing in the water and blowing soap bubbles as a fun way to get clean before heading off to bed. Typically, parents bathe their infants in a household bath tub, filling the tub with several inches of water and then holding their child with one arm while they wash the child's body with their other arm and hand. Maintaining a secure grip on a wiggly infant or toddler during bath time sometimes is challenging especially since soap, shampoos and other hygiene products tend to be very viscous and slippery in texture. For a parent or caregiver, maintaining a careful and steady grip on a child while simultaneously attempting to perform simple tasks, such as washing a child's hair or body, is awkward at best. This problem is particularly prevalent for those people who have large garden style bathtubs or old fashioned basin tubs as the tub's placement low to the ground coupled with height of the side walls of the tub make maintaining a firm grip on the child a nearly impossible task, particularly when attempting to gently wash the child's body. If a parent fails to maintain a firm hold on their child, a potential result is that the child slips under water or falls over and bumps their head on the sides or base of the tub; both occurrences are extremely dangerous scenarios.
[0013] To ensure a child's safety when bathing an infant, many parents utilize a baby bath ring which is a vertical and circular shaped support structure inside of which the child comfortably sits. The open style of the baby bath ring's framework supports the child in a comfortable, upright position. Typically, these frameworks are constructed so the child can rest their arms on the top of the framework while a vertical support bar extends between the child's legs to facilitate the child in comfortably sitting upright while preventing the child from sliding below the surface of the water. Perhaps one drawback associated with these devices is difficulty in removing the child from the device after the bath. Another drawback is that children outgrow them fairly quickly. Most baby bath rings accommodate children up to fourteen to sixteen months in age. For children who are larger than average or are simply unable to sit upright unassisted past the targeted age range of these devices, standard baby bath rings are simply too small to accommodate these children. This is especially true for children with special needs who, because of mental or physical disabilities, are unable to sit upright on their own. Assisting a child into or out of a bath ring that is too small to accommodate their build is extremely difficult and causes strain and injury to both the child and their caregiver. As such, bathing a child with special needs or who is otherwise too large to utilize a traditional baby bath ring is a challenging endeavor.
[0014] The present invention, hereinafter referred to as the Gated Bath Ring, is an assistive baby bath ring comprising adjustable components that accommodate older or larger children. Ideal for use with any able bodied infant or toddler who is too large for a traditional bath ring, the Gated Bath Ring is well suited for use with children who suffer various developmental disabilities that compromise their ability to sit upright unassisted in the bath tub. The Gated Bath Ring is a specially designed bath ring which is easily expandable to accommodate the needs of the growing or special needs child. The Gated Bath Ring comprises an integrated safety gate incorporated into the ring which enables the child to enter and exit the ring from the side of the device, as opposed to requiring the caregiver to lower or lift the child into or out of the center of the unit.
[0015] Please refer to the Figures. As with traditional bath rings, the Gated Bath Ring 10 is manufactured primarily of heavy duty, water resistant plastic material and contains coated metal components. The Gated Bath Ring, similar in mechanical style and basic function to traditional bath rings, is comprised of a cylindrically shaped framework. The base 14 of the Gated Bath Ring contains a solid platform on which the child sits, while the top of the present invention is comprised of a circularly shaped ring 16 like arm rail that provides support and stability to the child seated within it. A multiplicity of heavy duty suction cups 18 are positioned appropriately on the underside of the base, providing further stability and structural integrity to the present invention during use. Measuring the same diameter or larger in diameter than traditional bath rings, the Gated Bath Ring includes telescoping leg components 20 that enable the user to adjust the height of the ring in accordance to the size of the child. The four vertical support leg components 20 that connect the upper ring 22 to the base platform 14 are telescoping, enabling the user to raise or lower the ring as necessary, simply by expanding or contracting the legs. Simple interlocking fasteners or a comparable locking mechanism 24 are incorporated into the construction of these support legs, enabling the user to securely lock in the Gated Bath Ring at a designated height. The back and two side support legs 20 connect at the top and bottom to the upper ring and base of the Bath Ring. The front vertical post 26 connects at the base of the seat and its top rounded section 42 rests against an indentation 46 in the closed gate arm.
[0016] In the embodiment shown in FIGS. 1 and 2 , post 26 is mounted to the upper ring 22 , which functions as the gate 32 , and is designed for the child to be seated facing front 30 . Gate 32 is closed after the child is seated and gate 32 is closed behind the seated child. Also in this embodiment, base 14 comprises indentation 52 , for securely receiving expanded base 54 at the bottom of post 26 , when the gate 32 is in the closed position.
[0017] In the embodiment shown in FIGS. 3 and 4 , post 26 is mounted to base 14 , and the child faces front 30 , with post 26 situated between the legs of the child. The back of the child rests against the rear 34 . Also, in this embodiment, the terminus 42 of post 26 is round or ball shaped to prevent injury to the child. Terminus 42 fits into recess 46 when the gate 30 is closed.
[0018] Both embodiments comprise structurally incorporated into the upper ring 22 of the gate is a swivel pinch-free knuckle joint 36 hinged access panel that enables the user to open or close the ring to facilitate access to the child. A simple safety lock secures the gate in a closed position during use. The Gated Bath Ring is manufactured in a variety of whimsical colors to appeal to children. Both embodiments also comprise a raised portions 38 at the front 30 and rear 32 , 34 of ring 22 to facilitate support of the child.
[0019] Application and use of the Gated Bath Ring is very simple and straight forward. The user installs the Gated Bath Ring within their bath tub. Positioning the Gated Bath Ring so the base rests atop the bottom of the tub, the user presses firmly to adhere suction cups, located on the underside of the present invention, to the tub and thus secure it in place. The user raises or lowers the telescoping support arms in accordance to the height of their child, allowing the child to access the ring like arm rail at a comfortable level. After filling the tub to a safe level with warm water, the user simply opens the gate and assists their child into the Gated Bath Ring. The child sits on the circular platform with one of the vertical support arms positioned between their legs to prevent the child from slipping downwards as they take their bath. Propped up and stabilized with the Gated Bath Ring, the child enjoys their bath as usual with the parent or caregiver assisting the child in washing their hair or performing other hygiene rituals. After use, the tub is drained of water and the Gated Bath Ring is removed from the tub and stored away until again needed.
[0020] A cleverly constructed bath ring that is fully adjustable, the Gated Bath Ring is utilized by typical children from about six months of age, as well as those who are older than sixteen-eighteen months of age, yet are unable to sit comfortably upright on their own. Providing reliable stability and support to children who are unable to sit upright in a bath tub, yet are too large for a traditional bath ring, the Gated Bath Ring ensures that bath time is a safe and comfortable activity for the child. Fully adjustable, the Gated Bath Ring is easily raised or lowered to accommodate the height of the child. This advantage will prove especially useful in households where more than one child is present as the device is easily adjusted to accommodate individual children. Durably constructed, the Gated Bath Ring will withstand repeated use with ease.
[0021] Although this invention has been described with respect to specific embodiments, it is not intended to be limited thereto and various modifications which will become apparent to the person of ordinary skill in the art are intended to fall within the spirit and scope of the invention as described herein taken in conjunction with the accompanying drawings and the appended claims. For example, older individuals with specific disabilities might benefit from a larger version of the Gated Bath Ring.
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An assistive bath ring for use by a child or adult to provide support for the user to sit in a bathtub. The bath ring comprises an essentially cylindrically shaped framework comprising a circular solid base, a circularly shaped ring attached to the base by height adjusting telescoping leg components; wherein the ring has a front and a rear; and further comprising a hinge in the circular shaped arm rail creating a gate to allow the circularly shaped ring arm rail to open and close.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a sports implement (an implement used in sporting, sports goods, sports equipment) having a circuit comprising a thin film transistor (hereinafter, referred to as a TFT) using a semiconductor thin film (the thickness of about several nm to several hundred nm), specifically, to a sports implement including a light emitting display device having a piezoelectric element, a semiconductor circuit or an organic light emitting element as a component. Further, the present invention also relates to an amusement tool or a training tool having a circuit configured by a TFT.
[0003] In this specification, the term “semiconductor circuit” includes general circuits that can function using semiconductor characteristics.
[0004] 2. Description of the Related Art
[0005] In recent years, a sports implement including an IC hip, (e.g., manufactured by HEAD) such as a tennis racket, a ski or a snowboard has been sold. Reference 1 (U.S. Pat. No. 5,857,694) describes a specific configuration of such a sports implement. According to Reference 1, such sports implement includes an electric actuator and a circuit attached with the electric actuator. The electric actuator eliminates vibration and adjusts performance of such a sports implement to various situations.
[0006] A circuit used in such a sports implement is a processing circuit for amplifying and controlling mutually to compensate strain detected in the sports implement or to only influence on performance by varying stiffness of the sports implement. A circuit used in such a sports implement is mounted as a chip.
SUMMARY OF THE INVENTION
[0007] A conventional sport implement having a chip changes vibration or an impact into electric energy, and changes the stiffness using the electric energy. Although the conventional sport implement is adjusted depending on the use situation, it is unchanged that a user still operates the sports implement according to characteristics of the sports implement.
[0008] Such a conventional sports implement installing a chip is developed so as to enhance stiffness or performance of impact absorption and the like.
[0009] For example, an effect that a frame shape is recovered by electric energy that is changed from mechanical energy of an impact from a ball or an impact absorption effect is obtained, as for a tennis racket. A tennis player can hit back a ball with power since bending of the racket frame is suppressed and the ball impact is eased, but he/she has to be accustomed to the behavior. Such a racket is a high-performance racket that can reduce impacts by 20 to 50 percents, but the user get tired of the racket since it has one pattern behavior.
[0010] In view of the above problems, the present invention provides a sports implement whose characteristics a user can adjust freely and minutely.
[0011] The present invention provides a sports implement, an amusement tool or a training tool in which a high functional circuit can be provided on a curved surface as well as a plane face, which is light-weight, and which has a high functional circuit can resist bending or an impact
[0012] According to the present invention, a circuit used in a sports implement has a function that a user can conduct an input operation to the circuit and adjust a sports implement characteristics in a phased manner. To achieve that, a circuit is more integrated and various functional circuits are installed in a sports implement. It is necessary to enlarge a chip in size for integrating a circuit. However, a single crystal silicon chip used in a conventional sports implement is stronger mechanically as the size is smaller, and it has an adverse effect that the single crystal silicon chip is weaker in an impact as the size is larger. When such a single crystal silicon chip becomes larger in size, the number of chips manufactured on an expensive single silicon substrate (disc-shaped) is reduced and the manufacturing cost is high, which is an adverse effect. Thus, there is a limitation on a chip size as long as a single crystal silicon substrate is used.
[0013] According to the description of Reference 1 , a used circuit incorporates a dual FET amplifier, a sensor element, a diode chip, a resistor, and a capacitor. A space is needed in a sports implement so that the chip can be incorporated in the sports implement. In addition, such parts are mounted on a printed board and noise is easy to superpose.
[0014] According to the present invention, it is realized that a light-weight high functional circuit (a CPU, a power supply circuit, a memory, a receiving circuit, a transmitting circuit, an amplifier circuit, a switch circuit, a display portion or the like) is installed in various sports implements by constituting various functional circuits with a TFT formed on a film, without using a printed board. It is possible to form a plurality of circuits integrally on the same substrate, to reduce the cost and to eliminate the area for mounting. Since a TFT is a film-like, the TFT occupies little space for being incorporated in a sports implement, and attachment/detachment such that a high function circuit can be attached thereto or separated is possible. For example, a high functional circuit (a CPU, a power supply circuit, a memory, a receiving circuit, a transmitting circuit, an amplifier circuit, a switch circuit, a display portion or the like) can be attached onto a ball. Because a plurality of circuits are connected on the same substrate, noise is hard to superpose.
[0015] Specifically, a high functional circuit is attached onto a curved surface of a ball and energy (an impact or a vibration) applied to the ball is changed into electricity and amplified, and light can be emitted by the electricity. The ball becomes also a novel amusement tool. For example, the ball can be applied to a sports game of soccer in a game arcade or the like. If a player kicks a soccer ball toward a light transmitting sheet, a kicked portion of the soccer ball emits light at the instance when the soccer ball is kicked, and the ball also emits light at the instance when the ball is hit on the sheet. If an imaging unit is provided on the opposite side of the player through the sheet, the position of the sheet on which the ball is hit or the kicked position of the ball can be recognized.
[0016] For example, an amplifier circuit is formed from a TFT, and a TFT connecting a gate and a drain (such a connection is referred to as a diode connection) is used as a diode. A central processing unit (CPU) including an arithmetical portion and a control portion, or a memory portion (memory) can be also configured by a TFT using a polycrystalline semiconductor as an active layer. If a CPU can be provided in a sports implement, various setting is possible.
[0017] In addition, when using a circuit in which high electron field-effect mobility is not needed for a TFT (e.g., a switch circuit), a TFT using a semiamorphous semiconductor or organics (such as pentacene or carbon nanotube) may be used without limiting to a TFT using a polycrystalline semiconductor as an active layer
[0018] In addition, a TFT is provided over a flexible substrate, typically, a flexible plastic film according to the present invention. The applicant uses the separation method that does not damage a layer to be peeled and the separation method that does not give a limitation to a process of a layer to be peeled by a technique as claimed in Japanese Patent Laid-Open No. 2003-174153, and thus it is possible to separate and transfer an element having high electric characteristics and a circuit including the element.
[0019] A TFT using a polysilicon as an active layer can be provided over a flexible substrate or a film by the technique as described in Japanese Patent Laid-Open No. 2003-174153, and thus, the size can be designed depending on each shape of various sports implements. Note that the method for providing a TFT over a flexible plastic film is not limited to the above described method (Japanese Patent Laid-Open No. 2003-174153). For example, a method by which a separation layer is formed between a layer to be peeled and a substrate, and the layer to be peeled is separated from the substrate by removing the separation layer with a chemical (etchant) or an etching gas, or a method by which a separation layer made of an amorphous silicon (or polysilicon) is provided between a layer to be peeled and a substrate and the amorphous silicon is dehydrogenized by laser irradiation through the substrate and a space is generated, thereby separating the layer to be peeled from the substrate, or the like can be employed. Note that it is preferable that an element included in the layer to be peeled is formed at a heat treatment temperature of 410° C. or lower so that hydrogen is not released before the separation, in the case of using laser light.
[0020] A cross sectional SEM photography of a TFT which is actually transferred onto a film substrate is shown in FIG. 11 and FIG. 12 . FIG. 12 is an enlarged view of the FIG. 11 . As apparent from FIG. 12 , a TFT having a single drain structure with the gate length of 1.2 μm can be confirmed.
[0021] It is possible to configure a CPU that is a representative high functional circuit with about 27000 TFTs and to realize a layout of a chip area of 100 mm 2 . As shown in FIG. 13 , twelve chips can be obtained from a five-inch substrate.
[0022] FIG. 14 is a photograph of one chip to which is pressure-bonded by an FPC after sectioning. When the FPC is pressure-bonded, it can be mounted on without defects of a wire-breaking such as crack.
[0023] FIG. 17 shows a block diagram of one chip and is describes hereinafter.
[0024] When an opecode is inputted into an interface 1701 , the code is decrypted in an analysis unit 1703 (also referred to as an Instruction Decoder), and a signal is inputted into a control signal generation unit 1704 (a CPU Timing Control). When the signal is inputted, a control signal is outputted from the control signal generation unit 1704 to an arithmetic logical unit 1709 (hereinafter, an ALU) and a memory unit 1710 (hereinafter, a Register).
[0025] The control signal generation unit 1704 includes an ALU controller 1705 for controlling the ALU 1709 (hereinafter, an ACON), a unit 1706 for controlling the Register 1710 (hereinafter, a RCON), a timing controller 1707 for controlling timing (hereinafter, a TCON), and an interruption controller 1708 for controlling interruption (hereinafter, an ICON).
[0026] On the other hand, when an operand is inputted into the interface 1701 , the operand is outputted to the ALU 1709 and the Register 1710 . Then, a processing based on a control signal, which is inputted from the control signal generation unit 1704 (for example, a memory read cycle, a memory write cycle, an I/O read cycle, an I/O write cycle, or the like), is carried out.
[0027] The Register 1710 includes a general resister, a stack pointer (an SP), a program counter (a PC), and the like.
[0028] An address controller 1711 (hereinafter, an ADRC) outputs 16 bits address.
[0029] A structure of the CPU described in FIG. 17 is an example of a CPU and does not limit the structure of the invention. Therefore, it is possible to use a known structure of a CPU other than that shown in FIG. 17 .
[0030] According to the present invention, a higher functional circuit (a CPU, a power supply circuit, a memory, a receiving circuit, a transmitting circuit, an amplifier circuit, a switch circuit, a display portion or the like) is installed in a sports implement and therefore, it is realized that a user operates an installed high functional circuit and adjusts characteristics of a sports implement. A high functional circuit using a TFT formed over a flexible plastic film is light-weight and strong in bending and impacts.
[0031] A high functional circuit (a CPU, a power supply circuit, a memory, a receiving circuit, a transmitting circuit, an amplifier circuit, a switch circuit, a display portion or the like) can be provided for clothes. It is possible to conduct motion interpretation or movement analysis by installing a plurality of high functional circuits in each point of shirts or spats, and chasing a movement at each point of a human body in sports and rehabilitation. A user wears clothes having a high functional circuit at least having a transmitting circuit or a receiving circuit, a gate having a transmitting circuit or a receiving circuit is installed at a start point and a goal point respectively, thereby making it possible to train alone and to measure a time by himself/herself.
[0032] Note that one or both of the transmitting circuit and the receiving circuit has/have an antenna in this specification.
[0033] One feature of the present invention is that a plurality of piezoelectric elements are provided for a sports implement because a large amount of electric power is required to drive various circuits. Electric power is generated by warping a piezoelectric element and amplified by an amplifier circuit to be used. Electric power may be generated by warping a piezoelectric element and charged in a charging unit every time electric power is generated.
[0034] A pointless electric power transmission module capable of charging without contact may be provided in a sports implement. The pointless electric power transmission module conducts charging by a method of supplying electric power to a secondary coil without contact by an electromagnetic induction method in which a primary coil (battery charger) is coupled with the secondary coil (main body) electromagnetically and voltage is generated in the secondary coil by an alternating magnetic field generated from the primary coil.
[0035] An auxiliary power (a primary battery or a secondary battery) to assist insufficient electric power, e.g., a sheet-like battery can be installed or attached.
[0036] A structure described in this specification is a sports implement comprising: a piezoelectric element which generates a signal by warping the piezoelectric element due to a vibration or impact applied thereto; an amplifier circuit which amplifies the signal to produce an amplified signal and which is operationally connected to the piezoelectric element; and an instruction unit which determines an application of the amplified signal to the piezoelectric element.
[0037] In the above described structure, the sports implement further comprising a rectifier unit for rectifying the amplified signal prior to the application thereof to the piezoelectric element.
[0038] One feature of the above-mentioned configuration is that further comprising a rectifier unit for rectifying the amplified signal prior to the application thereof to the piezoelectric element.
[0039] In the above described structures, the amplifier circuit includes at least a TFT.
[0040] One feature of the above-mentioned configuration is that further comprising a display portion for displaying a result of the voltage application obtained in the instruction unit.
[0041] One feature of the above-mentioned configuration is that further comprising a receiving circuit including an antenna for receiving a signal voltage application to the piezoelectric element.
[0042] One feature of each above-mentioned configuration is that further comprising a central processing unit.
[0043] One feature of each above-mentioned configuration is that further comprising a memory element.
[0044] One feature of each above-mentioned configuration is that the piezoelectric element is warped by being applied to a vibration or impact to generate electric power, and the sports implement becomes warm or cool by the electric power.
[0045] In the above described structures, the sports implement is one of a hitting sports implement, a winter sports implement, a training wear, an insole, and shoes.
[0046] Another structure described in this specification is a sports implement comprising: a first piezoelectric element; a second piezoelectric element; a first amplifier circuit including a TFT; a second amplifier circuit including a TFT; an instruction unit for determining voltage application to the first piezoelectric element; and a charging unit for storing electric power, wherein electric power is generated by warping the second piezoelectric element with a given vibration or impact to produce a signal, and the signal is amplified in the second amplifier circuit.
[0047] It is possible to provide a sports implement that is favorable in operationality and friendly to many users in a wide range regardless of the muscle strength or physical constitution and the like of a user, since the user can adjust characteristics of a sports implement.
[0048] Another structure described in this specification is a sports implement described in the comprising: a piezoelectric element; an amplifier circuit including a TFT; an instruction unit for determining voltage application to the piezoelectric element; a display portion for displaying a result of the voltage application obtained in the instruction unit; an electric power generation unit; and a charging unit for storing electric power, wherein a signal is amplified in the amplifier circuit.
[0049] According to the present invention, a display portion is provided for a sports implement and an adjusted value is output and displayed thereon so as to be recognized by a user so that the user can adjust a sports implement, which is convenient. The output display is preferably conducted in a display device using an electroluminescent element (EL element). In addition, the display device may be used for simple monochrome display or display of figures. According to the present invention, a circuit can be formed over the same substrate as a display device and installed in a sports implement.
[0050] As for a sports implement which has a difficulty in installing a display portion therein, a transmitting circuit may be provided in a sports implement and may receive a signal from a receiving circuit provided in an external terminal to confirm the display with the external terminal.
[0051] Another structure described in this specification is a sports implement comprising: a first piezoelectric element; a second piezoelectric element; a first amplifier circuit including a TFT; a second amplifier circuit including a TFT; a receiving circuit for receiving a signal voltage application to the first piezoelectric element; and a charging unit for storing electric power, wherein electric power is generated by warping the second piezoelectric element with a given vibration or impact to produce a signal, and the signal is amplified in the second amplifier circuit.
[0052] A sports implement may be adjusted by using an external terminal through remote-controlling. In that case, it is preferable to employ an adjustable system by which a receiving circuit is provided for a sports implement, receives a signal from a receiving circuit provided in an external terminal, and the signal is processed in a central processing unit to rewrite setting of a memory portion. If a transmitting circuit and a receiving circuit are provided for a sports implement, it can be checked whether circuits provided for the sports implement operate normally or not.
[0053] A charging unit is preferably for driving the central processing unit. Another structure described in this specification is a sports implement comprising: a first piezoelectric element; a second piezoelectric element; a first amplifier circuit including a TFT; a second amplifier circuit including a TFT; a central processing unit for controlling application of voltage to the first piezoelectric element; and a charging unit for storing electric power, wherein electric power is generated by warping the second piezoelectric element with a given vibration or impact to produce a signal, and the signal is amplified in the second amplifier circuit, and the central processing unit includes a TFT.
[0054] There is a possibility that electric power of an piezoelectric element obtained by an impact on a sports implement is insufficient for driving a high functional circuit such as a central processing unit. For this reason, it is preferable that an electric power generation unit for compensating insufficient electric power, such as a photovoltaic device (e.g., solar battery) or a thermo electric generator (e.g., Seebeck element) can be installed in or attached onto a sports implement.
[0055] Another structure described in this specification is a sports implement comprising: a piezoelectric element; an amplifier circuit including a TFT; a central processing unit for controlling application of voltage to the piezoelectric element; an electric power generation unit; and a charging unit, wherein a signal is amplified in the amplifier circuit, and the central processing unit includes a TFT.
[0056] In the above structures, a single crystal such as a quartz crystal, LiNbO 3 or LiTaO 3 ; a ceramics material such as PZT; a polymer material (high-weight molecular material) such as polyvinylidene fluoride (PVDF), or a copolymer with vinylidene fluoride and ethylene fluoride; or a semiconductor thin film that is formed made of ZnO, CdS, AiN or the like by sputtering is given as a piezoelectric element used for a piezoelectric element. In addition, a ceramic fiber generating a piezoelectric effect (typically, Intellifiber) or a plastic sheet generating a piezoelectric effect (a plastic sheet containing ceramic powders, tourmaline powders, small bits of quartz crystal or Rochelle salt or small bits of barium titanate) may be used. The polymer material, the sputtered semiconductor film or the plastic sheet is preferably used if a TFT and a piezoelectric element are formed integrally.
[0057] A circuit using a TFT (hereinafter, referred to as a TFT circuit) and a piezoelectric element are arranged appropriately in a sports implement with the use of an effect that a TFT generates heat by being driven.
[0058] Another structure described in this specification is a sports implement comprising: a piezoelectric element; and a circuit including a TFT, wherein the piezoelectric element is warped by a given vibration or impact to generate electric power, and the circuit including a TFT is driven by the electric power to heat.
[0059] For example, if a TFT circuit is provided in a position near a face contacting a snow surface of a ski or a snowboard (excluding a sole face), the sole can be heated indirectly by heat of the TFT, and thus, the speed of skiing or snowboarding is increased. The speed of skiing or snowboarding may be increased by installing a TFT circuit in a position close to an edge of a ski or a snowboard and heating the edge indirectly. If a TFT circuit is installed in a position close to the edge, the TFT is preferably installed on a nose side, not on a tail side that makes a pile of snow in stopping.
[0060] A piezoelectric element is provided for a sole of ice skating shoes, and a TFT circuit is installed in a position close to the edge to heat the edge indirectly so as to increase the skating speed.
[0061] Further, an amplifier circuit including a piezoelectric element and a TFT may be installed in bindings of snowboard boots or ski boots. In addition, a central processing unit (CPU) including a TFT is preferably installed when various circuits are installed. A binding and boots also receive a vibration or an impact similarly to a ski or a snowboard in skiing or snowboarding. For example, a piezoelectric element is arranged in a sole portion of boots, generated electric power is charged in a charging portion, the fixation degree in a portion covering a foot excluding its bottom may be adjusted by switching with an instruction of a user. Impact absorption is done effectively by providing the piezoelectric element for a sole portion of boots.
[0062] A piezoelectric element is provided in a sole portion of boots, preferably in a shank, a TFT circuit arranged in the toe portions of the boots generates heat using electric power obtained by a vibration or an impact on the sole portion, thereby indirectly warming the toes that are easily chilled or preventing heat radiation to the outside by a rapid temperature change. An insole having an amplifier circuit including a piezoelectric element and a TFT may be arranged in boots without being directly incorporated in boots themselves.
[0063] A amplifier circuit including a piezoelectric element and a TFT may be formed in running shoes. In addition, it is preferable that a central processing unit (CPU) including a TFT is arranged when various circuits are installed. A piezoelectric element is arranged in a sole portion and warming foots is conducted by heating a TFT circuit using a power generated by a vibration or an impact to the sole portion when it is cold. When it is hot, a peltiert element is provided separately and the peltiert element is driven with the power from the piezoelectric element to cool foots down. A temperature sensor is arranged and heating and cooling are switched automatically by being controlled with a CPU depending on a temperature of the temperature sensor.
[0064] An amplifier circuit including a piezoelectric element and a TFT may be arranged in indoor sports shoes. In addition, if various circuits are installed, a central processing unit (CPU) including a TFT is preferably provided. For example, as for basket shoes, shoes whose sole face is soft have strong grip and does not slip easily. If the thickness of the sole is reduced, it can be warmed by the feet temperature of a user. However, there has been only a method of warming by floor friction since the thickness enough to absorb an impact is needed or an aircushion is provided. For this reason, a piezoelectric element is provided in a sole portion of shoes, preferably in a shank, and the entire sole is warmed rapidly by electric power obtained by a vibration or an impact onto the sole portion and the sole surface made of resin is softened.
[0065] In the above described structures, the sports implement includes a hitting sports implement such as a tennis racket, a baseball bat, a baseball glove, a boxing glove, and a golf club, winter sports implements such a ski, a snowboard, a skiwear, and a snowboardwear, and shoes.
[0066] Various circuits may be provided for training tools, e.g., training machine to be deformed by a user, health appliances for muscles, amusement tools and the like without being limited to the above described sports implements. In the training machines, load can be changed according to the number of repeated vibrations by installing a circuit.
[0067] According to the present invention, various circuits can be integrated and a sports implement having adjustment mechanism can be provided. In addition, a user can adjust characteristics of a sports implement freely by himself/herself (on his/her own).
[0068] Another structure described in this specification is a sports implement comprising: a piezoelectric element which generates a signal by warping the piezoelectric element due to a vibration or impact applied thereto; an amplifier circuit which amplifies the signal to produce an amplified signal and which is operationally connected to the piezoelectric element; an instruction unit which determines an application of the amplified signal to the piezoelectric element; a power supply circuit operationally connected to the amplifier circuit; and a charging unit for storing electric power, that operationally connected to the power supply circuit.
[0069] In the above described structure, the sports implement further comprising a rectifier unit for rectifying the amplified signal prior to the application thereof to the piezoelectric element.
[0070] One feature of the above-mentioned configuration is that further comprising a rectifier unit for rectifying the amplified signal prior to the application thereof to the piezoelectric element.
[0071] In the above described structure, the amplifier circuit includes at least a TFT.
[0072] One feature of the above-mentioned configuration is that further comprising a display portion for displaying a result of the voltage application obtained in the instruction unit.
[0073] One feature of the above-mentioned configuration is that further comprising a receiving circuit including an antenna for receiving a signal voltage application to the piezoelectric element.
[0074] One feature of each above-mentioned configuration is that further comprising a central processing unit.
[0075] One feature of each above-mentioned configuration is that further comprising a memory element.
[0076] One feature of each above-mentioned configuration is that the piezoelectric element is warped by being applied to a vibration or impact to generate electric power, and the sports implement becomes warm or cool by the electric power.
[0077] In the above described structure, the sports implement is one of a hitting sports implement, a winter sports implement, a training wear, an insole, and shoes.
[0078] Another structure described in this specification is a sports implement comprising: a piezoelectric element which generates a signal by warping the piezoelectric element due to a vibration or impact applied thereto; an amplifier circuit which amplifies the signal to produce an amplified signal and which is operationally connected to the piezoelectric element; an instruction unit which determines an application of the amplified signal to the piezoelectric element; a power supply circuit operationally connected to the amplifier circuit; a charging unit for storing electric power, that operationally connected to the power supply circuit; and an electric power generation unit operationally connected to the charging unit.
[0079] In the above described structure, the sports implement further comprising a rectifier unit for rectifying the amplified signal prior to the application thereof to the piezoelectric element.
[0080] One feature of the above-mentioned configuration is that further comprising a rectifier unit for rectifying the amplified signal prior to the application thereof to the piezoelectric element.
[0081] In the above described structure, the amplifier circuit includes at least a TFT.
[0082] One feature of the above-mentioned configuration is that further comprising a display portion for displaying a result of the voltage application obtained in the instruction unit.
[0083] One feature of the above-mentioned configuration is that further comprising a receiving circuit including an antenna for receiving a signal voltage application to the piezoelectric element.
[0084] One feature of each above-mentioned configuration is that further comprising a central processing unit.
[0085] One feature of each above-mentioned configuration is that further comprising a memory element.
[0086] One feature of each above-mentioned configuration is that the piezoelectric element is warped by being applied to a vibration or impact to generate electric power, and the sports implement becomes warm or cool by the electric power.
[0087] In the above described structure, the sports implement is one of a hitting sports implement, a winter sports implement, a training wear, an insole, and shoes.
[0088] Another structure described in this specification is a sports implement comprising: a first piezoelectric element which generates a signal by warping the first piezoelectric element due to a vibration or impact applied thereto; a first amplifier circuit which amplifies the signal to produce an amplified signal and which is operationally connected to the first piezoelectric element; an instruction unit which determines an application of the amplified signal to the first piezoelectric element; a power supply circuit operationally connected to the first amplifier circuit; a second piezoelectric element which generates an electric power by warping the second piezoelectric element due to a vibration or impact applied thereto; and a second amplifier circuit operationally connected to the power supply circuit and the second piezoelectric element wherein the electric power is amplified by the second amplifier circuit to produce an amplified electric power.
[0089] In the above described structure, the sports implement further comprising a charging unit for storing electric power, that operationally connected to the power supply circuit.
[0090] One feature of the above-mentioned configuration is that further comprising a rectifier unit for rectifying the amplified signal prior to the application thereof to the first piezoelectric element.
[0091] In the above described structure, the first amplifier circuit is includes at least a TFT.
[0092] One feature of the above-mentioned configuration is that further comprising a display portion for displaying a result of the voltage application obtained in the instruction unit.
[0093] One feature of the above-mentioned configuration is that further comprising a receiving circuit including an antenna for receiving a signal voltage application to the first piezoelectric element.
[0094] One feature of each above-mentioned configuration is that further comprising a central processing unit.
[0095] One feature of each above-mentioned configuration is that further comprising a memory element.
[0096] One feature of each above-mentioned configuration is that the first piezoelectric element and the second piezoelectric element are warped by being applied to a vibration or impact to generate electric power, and the sports implement becomes warm or cool by the electric power.
[0097] In the above described structure, the sports implement is one of a hitting sports implement, a winter sports implement, a training wear, an insole, and shoes.
[0098] Another structure described in this specification is an amusement tool comprising: a piezoelectric element; an amplifier circuit operationally connected to the piezoelectric element; and a light emitting element, wherein the piezoelectric element is warped by being applied to a vibration or impact to generate electric power, and the light emitting element emits light using the electric power.
[0099] In the above described structure, the amplifier circuit includes at least a TFT.
[0100] One feature of each above-mentioned configuration is that further comprising a central processing unit.
[0101] In the above described structure, the amusement tool is one of a ball, a glove, and shoes.
[0102] Another structure described in this specification is a training tool comprising: a piezoelectric element; an amplifier circuit operationally connected to the piezoelectric element; and a receiving circuit including an antenna, wherein the piezoelectric element is warped by being applied to a vibration or impact to generate electric power, and the amplifier circuit and the receiving circuit are supplied with the electric power.
[0103] One feature of each above-mentioned configuration is that further comprising a central processing unit.
[0104] One feature of each above-mentioned configuration is that further comprising a memory element.
[0105] In the above described structure, the amplifier circuit includes at least a TFT.
[0106] In the above described structure, the training tool is one of a training machine, a training wear, a skiwear, a snowboardwear, and shoes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0107] In the accompanying drawings:
[0108] FIG. 1 is a block diagram showing Embodiment Mode 1;
[0109] FIGS. 2A and 2B are a cross sectional view and an equivalent circuit diagram of a piezoelectric element and a TFT, respectively (Embodiment Mode 1);
[0110] FIG. 3 is a block diagram showing Embodiment Mode 2;
[0111] FIG. 4 is a block diagram showing Embodiment Mode 3;
[0112] FIGS. 5A to 5 D are each a circuit diagram showing Embodiment Mode 1;
[0113] FIG. 6 shows an example of a sports implement (Embodiment 1);
[0114] FIG. 7 shows an example of a sports implement (Embodiment 2);
[0115] FIG. 8 shows an example of a sports implement (Embodiment 3);
[0116] FIG. 9 shows an example of a sports implement (Embodiment 4);
[0117] FIGS. 10A and 10B show an example of a sports implement (Embodiment 5);
[0118] FIG. 11 is a photograph of a surface and a cross-section after transferring;
[0119] FIG. 12 is a SEM picture of a TFT cross-section;
[0120] FIG. 13 is a photograph of a plurality of CPUs formed on a film substrate;
[0121] FIG. 14 is a photograph of a CPU of one chip formed on a film substrate;
[0122] FIGS. 15A and 15B each show an example of a sports implement (Embodiment 6); and
[0123] FIGS. 16A to 16 C each show an example of a sports implement (Embodiment 7).
[0124] FIG. 17 is a block diagram.
DETAILED DESCRIPTION OF THE INVENTION
[0125] Hereinafter, Embodiment Modes of the present invention will be described. Embodiment modes of the present invention are hereinafter described with reference to accompanying drawings. The present invention can be implemented in various modes. It is to be understood that various changes and modifications will be apparent to those skilled in the art, unless such changes and modifications depart from the spirit and scope of the present invention hereinafter defined. Therefore, the present invention is not limited to Embodiment Modes.
Embodiment Mode 1
[0126] FIG. 1 is a block diagram of a circuit and an element installed in a sports implement.
[0127] A plurality of piezoelectric elements are provided for a sports implement. Herein two piezoelectric elements (a first piezoelectric element 100 and a second piezoelectric element 105 ) are shown for simple explanation herein.
[0128] When a sports implement of a user is added with a vibration or an impact, strain is added to each piezoelectric element to generate electric power. Since the vibration or impact is converted into electric energy by a piezo effect, the vibration of the sports implement can be reduced.
[0129] Electric power generated in the first piezoelectric element 100 is rectified with a first rectifier unit 102 . The first rectifier unit 102 is configured by using an amplifier circuit, a smoothing circuit, a waveform shaping circuit, a buffer amplifier, a switching circuit, a resistor and the like appropriately. At least an n-fold amplifier circuit 101 of the first rectifier unit 102 is formed from a TFT. Note that a TFT has a small current ability as an element, and thus, the element is needed to be large so as to enhance the current ability.
[0130] The smoothing circuit can include a resistor and a capacitor, and can be formed concurrently with manufacturing steps of a TFT. The waveform shaping circuit can be also formed by using an inverter using a TFT.
[0131] FIG. 2 shows one example in which an amplifier circuit using a TFT and a piezoelectric element are formed integrally. FIG. 2A shows a cross-sectional structure and FIG. 2B shows an equivalent circuit.
[0132] In FIG. 2A , reference numeral 10 denotes a film substrate, 11 denotes an adhesive layer, 12 denotes a base insulating film, and 13 denotes a gate insulating film. A vibration travels through the film substrate 10 , the adhesive layer 11 , and the base insulting film 12 and the gate insulating film 13 . Thus, the materials of the film substrate 10 , the adhesive layer 11 , and the base insulting film 12 and the gate insulating film 13 are all preferably flexible. In addition, a plastic substrate (200 to 500 μm thick) is used as the film substrate 10 . The film substrate 10 preferably has a low thermal expansion property.
[0133] A piezoelectric element 25 comprises a first electrode 23 , a second electrode 19 and a piezoelectric material layer 21 interposed between the first electrode and the second electrode.
[0134] In addition, an amplifier circuit provided on the substrate to amplify output value of the piezoelectric element 25 comprises a current mirror circuit including n-channel TFTs 30 , 31 and 60 . In FIG. 2B , one n-channel TFT 30 , a first n-channel TFT 31 and an X-th TFT 60 , namely, in total (X+1) pieces TFT, are provided to obtain X-fold output. For example, one n-channel TFT 30 (channel size: L/W=8 μm/50 μm) and 100 (a first to a hundredth) n-channel TFTs (channel size: L/W=8 μm/50 μm) are provided to obtain 100-fold output. If two n-channel TFTs 30 are used, the two n-channel TFTs 30 and ten n-channel TFTs 31 are provided so that the output value becomes five times higher.
[0135] In order to amplify the output value further, the amplifier circuit may have an operational amplifier in which the n-channel TFT or the p-channel TFT is combined appropriately. In this case, however, the number of terminals is five. It is possible to decrease the number of terminals to four by decreasing the number of power supplies when the amplifier circuit has the operational amplifier and when a level shifter is used.
[0136] Although this embodiment mode shows an example in which the n-channel TFTs 30 and 31 are top-gate TFTs each having a single gate structure, they may have a double gate structure to reduce a variation. Furthermore, in order to decrease the off current value, the n-channel TFTs 30 and 31 may have an LDD (Lightly Doped Drain) structure. The LDD structure is a structure in which a region added with an impurity element at low concentration, which is referred to as an LDD region, is provided between the channel-forming region and a source region or a drain region formed by adding the impurity element at high concentration. The LDD structure has an advantageous effect of relaxing the electric field near the drain and preventing the deterioration due to the hot-carrier injection. Moreover, in order to prevent the lowering of the on-current value due to the hot carrier, the n-channel TFTs 30 and 31 may have a GOLD (Gate-drain Overlapped LDD) structure. The GOLD structure, which is a structure where the LDD region is disposed through the gate insulating film so as to overlap the gate electrode, has a higher advantageous effect of relaxing the electric field near the drain and preventing the deterioration due to the hot-carrier injection than the LDD structure. Thus, the GOLD structure is effective in preventing the deterioration by relaxing the electric field intensity near the drain and by preventing the hot-carrier injection.
[0137] A wiring 14 is connected to a first electrode 19 and extends into the channel-forming region of the TFT 30 of the amplifier circuit and therefore the wiring also serves as a gate electrode.
[0138] A wiring 15 is connected to a second electrode 23 and to a drain electrode or a source electrode of the TFT 31 . Reference numerals 16 and 18 denote inorganic insulating films, 17 denotes an insulating film formed by a coating method, and 20 denotes a connection electrode.
[0139] A terminal electrode 50 is formed in the same process as the wirings 14 and 15 . A terminal electrode 51 is formed in the same process as the electrodes 19 and 20 .
[0140] In this way, noise can be reduced because a piezoelectric element and an amplifier circuit are formed on the same substrate. The output value can be amplified efficiently. In addition, other circuits can be made with a TFT, as well as an amplifier circuit. FIGS. 5A to 5 D each show an example thereof.
[0141] FIG. 5A shows an equivalent circuit of a switch circuit including a p-channel TFT and an n-channel TFT. FIG. 5B shows an equivalent circuit of an inverter circuit including a TFT. FIG. 5C shows an equivalent circuit of a circuit including a p-channel TFT in which a rectification element is diode-connected in the circuit in which two switching elements and the rectification element are used together. FIG. 5D shows an equivalent circuit of a circuit including an n-channel TFT in which a rectification element is diode-connected in the circuit in which a switching element and the rectification element are used together.
[0142] An instruction unit 103 is provided with a switch and this switch is a switch which is turned on by temperature, pressure or a signal from the outside, a switch operated by a man and the like. Herein, the instruction unit 103 is an instruction unit for switching a signal switch on and off freely by a user. If a user makes the signal switch on, a control signal is formed by a control signal generation circuit 104 and the signal is supplied to the first piezoelectric element 100 to control the strain of a sports implement. That is to say, the control signal generation circuit 104 forms an electric signal to produce a vibration in the antiphase canceling a wavelength generated by the vibration or impact on the sports implement.
[0143] Therefore, a piezoelectric material having characteristics of recovering the shape of the piezoelectric element by the electric signal is preferably used as a piezoelectric material of the first piezoelectric element 100 . In addition, it is preferable that the first piezoelectric element 100 is as large as possible when the characteristics of a sports implement are changed drastically, since the first piezoelectric element 100 varies characteristics thereof by recovering the shape of the piezoelectric element.
[0144] When a user turns off the signal switch, a signal for controlling strain is not formed.
[0145] In this way, sports implement having two-types behaviors can be provided by switching on and off of a signal switch by a user.
[0146] The present invention is not limited to the two types of behaviors. If a circuit (e.g., a CPU or the like) by which fine regulation can be conducted at more multiples stages is installed, a user can adjust characteristics of a sports implement at multiples stages.
[0147] According to the present invention, operation can be conducted without power supply from the outside, since a charging portion is included. Electric power generated in the second piezoelectric element 105 is rectified with a second rectifier unit 107 . The second rectifier unit 107 comprises an amplifier circuit, a smoothing circuit, a waveform shaping circuit, a buffer amplifier, a switching circuit, a resistor, and the like appropriately. At least an m-fold amplifier circuit 106 of the second rectifier unit 107 is formed by using a TFT.
[0148] A charging control circuit 108 and a charging unit 109 are charged with pulsating flow obtained by the second rectifier unit 107 as a direct current. A secondary battery is preferable for the charging unit 109 . Voltage adjustment of each circuit is performed in a power supply circuit 110 using the electric power supplied from the charging unit 109 .
[0149] If the switch of the instruction unit 103 is off, the electric power generated by the first piezoelectric element 100 may be stored in the charging unit 109 in order to secure much more electric power.
[0150] Since the second piezoelectric element 105 only generates electric power, the second piezoelectric element 105 may be smaller than the first piezoelectric element if the magnification of the amplifier circuit 106 is increased. A piezoelectric material having characteristics of recovering the shape of the piezoelectric element by the electric signal is not particularly needed for the second piezoelectric element 105 , unlike the first piezoelectric element, and a piezoelectric material different from that of the first piezoelectric element may be used for the second piezoelectric element 105 .
Embodiment Mode 2
[0151] An example of installing a display portion in a sports implement to display on and off by the instruction unit is shown in Embodiment Mode 2. A block diagram is shown in FIG. 3 .
[0152] FIG. 3 is similar to FIG. 1 except that a display portion 130 and a power generation unit 150 are provided. Thus, detailed description of the same elements is omitted. Note that the same elements in FIG. 3 as those in FIG. 1 are denoted by the same reference numerals.
[0153] For the display portion 130 , a display device using an electroluminescence element (an EL element) is preferable. If an active matrix display device using an electroluminescence element is employed, it can be formed integrally on the same substrate as an amplifier circuit and installed in a sports implement. The display device to be installed may be a passive matrix display device when the display device may be used for simple monochrome display or display of figures only.
[0154] A photovoltaic device (such as solar battery) or a thermo electric generator (such as Seebeck element) may be used for the power generation unit 150 without limiting to the piezoelectric element. A plurality of kinds of power generators may be installed in a sports implement. A solar battery using amorphous silicon can be formed integrally on the same substrate as the amplifier circuit and installed in a sports implement.
[0155] This embodiment mode can be freely combined with Embodiment Mode 1.
Embodiment Mode 3
[0156] As for a sports implement which is difficult in installing a display portion or an instruction unit, a sports implement is provided with a transmitting circuit and receives a signal from a receiving circuit formed in an external terminal and thus the display may be confirmed by the external terminal.
[0157] An example of installing a receiving circuit in a sports implement is shown in Embodiment Mode 3. A block diagram is shown in FIG. 4 .
[0158] FIG. 4 is the same as FIG. 1 except that a receiving circuit 406 , a CPU 410 and a memory portion 411 are provided and an external terminal 400 is used. Thus, the detailed description of the same elements is omitted. Note that the same elements in FIG. 4 as those in FIG. 1 are shown by the same reference numerals.
[0159] A flow of adjustment by remote-controlling of a sports implement using an external terminal 400 is described. A person (including a user) who wants to change characteristics of a sports implement selects desired setting with an instruction unit 403 formed in an external terminal 400 and a signal is transmitted. The signal is transmitted to the receiving circuit 406 provided in a sports implement from a transmitting circuit 405 through a communication control circuit 404 .
[0160] The desired setting can be confirmed in a display portion 430 . Reference numeral 409 denotes a power supply of the external terminal 400 which supplies power to each circuit of the external terminal 400 .
[0161] The signal is received by the receiving circuit 406 and processing is conducted in the central processing -unit 410 to rewrite setting of the memory portion 411 based on the signal. A signal is generated based on the rewritten setting of the memory portion 411 and strain is controlled.
[0162] Note that reference numeral 410 denotes a central processing unit (CPU), 402 denotes a control portion, 401 denotes an arithmetic portion and 411 denotes a memory portion (memory) in FIG. 4 .
[0163] The central processing unit 410 comprises the arithmetic portion 401 and the control portion 402 . The arithmetic portion 401 includes an arithmetic logic unit (ALU) that conducts an arithmetic operation such as addition or subtraction, or a logical operation such as AND, OR or NOT, various registers that temporarily store data or the results of the operations, a counter that counts the number of inputted 1 , and the like. A circuit for the arithmetic portion 401 , such as an AND circuit, an OR circuit, NOT circuit, a buffer circuit, or a register circuit can be formed by using a TFT. A semiconductor film crystallized by continuous wave laser light may be formed as an active layer of a TFT to obtain a high electron field-effect mobility.
[0164] The control portion 402 has a function of carrying out an instruction stored in the memory portion 411 and controlling the entire operation. The control portion 402 comprises a program counter, an instruction register, and a control-signal generating portion. In addition, the control portion 402 can be also formed by using a TFT, too and may be formed by using the crystallized semiconductor film as an active layer of the TFT.
[0165] The memory portion 411 stores data and an instruction for an operation, and stores data or a program that is frequently conducted in the CPU. The memory portion 411 comprises a main memory, an address register and a data register. A cache memory may be employed in addition to the main memory. These memories may be a SRAM, a DRAM, a flash memory or the like. If the memory portion 411 is also formed by using a TFT, a crystallized semiconductor film can be used as an active layer of the TFT.
[0166] Initially, a tungsten film and a silicon oxide film are formed by a sputtering method over a glass substrate, a base insulating film (a silicon oxide film, a silicon nitride film or a silicon oxynitride film) is formed thereover, and an amorphous silicon film is formed thereover. In a later step, a separation is conducted by using a tungsten oxide film formed between the tungsten film and the silicon oxide film.
[0167] The following methods may be used for crystallization: a method of adding a metal element serving as a catalyst to an amorphous silicon film, heating it to obtain a polysilicon film and obtaining a more crystallized polysilicon film by being irradiated with pulsed laser light; a method of emitting continuous wave laser light on an amorphous silicon film to obtain a polysilicon film; a method of heating an amorphous silicon film to obtain a polysilicon film and emitting continuous wave laser light onto the polysilicon film to obtain a more crystallized polysilicon film; and a method of adding a metal element serving as a catalyst to an amorphous silicon film, heating it to obtain a polysilicon film and obtaining a more crystallized polysilicon film by being irradiated with continuous wave laser light. Thereafter, a TFT is completed by using a known technique.
[0168] In this way, the memory portion or the CPU is configured by a TFT using the thusly obtained polysilicon film as an active layer, a layer to be peeled including the CPU or the memory portion is separated from the glass substrate and transferred onto a plastic substrate. If such a CPU can be installed, a variety of settings in a sports implement are possible.
[0169] Another power generation unit may be provided instead of the second piezoelectric element 105 . For example, a photovoltaic device (such as solar battery) or a thermo electric generator (such as Seebeck element) may be used. A plurality of kinds of power generators may be installed in a sports implement. A solar battery using amorphous silicon can be formed integrally on the same substrate as an amplifier circuit and installed in a sports implement.
[0170] This embodiment mode can be freely combined with Embodiment Mode 1 or 2.
[0171] The present invention having above-mentioned structures is described more in detail in embodiments hereinafter.
Embodiment 1
[0172] In Embodiment 1, an example in which the present invention is applied to a tennis racket as an example of a sports implement for hitting a ball is shown in FIG. 6 .
[0173] Since a circuit is configured by a TFT provided on a flexible plastic film, the circuit can be attached and installed in a portion having a free shape, for example, a curved portion, a slim portion or the like. Therefore, the circuit can be provided for a thin part of a frame without limiting to the grip of the racket. Various circuits including TFTs can be arranged since an installation space can be secured. Here, the circuit is provided in only a part of the frame, but the circuit can be arranged in many portions, e.g., the entire frame.
[0174] A piezoelectric element and a circuit including a TFT can be integrally formed. When they are integrally formed, superimposing of noise can be prevented.
[0175] Specifically, piezoelectric elements 601 , 603 and 608 are provided for a plurality of portions and amplifier circuits 602 , 604 and 609 including TFTs are installed in the frame portion as shown by an example in FIG. 6 . Such circuits may be installed inside the frame, or attached onto the frame and covered with a protective film. In addition to the amplifier circuit, other rectifier units, e.g., a smoothing circuit, a waveform shaping circuit, a buffer amplifier, a switching circuit, a resistor or the like may be integrally formed with the amplifier circuit.
[0176] In a grip portion, a switch 606 , a control signal generation circuit 605 , an integrated circuit (a power supply circuit, a memory, a CPU, a receiving circuit or the like) 607 including a TFT and a battery (preferably, the second battery which is rechargeable) 610 are provided for the grip portion. A rectifier unit, e.g., a smoothing circuit, a waveform shaping circuit, a buffer amplifier, a switching circuit, a resistor or the like may be formed integrally with the integrated circuit 607 . Note that the block diagram may be referred to FIG. 1 or FIG. 4 .
[0177] Mechanical energy of an impact from a ball is changed into electric energy by the piezoelectric elements 601 , 603 and 608 , and the electric energy is amplified by the amplifier circuits 602 , 604 and 609 . The amplifier circuit can be provided in contact with or in the periphery of the piezoelectric element by being configured by a plastic film TFT. Therefore, the electric power generated in the piezoelectric element can be amplified immediately, and used.
[0178] The first piezoelectric elements 601 and 608 also serve to control strain of the frame by a signal from the control signal generation circuit 605 . The amplification factors of the amplifier circuits 602 and 609 are preferably 2 times or more, preferably 10 to 50 times. Note that the control signal generation circuit 605 generates an electric signal to produce vibration of the antiphase canceling a wavelength generated by the vibration or impact on the racket
[0179] In this embodiment, a second piezoelectric element 603 to ensure electric power and an amplifier circuit 604 having a large amplification factor, e.g., the 100-fold amplification factor are provided to install various circuits in the racket. The second piezoelectric element 603 may be small, and may be formed by using a piezoelectric material or an element structure higher in conversion efficiency than the first piezoelectric element.
[0180] For example, when a tennis racket of FIG. 6 is used, setting at two stages can be employed: neutral setting that a switch 606 is turned off and plus setting that the switch 606 is turned on to supply a signal from the control signal generation circuit 605 to the first piezoelectric elements 601 and 608 to control strain of the frame and the stiffness of the frame is enhanced.
[0181] In the neutral setting, vibration of the racket is reduced by converting the vibration or impact to electric energy by the piezoelectric effects of the piezoelectric elements 601 , 603 and 608 . Note that, in neutral setting, the second piezoelectric element 603 immediately amplifies and rectifies the generated electric power and charges the battery 610 with the electric power.
[0182] In the plus setting, a vibration or impact is converted to electric energy by the piezoelectric effects of the piezoelectric elements 601 and 608 to control strain of a part of the frame provided with the piezoelectric elements 601 and 608 by using the electric energy. A signal for controlling the strain of the frame is formed in the control signal generation circuit 605 or the integrated circuit 607 . Electric power is supplied to each circuit from the battery 610 .
[0183] Setting of a racket can be selected based on the intention of a user by switching the switch 606 provided in the racket by the user. Therefore, two types of returning balls are possible by changing the setting of a racket, even if the user does not change physical strength in swinging.
[0184] In the case of the plus setting, the stiffness of a frame is enhanced, and a user can return a high speed ball with small power and high speed by controlling the speed, even if the coming ball is fast or slow. In the plus setting, a contact time with a ball is short and the ball is not easily spun since the frame has high stiffness. Therefore, in the plus setting, a user needs a technique for spinning a ball in returning. Further, the user also needs a technique for returning a slow ball when the coming ball is fast.
[0185] If a user wants to spin the ball in returning, he/she selects the neutral setting and lengthen the contact time with the ball, thereby realizing high speed spinning and controlling the direction of the retuning ball. The user can return a slow ball by selecting the neutral setting and slowing down the speed of the fast ball.
[0186] Conventionally, a user needs high technique for returning various types of balls with one racket, but the user can return various types of balls with a racket according to the present invention even if the user does not have such high technique.
[0187] Since various types of balls can be returned even if the user's form or power is not changed, an opponent can hardly read the returning ball and the user can play a game dominantly.
[0188] As for a conventional racket, a professional player change a racket in the middle of a game in many cases since the tension of strings falls down as the racket is used more. If a racket according to the present invention is used, the same level response can be maintained by selecting the plus setting, even if the tension of strings falls down in the neutral setting by more use of the racket.
[0189] The switch 606 is not limited to the two-stage setting. If a CPU or a memory by which fine adjustment can be conducted at more stages is incorporated in the integrated circuit 607 , a user can set a racket freely and return a ball as he/she wants to. If a technique as claimed in Japanese Patent Laid-Open No. 2003-174153 is employed, a memory or a CPU can be formed by using a TFT and formed on a plastic film.
[0190] An integrated circuit 607 incorporating a CPU and a memory may be attached or removed freely. A racket can be set by attaching or removing the integrated circuit 607 incorporating a CPU and a memory.
[0191] This embodiment can be freely combined with any one of Embodiment Modes 1 to 3. For example, this embodiment is combined with Embodiment Mode 2, and a simple display portion may be provided in the racket 600 so that a user can recognize the present state of the racket. In addition, an integrated circuit 607 incorporating a power generation unit such as a solar battery may be provided. A contactless power transfer module that can charge electric power without contact may be provided in a racket 600 , since it does not require replacement of the battery 610 .
[0192] This embodiment is combined with Embodiment 3, and a receiving circuit may be incorporated in the integrated circuit 607 , and a signal from an external terminal (not shown) including a transmitting circuit is received and processed in the integrated circuit 607 , thereby making it possible to set a racket. If the setting of a racket 600 can be changed by the external terminal, the structure of the racket can be simple without providing a switch for the racket 600 .
Embodiment 2
[0193] In Embodiment 2, an example in which the present invention is applied to a snowboard as an example of a winter sports implement is shown with reference to FIG. 7 .
[0194] As for a conventional snowboard, a user can only set a stance width and an angle, and a flexibility of a snowboard, namely, stiffness is different depending on boards. Therefore, snowboards having various flexibilities are prepared in shops.
[0195] Conventionally, a user must buy a snowboard having little flexibility if the user needs a hard snowboard, and a snowboard having more flexibility if the user needs a soft snowboard.
[0196] Actually, the needed flexibility is different depending on snow quality or application, for example, if the snow is light, a more flexible snowboard is needed and superior in an operational property in snowboarding, and if the snow is heavy, a hard snowboard is superior in stability in snowboarding.
[0197] As for snowboarding, various types of snowboarding sports, e.g., snowboarding on a metal tube called a rail or over a box-type obstacle called a box, are conducted in recent years, as well as a half pipe or jump in snowboarding. A hard snowboard in less flexibility is superior in stability in a half pipe, jump or a rail.
[0198] However, when using a hard snowboard, if a user must warp the board in snowboarding by the user's weight, more weight is needed than when using a soft snowboard, and thus, a user that has weak muscle or an unskilled user has difficulties in handling a hard snowboard. It is commonly said that a soft snowboard is suitable for a beginner and a hard snowboard is suitable for the experienced. That is to say, as a user improves his/her skill in snowboarding, the flexibility of a board suitable for the user is also changed, and thus, the user buys a new snowboard in each case.
[0199] According to the present invention, as shown by an example of FIG. 7 , it is possible for a user to adjust the flexibility of a snowboard by installing an integrated circuit such as piezoelectric elements 702 and 703 or an amplifier circuit 704 including a TFT is a snowboard 700 . Such elements may be installed inside the board or attached onto the board and covered with a protective film.
[0200] Conventionally, a user must change a board as he/she improves the skill. However, if a user uses a snowboard according to the present invention, the flexibility of the snowboard can be adjusted according to the improvement of the user's skill and a board suitable for each user can be provided. Further, the flexibility of the snowboard can be freely adjusted in accordance with snow quality or application, by using a snowboard according to the present invention.
[0201] Specifically, a first piezoelectric element 702 is provided in a portion of a board that is to be hard, typically, in the vicinity of an edge, and a second piezoelectric element 703 is provided in a portion of a board that is most easily deformed, typically, in the vicinity of a position 701 where a binding is set. The second piezoelectric elements 703 are provided symmetrically on the both of the toe and heel sides with the binding setting position 701 interposed between the second piezoelectric elements 703 . Four piezoelectric elements 703 are disposed at four positions, but the arrangement or the number thereof is not limited thereto. A snowboard is so wide that a circuit can be arranged at any position. Mechanical energy produced due to transformation of a board by vibration or an impact from a snow surface in snowboarding is changed into electric energy with the piezoelectric element 703 , and the electric energy is amplified in the amplifier circuit 704 . The amplifier circuit 704 is configured by a plastic film TFT, and thus, the amplifier circuit 704 can be provided in contact with or in the vicinity of the second piezoelectric element. Therefore, the electric power generated in the second piezoelectric element can be amplified immediately, and used.
[0202] The generated electric power is immediately amplified and rectified in the integrated circuit 706 including a TFT, and further stored in a battery 707 .
[0203] In addition, an instruction unit 705 includes a switch, and this switch is a switch which is turned on by temperature, pressure or a signal from the outside, a switch operated by a man, and the like. Herein, the instruction unit 705 is an instruction unit for switching a signal switch on and off freely by a user.
[0204] If a user turns the signal switch on, electric power is supplied from a battery and a signal for controlling strain of a board is generated in an integrated circuit (such as a power supply circuit, a control signal generation circuit, a memory, a CPU, or a receiving circuit) and the signal is supplied to the first piezoelectric element 702 . The first piezoelectric elements 702 are provided symmetrically on the toe and heel sides with the binding setting position 701 interposed between the second piezoelectric elements 702 . The first piezoelectric element 702 is arranged closer to an edge than the piezoelectric element 703 , and four piezoelectric elements 702 are disposed at four positions, but the arrangement or the number thereof is not limited thereto. An electric signal to produce vibration of the antiphase canceling a wave generated by the vibration or impact onto the board is supplied to the first piezoelectric element 702 . In this way, a user can harden a board by turning a signal switch on.
[0205] Muscle strengths of the right leg and the left leg are different commonly, and different signals may be supplied to the first piezoelectric element on the right side and to the first piezoelectric element on the left side, thereby making the stiffness in the vicinity of the right foot and the stiffness in the vicinity of the left foot of the board different. By changing each stiffness of the board in accordance with muscle strengths of the right and left legs by a user, the identical warp in the right and left skies is obtained and the user can do a symmetrical turn even if difference weights are put on by the right and left legs.
[0206] The stiffness on the toe side and the heel side may be different by supplying different signals to the first piezoelectric element on the toe side and the first piezoelectric element on the heel side, respectively. A board is easily twisted when weight is put thereon, namely, the torsion becomes large, and thus a curve can be easily made with low weight.
[0207] When a TFT is driven, it generates heat. Heat is generated by driving the integrated circuit 706 or the amplifier circuit 704 including a TFT. The sole surface may be heated indirectly by the generated heat and thus the friction resistance with the snow face is reduced, thereby increasing the snowboarding speed.
[0208] A heating element (such as a resistor) may be provided instead of the first piezoelectric element. For example, the stiffness of the board may be reduced by softening a material in the vicinity of the portion that has been heated by heating a portion of the board having high stiffness entirely. Resin used in one layer of the board is a material that can be softened by heating. The friction resistance with the snow face may be reduced by heating the board by using a heating element, thereby increasing the snowboarding speed. It should be noted that it is difficult to change the setting of a board instantly, since the flexibility of the board is enhanced by heating by turning a switch on if a heating element is provided.
[0209] A snowboard has a structure of stacked layers and the circuits 706 and 704 including TFTs that are sheet-like may be provided as one layer thereof.
[0210] This embodiment can be freely combined with any one of Embodiment Modes 1 to 3. For example, this embodiment is combined with Embodiment Mode 2, and a simple display portion may be provided in the snowboard 700 so that a user can recognize the present state of the snowboard. In addition, an integrated circuit 706 incorporating a power generation unit such as a solar battery may be provided. A contactless power transfer module that can charge electric power without contact may be provided in the snowboard 700 , since it does not require replacement of the battery 707 .
[0211] This embodiment is combined with Embodiment 3, and a receiving circuit may be incorporated in the integrated circuit 706 , and a signal from an external terminal (not shown) including a transmitting circuit is received and processed in the integrated circuit 706 , thereby changing the setting of the snowboard. If the setting of the snowboard 700 can be changed by an external terminal, the appearance of the snowboard can be simple without providing a switch for the snowboard 700 .
Embodiment 3
[0212] In Embodiment 3, an example in which the present invention is applied to a pair of skies as an example of a winter sports implement is shown in FIGS. 8A and 8B . FIG. 8A is a top view of one side of a pair of skies and FIG. 8B is a schematic diagram showing a circuit layout in the backside on one side of the skies.
[0213] As for a conventional ski, a user can set only a binding position, a fixing intensity of boots in a binding, and a flexibility of a ski, namely, stiffness is different depending on boards. Therefore, skis having various flexibilities are prepared in shops.
[0214] In this embodiment, as shown by an example of FIGS. 8A and 8B , it is possible for a user to adjust the flexibility of a ski by installing an integrated circuit such as piezoelectric elements 802 and 803 or an amplifier circuit 804 including a TFT is the ski 800 . Such elements may be installed inside the board or attached onto the board and covered with a protective film.
[0215] The ski has a structure of stacked layers and the circuits 806 and 804 including TFTs that are sheet-like may be provided as one layer thereof.
[0216] Specifically, a first piezoelectric element 802 is provided in a portion of a board that is to be hard, typically, in the vicinity of an edge, and a second piezoelectric element 803 is provided in a portion of a board that is most easily deformed, typically, in the vicinity of a position 801 where a binding is set. The second piezoelectric elements 803 are provided symmetrically on the big toe and small toe (right and left) sides with the binding setting position interposed between the second piezoelectric elements 803 . Four piezoelectric elements 803 are disposed at four positions in one pair of skies, but the arrangement or the number thereof is not limited thereto. Mechanical energy produced due to transformation of a board by vibration or an impact from a snow surface in skiing is changed into electric energy with the piezoelectric element 803 , and the electric energy is amplified in the amplifier circuit 804 . The amplifier circuit 804 is configured by a plastic film TFT, and thus, the amplifier circuit 804 can be provided in contact with or in the vicinity of the second piezoelectric element. Therefore, the electric power generated in the second piezoelectric element can be amplified immediately, and used.
[0217] The generated electric power is immediately amplified and rectified in the integrated circuit 806 including a TFT, and further stored in a battery 807 .
[0218] In addition, an instruction unit 805 includes a switch, this switch is a switch which is turned on by temperature, pressure or a signal from the outside, a switch operated by a man and the like. Herein, the instruction unit 805 is an instruction unit for switching a signal switch on and off freely by a user.
[0219] If a user makes the signal switch on, electric power is supplied from a battery and a signal for controlling strain of a board is generated in an integrated circuit (such as a power supply circuit, a control signal generation circuit, a memory, a CPU, or a receiving circuit) 806 and the signal is supplied to the first piezoelectric element 802 . An electric signal to produce vibration of the antiphase canceling a wave generated by the vibration or impact on the ski is supplied to the first piezoelectric element 802 . In this way, a user can harden a ski by making a signal switch on.
[0220] Muscle strengths of the right leg and the left leg are different commonly, and different signals may be supplied to the first piezoelectric element on the right ski and to the first piezoelectric element on the left ski, thereby making the stiffness of the right ski and the stiffness of the left ski different. By changing each stiffness of the board in accordance with muscle strengths of the right and left legs by a user, the identical warp in the right and left skies is obtained and the user can do a symmetrical turn even if difference weights are put on by the right and left legs.
[0221] When a TFT is driven, it generates heat. Heat is generated by driving the integrated circuit 806 or the amplifier circuit 804 including a TFT. The sole surface may be heated indirectly by the generated heat and the friction resistance with the snow face is reduced, thereby increasing the skiing speed.
[0222] A heating element (such as a resistor) may be provided instead of the first piezoelectric element 802 . For example, the stiffness of the ski may be reduced by softening a material in the vicinity of the portion that has been heated by heating a portion of the ski having high stiffness entirely. Resin used in one layer of the ski is a material that can be softened by heating. The friction resistance with the snow face may be reduced by heating the ski using a heating element, thereby increasing the skiing speed. It should be noted that it is difficult to change the setting of a ski instantly, since the flexibility of the ski is enhanced by heating with a switch turned on if a heating element is provided.
[0223] This embodiment can be freely combined with any one of Embodiment Modes 1 to 3.
Embodiment 4
[0224] In Embodiment 4, an example in which the present invention is applied to snowboard boots as an example of a winter sports implement is shown in FIGS. 9A and 9B . FIG. 9A shows the appearance of boots and FIG. 9B is a schematic diagram showing a circuit layout in a sole portion of the boots.
[0225] In this embodiment, a piezoelectric element 902 is provided in a sole portion 901 of boots 900 , and mechanical energy of an impact from the surface of the snow or a board is changed into electric energy with the piezoelectric element, and the electric energy is used. Impact absorption is done effectively by providing the piezoelectric element 902 in the sole portion 901 of the boots.
[0226] By using heat generated by driving a TFT, circuits 903 , 905 and 906 including TFTs are arranged in the sole portion of the boots 900 to warm feet. The circuits including TFTs are thin, and sheet-like devices that each uses a flexible film as a base material. Thus, a user does not feel uncomfortable with the feet. Note that the circuit 903 including a TFT is a rectifier unit including an amplifier circuit, the circuit 905 including a TFT is a temperature control generation circuit including a CPU and a temperature sensor, and the circuit 906 including a TFT is a circuit generating heat, a serpentine wiring or a heat-generating element. The electric power generated in the piezo electric element 902 may be charged in a charging portion 904 .
[0227] As shown in FIG. 9A , the circuits 903 and 905 including TFTs are arranged in the sole portion 901 of boots, preferably a shank portion in which an arrangement space can be secured, the circuit 906 including a TFT arranged in the toe portions of the boots generates heat using electric power obtained by vibration or impacts to the piezoelectric element 902 arranged in the heel portion of the sole portion, thereby warming the toes that are easily chilled or preventing heat radiation to the outside by a rapid temperature change. An insole having a piezoelectric element and a circuit including TFT may be arranged in boots instead of being incorporated directly in the boots themselves in manufacturing.
[0228] The electric power generated in the piezoelectric element is stored in the charging portion 904 and an instruction unit (not shown) is provided for a boot outer surface, and the fixation degree or stiffness in a portion covering a foot excluding its bottom may be adjusted under a CPU control by switching with an instruction of a user.
[0229] The present invention can be applied to ski boots, thermal boots and the like without limiting to snowboard boots shown in this embodiment.
[0230] This embodiment can be freely combined with any one of Embodiment Modes 1 to 3.
Embodiment 5
[0231] In Embodiment 4, an example in which the present invention is applied to shoes as an example of a sports implement is shown in FIGS. 10A and 10B . FIG. 10A shows the appearance of shoes and FIG. 10B is a schematic diagram showing a circuit layout in a sole portion of the shoes.
[0232] In this embodiment, a piezoelectric element 1004 is provided in a sole portion 1001 of shoes 1000 , and mechanical energy of an impact from the ground surface or a floor surface is changed into electric energy with the piezoelectric element, and the electric energy is used. Impact absorption is done effectively by providing the piezoelectric element 1004 in the sole portion 1001 of the shoes.
[0233] By using heat generated by driving a TFT, circuits 1003 , 1005 and 1006 including TFTs are arranged in the sole portion 1001 of the shoes to heat indirectly the sole face of the shoes. The circuits including TFTs are thin, and sheet-like devices that each uses a flexible film as a base material. Thus, a user does not feel uncomfortable with the feet. Note that the circuit 1005 including a TFT is a rectifier unit including an amplifier circuit, the circuit 1006 including a TFT is a temperature control generation circuit including a CPU and a temperature sensor, and the circuit 1003 including a TFT is a circuit generating heat, a serpentine wiring or a heat-generating element. The electric power generated in the piezoelectric element 1004 may be stored in a charging portion 1007 .
[0234] As shown in FIG. 10B , the circuits 1006 and 1008 including TFTs are arranged in the sole portion 1001 of the shoes, preferably a shank portion in which an arrangement space can be secured, the circuit 1003 including a TFT arranged partially generates heat using electric power produced by the vibration or impacts onto the piezoelectric element 1004 arranged in the heel portion of the sole portion.
[0235] For example, as for basket shoes, the sole face can be soft, can hold a floor strongly and does not slip easily by warming the sole face made of resin by heating the circuit 1003 including a TFT.
[0236] When various circuits are provided in shoes, it is desirable to install a central processing unit (CPU) including a TFT. A portion 1002 is preferable for the location for arranging a central processing unit (CPU), a sensor, a charging portion, a switch and the like.
[0237] In FIG. 10B , circuits that are driven separately are provided as a circuit group having a power 1007 , and a circuit group having a power 1002 , respectively. However, without limiting thereto, the circuits may be driven concurrently in cooperation with each other.
[0238] A circuit including a piezoelectric element or a TFT may be formed in running shoes. A piezoelectric element is arranged in a sole portion and warming feet is conducted by heating a TFT circuit using an electric power generated by vibration or impact on the sole portion when it is cold. In addition, a heat-generating element may be provided in the shoes separately, as well as such a TFT circuit. When it is hot, a peltiert element is provided separately in the shoes and the peltiert element is driven with the electric power from the piezoelectric element to cool foots down. In this way, a user can regulate temperature of shoes freely by himself/herself. A temperature sensor is arranged and heating and cooling are switched automatically by controlling with a CPU depending on a temperature of the temperature sensor.
[0239] This embodiment can be freely combined with any one of Embodiment Modes 1 to 3.
[0240] For example, if this embodiment is combined with Embodiment Mode 2, a simple display portion on which a user can recognize the present setting of the shoes may be provided in the portion 1002 of the shoes. In addition, an integrated circuit incorporating a power generation unit such as a solar battery may be provided in the shoes 1000 . In addition, a contactless power transfer module that can be charged with electric power without contact may be provided in the shoes 1000 , since it does not require replacement of the battery.
[0241] When this embodiment is combined with Embodiment Mode 3, a receiving circuit is incorporated in the portion 1002 , and receives a signal from an external terminal (not sown) having a transmitting circuit, and conducts signal processing in the integrated circuit, thereby making the setting of the shoes 1000 possible. If the setting of the shoes can be changed by the external terminal, the appearance of the shoes can be made simple without providing a switch in the shoes 1000 .
Embodiment 6
[0242] Embodiment 6 shows an example in which the present invention is applied to a soccer ball as an example of a sports implement in FIG. 15A .
[0243] In FIG. 15A , a soccer ball 1501 to which a plurality of integrated circuits 1502 each having a piezoelectric element, an amplifier circuit and a light emitting element are attached is shown. In addition, it is preferable that the integrated circuit 1502 having a piezoelectric element, an amplifier circuit and a light emitting element can be freely attached onto and removed from the ball.
[0244] When a soccer ball 1501 of the present invention is kicked, a piezoelectric element of the kicked point generates electric power, the electric power is amplified by the amplifier circuit, and then the light-emitting element can emit light using the electric power Therefore, only the point where an impact or vibration is given emits light instead of emitting light from the entire surface of the soccer ball. The light emitting element emits light similarly when the soccer ball is hit on the ground or a wall. In general, it is difficult to practice soccer in the night, since soccer is played in a wide place. It is greatly expensive to use a place provided with outdoor lightning for nights. If a soccer ball of the present invention is employed, practicing soccer in the night is possible since the ball emits light partially. When the integrated circuit 1502 having a piezoelectric element, an amplifier circuit and a light emitting element is broken by the impact given to the ball, it may be replaced by a new integrated circuit. The integrated circuit 1502 having a piezoelectric element, an amplifier circuit and a light emitting element is provided on a flexible film and the flexible film has an adhesive surface. Therefore, the integrated circuit 1502 having a piezoelectric element, an amplifier circuit and a light emitting element can be freely attached onto and removed from even a spherical surface like a ball. The integrated circuit 1502 may include a charging unit for storing electric power.
[0245] The soccer ball of the present invention becomes also a novel amusement tool. For example, the soccer ball can be applied to a sports game of soccer in a game arcade or the like. An amusement with the use of the ball of the present invention is shown briefly in FIG. 15B . If a player 1505 kicks a soccer ball 1501 toward a light transmitting sheet 1503 , the kicked portion of the soccer ball emits light at the instance when the soccer ball is kicked, and also emits light at the instance when the ball is hit on the sheet. The sheet 1503 that is flexible absorbs the impact from the ball and prevents the ball from bouncing to the player. The sheet 1503 is light-transmitting, and thus light-emission from the ball is emitted to the opposite side of the player 1505 through the sheet. If an imaging unit 1504 such as a CCD camera is provided on the opposite side of the player 1505 through the sheet, the position of the sheet on which the ball is hit or the kicked position of the ball can be recognized. Thus, the orbit of the ball can be determined. If the distance between the position where a user kicks a ball and the sheet on which the ball is hit is fixed, the speed of the ball can be calculated and measured from the time difference between two light-emission, which are obtained by a CCD camera or the like.
[0246] An integrated circuit having a piezoelectric element, an amplifier circuit and a light emitting element can be installed in various types of balls, without limiting to soccer balls. For example, an integrated circuit having a piezoelectric element, an amplifier circuit and a light emitting element can be installed in a tennis ball or a squash ball. For example, if the method shown in FIG. 15B is employed, an auto tennis field can be provided, which can determine whether or not a ball goes over a net by using a sheet having the same height as the net.
Embodiment 7
[0247] Embodiment 7 shows an example in which the present invention is applied to clothes (wear) such as a training wear as an example of a sports implement in FIG. 16 .
[0248] In FIG. 16A , a wear 1601 to which an integrated circuit 1602 having an antenna, a piezoelectric element, an amplifier circuit and a memory element is attached is shown. In addition, it is preferable that integrated circuit 1602 having an antenna, a piezoelectric element, an amplifier circuit and a memory element can be freely attached to a wear and removed from it. The wear 1601 is provided with the integrated circuit 1602 having at least a transmitting circuit or receiving circuit.
[0249] The clothes (wear) of the present invention become a novel training tool. For example, the wear of the present invention can be employed for measuring the run-time between two points. Training with the use of the wear 1601 of the present invention is shown briefly in FIG. 16C . A player 1605 wearing the wear 1601 of the present invention wears a watch 1603 and adjust the time of clocks incorporated in two gates. A gate 1604 is arranged at a starting point and a gate 1606 is arranged at a goal point. The player 1605 wearing the wear 1601 of the present invention comes close to a transmitting circuit or a receiving circuit incorporated in the gate 1604 at the starting point, and thus a signal can be sent and received with an integrated circuit installed in the wear. The integrated circuit 1602 is provided in the left arm of the player 1605 wearing the clothes 1601 of the present invention as shown in FIG. 16B in this embodiment.
[0250] The piezoelectric element generates strain by being provided with a vibration of body movements e.g., arm movements or by being warped by stretching of clothes or the like, the generated current is amplified in the amplifier circuit, and then electric power is supplied to the integrated circuit. Further, the integrated circuit 1602 may include a charging unit for storing electric power.
[0251] The player 1605 leaves the gate 1604 at the starting point, and the time is recorded in the gate. At the time transmission and reception of a signal is suspended. The player comes close to the gate 1606 installed at the goal point and passes beside the gate 1606 , and therefore, transmission and reception of a signal is conducted. And the time of the signal transmission and reception is recorded in the gate 1606 . By comparing each time stored in the gates 1604 and 1606 , the run-time between the two points can be measured by himself/herself. It has been difficult to perform precise measurement of time in field-and-track events on one's own.
[0252] This method is possible on the snow or the water. Conventionally, it has been difficult to perform precise measurement of time on one's own in winter sports. For example, by training according to the present invention, an integrated circuit at least having a transmitting circuit or a receiving circuit is provided for a skiwear, and gates are provided at a start point and a goal point respectively. If a skier is skiing therebetween, the time can be measured by the skier himself/herself. By training according to the present invention, an integrated circuit at least having a transmitting circuit or a receiving circuit is provided for a snowboardwear, and gates are provided at a start point and a goal point respectively. If a snowboarder is skiing therebetween, the time can be measured by the snowboarder himself/herself.
[0253] According to the present invention, an element or a circuit to be provided for a sports implement can be formed by using a TFT and a plurality of circuits or elements can be integrally formed. Therefore, the present invention is effective in mass-producing of a sports implement.
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The present invention provides a sports implement whose characteristics a user can adjust freely and minutely. According to the present invention, it is realized that a light-weight high functional circuit is installed in various sports implements by constituting various functional circuits with a TFT formed on a film, without using a printed board. A high functional circuit using a TFT formed over a flexible plastic film is light-weight and strong in bending and impacts. It is possible to provide a sports implement that is favorable in operationality and friendly to many users in a wide range regardless of the muscle strength or physical constitution and the like of a user, since the user can adjust characteristics of a sports implement.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Divisional Application of U.S. patent application Ser. No. 12/052,019, entitled SEMICONDUCTOR DEVICE WITH A SEMICONDUCTOR BODY AND METHOD FOR ITS PRODUCTION having a filing date of Mar. 20, 2008, and which is incorporated herein by reference
BACKGROUND
[0002] The application relates to a semiconductor device with a semiconductor body and to a method for its production. The semiconductor body includes drift zones of epitaxially grown semiconductor material of a first conduction type. The semiconductor body further includes charge compensation zones of a second conduction type complementing the first conduction type, which are arranged laterally adjacent to the drift zones. The charge compensation zones are provided with a laterally limited charge compensation zone doping, which is introduced into the epitaxially grown semiconductor material.
[0003] A minimum on resistance is desirable in charge compensation devices of this type. In order to achieve a further reduction of this on resistance, the level of drift zone doping material has to be increased further. Owing to the compensation principle, however, the doping of the charge compensation zones has to be increased in the same way. In order to ensure a complete depletion of charge carriers from the drift zones in the off phase of the semiconductor device in spite of such an increase in the level of doping material both in the drift zones and in the charge compensation zones, the geometrical period in the form of the step size of the charge compensation zones and possibly even of the drift zones has to be reduced further at the same time. In other words, the concentration of doping material per unit of area as integrated in the horizontal direction must not be higher than twice the breakdown charge. The term breakdown charge denotes the charge carrier quantity (doping material concentration quantity) per unit of area which, starting from a p-n junction, is depleted if the breakdown field strength is applied. As the compensation regions are depleted from both sides, the requirement that the regions should be capable of being depleted is equivalent to the requirement that the concentration of doping material per unit of area as integrated in the horizontal direction should not be higher than twice the breakdown charge. These conditions have to be met both by the compensation regions and by the drift zones. Similar to the breakdown field strength, the breakdown charge is determined by the concentration of doping material; for silicon is lies between 1×10 12 cm −2 at low doping and 3×10 12 cm −2 at high doping.
[0004] By using trench technology, wherein the charge compensation zones and/or the drift zones are arranged in trench structures, very small step sizes can be obtained in theory, but this technology has not yet penetrated the market, so that the concept of multiple epitaxy is used to build semiconductor devices of this type. In multiple epitaxy, epitaxial growth phases are interspersed with unmasked large-area and masked selective implantation processes for doping materials. To reduce costs, the number of epitaxial growth phases is limited.
[0005] The regions of a complementary conduction type for the charge compensation zones, which are introduced by masked or selective ion implantation and typically doped with boron, have to diffuse together through the epitaxial growth phases of finite thickness. This however unavoidably involves major widening of the columns or strips of charge compensation zone material. To reduce this widening problem caused by lateral diffusion, non-doped epitaxial layers can be grown in the epitaxial growth phase, whereupon both doping materials of the first conduction type and doping materials of the complementary second conduction type can be introduced in succession by ion implantation near the surface between individual epitaxial growth phases, so that the widening caused by lateral outdiffusion while the charge compensation zones diffuse together can be noticeably reduced by a relatively high adjacent n-doping of the drift zones.
[0006] However, initially high-impedance non-doped epitaxial layers are generated in the epitaxial growth phase, so that the on resistance of the drift zones cannot be reduced as desired. The n-doping in the middle of the epitaxial growth phase is relatively low can only be compensated by raising the general level of implanted doping material in order to reduce the on resistance. A high level of doping material, however, automatically complicates the manufacturing process, as breakdown voltage is highly dependent on wrong doping. The higher the level of doping material, the higher are its fluctuations and the more difficult is it to obtain the required breakdown voltage.
[0007] For these and other reasons, there is a need for the present invention.
SUMMARY
[0008] An embodiment of the invention relates to a semiconductor device with a semiconductor body. The semiconductor body includes drift zones of epitaxially grown semiconductor material of a first conduction type. The semiconductor body further includes charge compensation zones of a second conduction type complementing the first conduction type, which are arranged laterally adjacent to the drift zones. The charge compensation zones are provided with a laterally limited charge compensation zone doping, which is introduced into the epitaxially grown semiconductor material. The epitaxially grown semiconductor material contains 20 to 80 atomic % of the doping material of the drift zones and a doping material balance between 80 and 20 atomic % introduced by ion implantation and diffusion.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The accompanying drawings are included to provide a further understanding of the present invention and are incorporated in and constitute a part of this specification. The drawings illustrate the embodiments of the present invention and together with the description serve to explain the principles of the invention. Other embodiments of the present invention and many of the intended advantages of the present invention will be readily appreciated as they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale relative to each other. Like reference numerals designate corresponding similar parts.
[0010] FIGS. 1-8 illustrate production processes for a semiconductor device of an embodiment of the invention.
[0011] FIG. 1 illustrates a diagrammatic cross-section through a semiconductor wafer.
[0012] FIG. 2 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 1 following the completion of a first epitaxial growth phase with homogeneous doping of the epitaxial layer.
[0013] FIG. 3 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 2 following the large-area unmasked ion implantation of a doping material balance for a first conduction type.
[0014] FIG. 4 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 3 following the masked selective ion implantation of a complementary second conduction type.
[0015] FIG. 5 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 4 following a second epitaxial growth phase and a large-area unmasked ion implantation of a doping material balance of the first conduction type.
[0016] FIG. 6 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 5 following the masked selective ion implantation of a doping material of a complementary second conduction type.
[0017] FIG. 7 illustrates a diagrammatic cross-section through a section of the semiconductor wafer following the completion of six epitaxial growth phases.
[0018] FIG. 8 illustrates a diagrammatic cross-section through the section according to FIG. 7 following the diffusing together of the implanted charge compensation zone doping to form a column- or strip-shaped charge compensation zone.
[0019] FIG. 9 illustrates a diagram of the concentration behaviour of the doping material of the first conduction type in a drift zone.
[0020] FIGS. 10-18 illustrate production processes for a semiconductor device of a further embodiment of the invention.
[0021] FIG. 10 illustrates a diagrammatic cross-section through a semiconductor wafer.
[0022] FIG. 11 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 10 following the completion of a first epitaxial growth phase with inhomogeneous doping of the epitaxial layer.
[0023] FIG. 12 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 11 following the large-area unmasked ion implantation of a doping material balance for a first conduction type.
[0024] FIG. 13 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 12 following the masked selective ion implantation of a doping material for a complementary second conduction type.
[0025] FIG. 14 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 13 following a second epitaxial growth phase and a large-area unmasked ion implantation of a doping material balance of a first conduction type.
[0026] FIG. 15 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 14 following the masked selective ion implantation of a doping material of a complementary second conduction type.
[0027] FIG. 16 illustrates a diagrammatic cross-section through a section of the semiconductor wafer following the completion of six epitaxial growth phases.
[0028] FIG. 17 illustrates a diagrammatic cross-section through the section according to
[0029] FIG. 16 following the diffusing together of the implanted charge compensation zone doping to form a column- or strip-shaped charge compensation zone.
[0030] FIG. 18 is a diagram illustrating further reduced fluctuations of the charge carrier concentration in the drift zone.
[0031] FIG. 19 illustrates a diagrammatic cross-section through a semiconductor device according to an embodiment of the invention.
DETAILED DESCRIPTION
[0032] In the following Detailed Description, reference is made to the accompanying drawings, which form a part hereof, and in which is illustrated by way of illustration specific embodiments in which the invention may be practiced. In this regard, directional terminology, such as “top,” “bottom,” “front,” “back,” “leading,” “trailing,” etc., is used with reference to the orientation of the Figure(s) being described. Because components of embodiments can be positioned in a number of different orientations, the directional terminology is used for purposes of illustration and is in no way limiting. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope is defined by the appended claims.
[0033] FIG. 1 illustrates a diagrammatic cross-section through a semiconductor wafer 16 , which can be used as a semiconductor substrate 17 for a variety of semiconductor devices. This semiconductor wafer 16 may, for example, initially be highly doped with a doping material for a first conduction type, thus being n + -conducting, to produce MOSFET power transistors with a compensation structure. As doping materials, arsenic or phosphorus may be introduced during the single crystal growing phase in concentrations between 5×10 18 cm −3 and 5×10 20 cm −3 or generated in the crystal by appropriate neutron bombardment. A first epitaxial layer is deposited on the front side 20 , which has been polished mirror-bright in a chemical-mechanical process, in a first epitaxial growth phase.
[0034] FIG. 2 illustrates a diagrammatic cross-section through the semiconductor wafer 16 according to FIG. 1 following the completion of a first epitaxial growth phase. In this epitaxial growth phase, a thickness d of n-type silicon is grown in a monocrystalline manner; in this first embodiment of the invention, 20 to 80 atomic % of the doping material for drift zones are homogeneously distributed in this epitaxial layer. The missing doping material quantity of 80 to 20 atomic % can be introduced near the surface by ion implantation to limit the widening of the compensation regions by the lateral diffusion of the complementary-type doping materials for charge compensation zones.
[0035] This homogeneous pre-doping, which however only provides 20 to 80 atomic % of the doping materials of the drift zones, avoids the disadvantage of the relatively high resistance in the middle region of the epitaxial growth phase, which occurs in multiple epitaxial processes with non-doped epitaxial growth phases. In multiple epitaxial processes, a non-doped epitaxial layer is often applied, followed by the doping of the drift zones and the charge compensation zones by ion implantation. The pre-doping described above avoids such disadvantages of reduced conductivity in the middle of the epitaxial growth phase.
[0036] The missing doping material balance between 80 and 20 atomic % can then be introduced near the surface by ion implantation as illustrated in FIG. 3 , thereby limiting the lateral widening of the charge compensation columns. The on resistance is affected both by wide compensation regions and by insufficiently high doping in the middle of the epitaxial growth phases. By using simulations, it can be shown that the on resistance can be minimized by the combination of two methods described above, i.e. the doping of the epitaxy and implantation between the epitaxial growth phases.
[0037] FIG. 3 illustrates a diagrammatic cross-section through the semiconductor wafer 16 according to FIG. 2 following the ion implantation of a doping material balance Δn for a first conduction type. As FIG. 3 illustrates, a charge carrier concentration of n+Δn is obtained near the surface of the first epitaxial layer 18 by an additional ion implantation of, for example, phosphorus or arsenic for a first conduction type 4 of the drift zones. The near-surface zone with the doping material balance 9 of 80 to 20 atomic % of drift zone doping as illustrated in FIG. 3 will in the subsequent diffusion process be distributed in the illustrated epitaxial layer to a thickness d.
[0038] FIG. 4 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 3 following the selective ion implantation of a complementary conduction type 7 in windows 23 of a previously applied ion implantation mask 22 for the second complementary conduction type 7 . Boron may be used as a doping material for the complementary conduction type 7 . As a concentration of doping material increased by Δn prevails near the surface in the drift zone regions 3 , the lateral expansion of the charge compensation zone doping 8 in the subsequent diffusion process to form charge compensation zone columns or strips is limited, allowing for a smaller step size between the charge compensation zones and thus permitting a higher doping of the drift zones.
[0039] FIG. 5 illustrates a diagrammatic cross-section through the semiconductor wafer 16 according to FIG. 4 following a second epitaxial growth phase and an ion implantation of a doping material balance of the first conduction type, which is once again introduced into this second epitaxial layer 24 unmasked, over a large area and near the surface. This ion implantation of the first conduction type 4 for the drift zone 3 does not require any diffusion mask for the near-surface introduction of the doping material balance 9 . Only the next process illustrated in FIG. 6 requires a suitable ion implantation mask 22 for the selective introduction of a doping material of a complementary conduction type.
[0040] FIG. 6 illustrates a diagrammatic cross-section through the semiconductor wafer 16 according to FIG. 5 following the selective ion implantation of a doping material of a complementary second conduction type. This creates a further doping material reservoir in the open windows 23 of the ion implantation mask 22 , but without any connection to the complementary-type regions of the charge compensation zones as illustrated in FIG. 4 .
[0041] FIG. 7 illustrates a diagrammatic cross-section through a section of the semiconductor wafer following the completion of six epitaxial growth phases, wherein 20 to 80 atomic % of homogeneously distributed doping material of the first conduction type 4 have been introduced and the missing doping material balance is introduced near the surface in the regions 9 by ion implantation after each epitaxial growth phase, resulting in the structure illustrated in FIG. 7 , wherein the selectively introduced charge compensation zone doping 8 does not yet form a coherent charge compensation zone column or strip. This requires a further diffusion process, wherein the doping material balance 9 for the drift zones 3 is distributed further in the semiconductor material.
[0042] FIG. 8 illustrates a diagrammatic cross-section through the section according to FIG. 7 following the diffusing together of the implanted charge compensation zone doping to form a column- or strip-shaped charge compensation zone 6 . Whether column- or strip-shaped charge compensation zones 6 are generated depends on the ion implantation mask prepared for the semiconductor device. The doping material balance Δn has likewise been distributed further in the drift zones 3 by diffusion processes, so that relatively highly doped drift zones 3 of a small step size p in micrometers of p≦12 μm can be created, which reduces the on resistance of a semiconductor device with a drift zone structure of this type.
[0043] FIG. 9 illustrates a diagram with optimised concentration fluctuations of the doping material in a drift zone. The doping material concentration N is plotted on the abscissa, while the penetration depth, which is a measure for the blocking capability of the semiconductor device, is plotted on the ordinate. Compared to semiconductor devices with a non-doped epitaxy, where the maximum and minimum values fluctuate about twice as much, concentration fluctuations are noticeably minimized owing to the homogeneous pre-doping of the epitaxial layers in the range of 20 to 80 atomic %.
[0044] The homogeneously distributed proportion of doping material in the epitaxial growth phases can be limited to a third of the total concentration of doping material for the first conduction type, while two thirds subsequently have to be introduced near the surface by ion implantation. In this embodiment of the invention, it is on the other hand desirable that the proportion of doping material introduced by ion implantation is significantly larger than the proportion introduced into the semiconductor crystal by homogeneous doping in the epitaxial growth phase.
[0045] Fluctuations in the concentration of doping material for the drift zones can be reduced further by using a technology and a manufacturing process described below with reference to FIGS. 10 to 18 and resulting in a semiconductor device illustrated in FIG. 19 . This method is likewise based on a semiconductor wafer 16 as illustrated in FIG. 10 , which is highly doped with an n + -type doping material.
[0046] FIG. 11 illustrates a diagrammatic cross-section through the semiconductor wafer 16 according to FIG. 10 following the completion of a first epitaxial growth phase. In this epitaxial growth phase, however, the doping material is not introduced homogeneously, but rather inhomogeneously, i.e. the addition of doping material is reduced or stopped completely during the epitaxial growth process, resulting in a maximum of doping material approximately in the middle of the epitaxial growth phase. The boundaries of the region with a maximum doping n max are indicated by dot-dash lines in the epitaxial layer 18 of FIG. 11 .
[0047] In the subsequent ion implantation to introduce a doping material balance Δn, the relatively lightly doped, near-surface region is filled unmasked with the doping material balance over a large area by using ion implantation as illustrated in FIG. 12 .
[0048] FIG. 13 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 12 following the selective ion implantation of a doping material for a complementary second conduction type. This FIG. 13 corresponds to FIG. 4 , and owing to the ion-implanted concentration of doping material, the lateral outdiffusion of the p-type material introduced by ion implantation is limited, allowing the production of compensated semiconductor devices with small step sizes of less than 12 μm.
[0049] FIG. 14 illustrates a diagrammatic cross-section through the semiconductor wafer according to FIG. 13 following a second epitaxial growth phase and an ion implantation of a doping material balance of a first conduction type, which is once again introduced unmasked and over a large area into the semiconductor wafer. Moreover, a maximum n max of doping material is introduced in the middle of the growth phase during the second epitaxial growth phase, in order to increase the doping in the drift zone further and to ensure that the on resistance for a compensated device of this type is further reduced. FIG. 14 also indicates by a dot-dash line that the doping of the epitaxial layer is initially reduced towards the surface, but the missing doping material balance is then introduced by large-area ion implantation, resulting in a concentration which is capable of impeding a lateral outdiffusion for the charge compensation zones to be formed.
[0050] FIG. 15 illustrates a diagrammatic cross-section through the semiconductor wafer 16 according to FIG. 14 following the selective ion implantation of a doping material of a complementary second conduction type in windows 23 of an ion implantation mask 22 , generating further p-type islands which are diffused together on completion of all of the epitaxial growth phases; in this process, the concentration of doping material in the drift zones becomes uniform.
[0051] FIG. 16 illustrates a diagrammatic cross-section through a section of the semiconductor wafer following the completion of six epitaxial growth phases, wherein initially a maximum doping n max of the first conduction type 4 is generated in each epitaxial growth phase, followed by the introduction of a doping material balance in the region of the future drift zones by large-area ion implantation.
[0052] FIG. 17 illustrates a diagrammatic cross-section through the section according to FIG. 16 following the diffusing together of the implanted charge compensation zone doping 8 to form a column- or strip-shaped charge compensation zone 6 . This column 10 illustrates a reduced lateral outdiffusion between individual epitaxial growth phases, allowing for a smaller step size in combination with higher doping of the drift zones 3 .
[0053] FIG. 18 illustrates further reduced fluctuations of the charge carrier concentration in the drift zone. The doping material concentration N is plotted on the abscissa, while the thickness or depth in the direction z of the individual epitaxial growth phases is once again plotted on the ordinate. The dot-dash line within each epitaxial growth phase indicates a maximum concentration of doping material introduced into each epitaxial layer, while ion implantation with a concentration of Δn is carried out between the epitaxial growth phases, which in turn prevents the lateral outdiffusion of the complementary-conducting material for the charge compensation zones.
[0054] The distribution of the charge carrier concentration Δn introduced by ion implantation is indicated by broken lines, while the fluctuation of the charge carrier concentration in the drift zones after diffusion is indicated by a continuous line. Any fluctuations which are still noticeable are so negligible that the charge compensation zones and the drift zones can come closer together, allowing for a higher drift zone doping.
[0055] FIG. 19 illustrates a diagrammatic cross-section through a semiconductor device 1 according to an embodiment wherein the lateral outdiffusion for the charge compensation zones 6 is significantly reduced by the methods described above, whereby the fluctuation of the doping material concentration in the drift zones is reduced in the vertical direction. This embodiment is a vertical MOSFET with a lateral gate structure, but the teaching of the invention can also be applied to JFET or other compensated device structures, provided that a multiple epitaxial structure is provided for the drift zone.
[0056] In this embodiment, the charge compensation zones are completed by the near-surface introduction of a p-type body zone 12 , which in turn accommodates a highly doped n + -type source zone 13 , wherein the highly doped n + -type source zone 13 and the body zone 12 are contacted by a metallic source electrode 14 , while a lateral gate structure insulated against the body zone 12 by a gate oxide 25 permits the control of this power transistor. As a result of the negligible lateral bulging of the charge compensation zones, a step size 15 of less than 12 μm can be achieved between the charge compensation zones.
[0057] Before the back side 21 of the semiconductor body 2 is metallised for a drain D, the substrate 17 or the original semiconductor wafer 16 can be ground thin, thus further minimising the on resistance of the semiconductor device 1 .
[0058] Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a variety of alternate and/or equivalent implementations may be substituted for the specific embodiments shown and described without departing from the scope of the present invention. This application is intended to cover any adaptations or variations of the specific embodiments discussed herein. Therefore, it is intended that this invention be limited only by the claims and the equivalents thereof.
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A semiconductor device with a semiconductor body and method for its production is disclosed. The semiconductor body includes drift zones of epitaxially grown semiconductor material of a first conduction type. The semiconductor body further includes charge compensation zones of a second conduction type complementing the first conduction type, which are arranged laterally adjacent to the drift zones. The charge compensation zones are provided with a laterally limited charge compensation zone doping, which is introduced into the epitaxially grown semiconductor material. The epitaxially grown semiconductor material includes 20 to 80 atomic % of the doping material of the drift zones and a doping material balance of 80 to 20 atomic % introduced by ion implantation and diffusion.
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BACKGROUND OF THE INVENTION
The present invention relates to paper machines in general, and more particularly to improvements in apparatus for shifting or moving suction heads, rolls, drums, cylinders and/or analogous components of a paper machine between several positions. More particularly, the invention relates to improvements in apparatus which can be used with advantage to move a suction head or a pick-up roll in a paper machine.
It is already known to mount a suction head or a pick-up roll in a paper machine in such a way that the suction head or the pick-up roll (either of these parts will be referred to as a movable component for the sake of brevity) can be moved between an operative position, an intermediate position not far away from the operative position, and a retracted position at a considerable distance from the operative position. For example, it is customary to maintain a suction head in engagement with the inner side of a foraminous felt to attract the paper web to the outer side of the felt at the locus where the web is to be separated from the wire in order to enter the press. In the event of malfunction, e.g., when the web breaks, the suction head is pivoted or otherwise moved from the operative position to an intermediate position and is simultaneously disconnected from the suction generating means so that the web continues to adhere to the wire and is caused to enter a collecting vat or an analogous receptacle for waste paper. The distance between the operative and intermediate positions of the suction head is relatively small, i.e., it does not suffice to facilitate convenient access to a wire or felt which must be removed for the purpose of inspection or replacement. Therefore, the suction head is also movable to a retracted position at a much greater distance from the operation position; this renders it possible to replace the wire and/or the felt without any or with minimal interference on the part of the suction head. The situation is the same or analogous if the component to be moved between operative, intermediate and retracted positions is a pick-up roll.
In presently known paper machines, the component to be moved between the just mentioned three positions is coupled to an electromechanical shifting or displacing apparatus, e.g., to an apparatus including a motor, transmission means, a feed screw, a servomotor and one or more limit switches. A drawback of such apparatus is their complexity; furthermore, many heretofore known apparatus employ a transverse shaft which extends between the front and rear sides of the paper machine and interferes with access to the parts which are to be reached when the movable component is held in the retracted position. Also, the presently known apparatus do not insure satisfactory engagement between the movable component and the adjacent part or parts, e.g., the felt or the paper web, because the axis of the movable component is often tilted with respect to the path of movement of the felt, wire or web. This can cause the web, wire and/or felt to run askew.
SUMMARY OF THE INVENTION
An object of the invention is to provide an apparatus which can shift a suction head, a pick-up roll or another movable component of a paper machine between several positions with a high degree of accuracy and reproducibility and whose construction is simpler and more compact than that of presently known apparatus.
Another object of the invention is to provide an apparatus which can repeatedly and rapidly shift a movable component of a paper machine to and from an operative position in which such component is not likely to adversely affect the movement of a wire, paper web or felt.
A further object of the invention is to provide novel and improved fluid-operated motors for use in the just outlined apparatus.
An additional object of the invention is to provide an apparatus which can be installed in existing paper machines as a simpler, more reliable and more compact substitute for conventional apparatus.
Still another object of the invention is to provide an apparatus which can be used with particular advantage to shift that component of a paper machine which normally causes the paper web to leave the wire and to advance into a press or the like.
The invention is embodied in a paper machine which comprises a movable component (particularly a suction head or a pick-up roll) which is movable between an operative position, a retracted position and an intermediate position, a lever arm or another suitable support which is connected to and movable with the component, a frame or housing, and a novel apparatus for moving the component (with the support) between the operative, retracted and intermediate positions. The apparatus comprises a fluid-operated motor having a cylinder member, a piston rod member, a first piston which is reciprocable in the cylinder member and is rigid with the piston rod member, an annular second piston which slidably surrounds the piston rod member, means for articulately connecting one of the two members (preferably the cylinder member) to the frame or housing, and means for articulately connecting the other member to the support for the movable component. The second piston is movable by fluid (preferably by pressurized hydraulic fluid) from a first to a second position to thereby move the component between the operative and intermediate positions through the medium of the first piston, and the first piston is movable by fluid relative to the second piston to thereby move the component between the intermediate and retracted positions.
The novel features which are considered as characteristic of the invention are set forth in particular in the appended claims. The improved apparatus itself, however, both as to its construction and its mode of operation, together with additional features and advantages thereof, will be best understood upon perusal of the following detailed description of certain specific embodiments with reference to the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic front elevational view of a portion of a paper machine which includes a suction head and embodies the novel apparatus which serves to move the suction head between three different positions; and
FIG. 2 is an enlarged central longitudinal sectional view of one of the fluid-operated motors in the apparatus of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring first to FIG. 1, there is shown a portion of a paper machine which comprises a wire 7 trained over a suction couch roll 1 and a driver roll 2, a press including rolls 3, 4, and a tubular suction head 5 which engages the paper web 6 (shown by a phantom line) intermediate the rolls 1 and 2. The suction head 5 extends between the front and rear sides of the machine and urges a felt 8 against the upper side of the web 6. The felt 8 is trained over several rolls including those shown at 8a and 8b. The suction head 5 attracts the web 6 to the adjacent portion of the felt 8, the web thereupon passing along the underside of the felt 8, past the roll 8a, and into the nip of the rolls 3, 4.
The support means for the suction head 5 comprises a lever arm 9 which is fulcrumed at 10 and the front part of which is articulately connected to the piston rod 12 of a hydraulic motor here shown as a cylinder and piston unit 111. The rear part of the arm 9 (i.e., that part which is more distant from the observer of FIG. 1) is articulately connected to the piston rod of an identical second hydraulic motor further including a cylinder 11' a portion of which is visible in FIG. 1 between the two portions of the cylinder 11 of the motor or unit 111. In accordance with a feature of the invention, the two units are designed to pivot the arm 9, and hence the suction head 5, in two stages. In the event of a malfunction, e.g., when the paper web 6 breaks, the cylinder and piston units are actuated to lift the suction head 5 through a relatively short distance (e.g., 30 millimeters). At the same time, the suction head 5 is disconnected from the suction generating means (not shown). The web 6 then continues to adhere to the wire 7 and passes along the driver roll 2 and downwardly into a collecting vat, not shown.
If the wire 7 and/or the felt 8 must be replaced with a fresh wire or felt, the aforementioned distance of 30 millimeters is not sufficient to afford convenient access to the member 7 and/or 8. The cylinder and piston units are then actuated to lift the suction head 5 through a distance which is preferably several times the aforementioned distance of 30 millimeters.
The details of the cylinder and piston unit 111 are shown in FIG. 2. This unit comprises an elongated cylinder 11 for a reciprocable piston 13 which is rigid with the adjacent end of the piston rod 12. An eye 12A serves to articulately connect the other or outer end of the piston rod 12 to the arm 9. The right hand end wall 11a of the cylinder 11 is articulately connected to the frame or housing 30 of the paper machine by an eye 11A. The cylinder 11 and piston 13 define two cylinder chambers 14, 14a the former of which extends between the piston 13 and an annular second piston 15 which surrounds and is slidable on an intermediate portion of the piston rod 12. The extent to which the second piston 15 is reciprocable in the cylinder 11 is determined by an end wall 17 and an annular member or stop 16 which is located in the path of movement of a larger-diameter portion or collar 15a of the piston 15. The chamber between the second piston 15 and the end wall 17 is shown at 18. The movement of the second piston 15 can also be determined by the end wall 17 and a stop arranged on a shell which surrounds the piston rod 12. The shell is connected with the end wall 17 and the piston rod 12 is slidable within the shell.
The cylinder 11 is formed with ports 19, 20 and 21 for admission of pressurized hydraulic fluid and with fluid evacuating ports 22, 23 and 24. The ports 19 and 22 communicate with the chamber 14a, the ports 20 and 23 communicate with the chamber 14, and the ports 21 and 24 communicate with the chamber 18. The source of pressurized fluid and the valves which regulate the flow of fluid to and from the chambers 14a, 14 and 18 of the cylinder 11 are not shown in the drawing. FIG. 2 shows the piston rod 12 in the fully retracted or inner end position in which the chamber 14a is just large enough to prevent the piston 13 from sealing the ports 19 and 22. Such position of the piston rod 12 corresponds to that angular position of the arm 9 in which the suction head 5 is fully retracted, i.e., in which the suction head is held at a maximum distance from the wire 7. This renders it possible to replace the wire 7 and/or the felt 8 without any interference on the part of the suction head 5.
The manner in which the suction head 5 is moved between three different positions is as follows:
1. Movement from the fully retracted position of FIG. 2 to an intermediate position: The aforementioned system of valves connects the source of pressurized fluid with the ports 19 and 21. The pressure of fluid flowing into the chamber 18 equals the pressure of fluid which is admitted into the chamber 14a. The piston 13 performs the stroke h 1 to move its left-hand end face into abutment with or close to the piston 15. This moves the suction head 5 to an intermediate position in which the suction head is located 30 millimeters above the operative position of FIG. 1. Since the effective area of the left-hand end face F 1 of the piston 15 is larger than the effective area of the right-hand end face F 2 of the piston 13, and since the pressure of fluid in the chamber 18 matches the fluid pressure in the chamber 14a, the piston 15 remains in abutment with the annular stop member 16 and arrests the piston 13 after the latter completes the stroke h 1 . The same result can be achieved if F 1 equals F 2 and the pressure of fluid in the chamber 18 exceeds the pressure fluid in the chamber 14a, or if F 2 is larger than F 1 but the fluid pressure in the chamber 18 is much higher than that in the chamber 14a. During movement of piston 13 toward the piston 15, the port 20 is sealed from the source of pressurized fluid and the port 23 is connected to the tank.
When the suction head 5 reaches the intermediate position, the leader of the web 6 is introduced into the nip of the rolls 3, 4.
2. Movement from the intermediate position to operative position: The port 19 continues to communicate with the source of pressurized fluid and the port 22 is sealed. The valve system connects the port 24 with the tank and seals the port 21 from the source of pressurized fluid. The piston 13 then performs a short additional stroke h 2 (e.g., 30 millimeters) and pushes the piston 15 into abutment with the end wall 17. This moves the suction head 5 back to the operative position of FIG. 1.
3. Movement from operative position to intermediate position: The port 19 continues to communicate with the source of pressurized fluid so that the chamber 14a is filled with pressurized fluid and the piston 13 bears against the piston 15. The port 24 is thereupon sealed and the port 21 is connected to the source of pressurized fluid whereby the piston 15 performs a short stroke h 2 and moves its collar 15a into abutment with the annular stop member 16. The piston 13 retracts the piston rod 12 through the same distance because the area of F 1 is greater than the area of F 2 . Since the suction head 5 is disconnected from the suction generating means as soon as it moves away from the operative position of FIG. 1, the web 6 adheres to the wire 7 and moves over the driver roll 2 and into the aforementioned collecting vat.
4. Rapid lifting to fully retracted position: Such procedure can be restored to in the event of danger to personnel and/or paper machine, .e.g., to prevent excessive damage to the machine. The port 21 is connected with the source of compressed fluid, the port 24 is sealed from the tank, the port 19 is sealed from the source of compressed fluid, and the port 22 is connected to the tank. This insures that the movement of suction head 5 from the operative or intermediate position to fully retracted position takes place with a minimum of delay, i.e., much more rapidly than described at (3).
5. Lifting from operative or intermediate position to fully retracted position: It is assumed that the piston 15 dwells in the position of FIG. 2, that the ports 21, 24 are sealed, and that the piston 13 abuts against the piston 15. The paper machine is assumed to be at a standstill and the operator wishes to replace the wire 7 and/or the felt 8. The port 23 is sealed and the port 20 is connected to the source of pressurized fluid. The port 19 is also sealed and the port 22 is connected to the tank. The fluid flows into the chamber 14 and pushes the piston 13 back to the position of FIG. 2 while the collar 15a of the piston 15 remains in abutment with the annular member 16.
When the replacement of the wire 7 and/or felt 8 is completed, the port 20 is sealed and the port 23 is connected to the tank. The port 22 is sealed and the port 19 is connected with the source of pressurized fluid so that the piston 13 completes the stroke h 1 , i.e., the suction head 5 is moved to its intermediate position at a relatively short distance from the operative position of FIG. 1.
The operation of the cylinder and piston unit 111 has been described without taking into consideration the weight of parts which must be moved if the suction head 5 is to be shifted between retracted, intermediate and operative positions or directly from the operative position to retracted position or vice versa. In actual practice, the pressure of fluid which is admitted into the chamber 18 is selected with a view to compensate for the weight of parts which are to be displaced in response to shifting of the suction head. Furthermore, and if the weight of parts to be moved varies in a direction at right angles to the plane of FIG. 1, the pressure of fluid which is admitted into the chambers of the second motor including the cylinder 11' of FIG. 1 may be different from the pressure of fluid which is admitted into the chambers of the cylinder 11. The purpose of two identical cylinder and piston units or motors whose pistons move in unison is to insure that the axis of the suction head 5 in the operative position of FIG. 1 is always parallel to the axes of the rolls 1, 2, 8a, 8b, 3 and 4 to thus prevent the web 6, the wire 7 and/or the felt 8 from running askew. The motor 111 is accessible at the front side and the other motor is accessible at the rear side of the paper machine.
The improved motors can be used with equal advantage for shifting of other component parts in a paper machine. For example, the suction head is replaced with a roll or cylinder if the part to be shifted is used in the glue pressing, hot glazing, double compacting or triple or fourfold pressing unit of the paper machine.
The improved apparatus exhibits several important advantages. Thus, it can operate with two relatively simple fluid-operated motors which replace conventional electric motors, transmissions and worm drives. Moreover, the two fluid-operated motors insure that the movable component can be moved to each of its positions with a heretofore unmatched degree of accuracy and reproducibility. Still further, the aforementioned transverse shaft, which extends between the front and rear sides of a paper machine utilizing conventional apparatus, can be omitted. Also, the improved apparatus can be actuated to move the suction head or another component at a high speed which is important when rapid retraction of such component prevents damage to or destruction of certain parts of the machine.
If the apparatus is used in a glue pressing, hot glazing, compacting or press unit of the paper machine, the movable component is normally a roll, cylinder or drum which must be rapidly disengaged from a neighboring roll, cylinder of drum when the operation of the machine is interrupted or is about to be interrupted. Still further, the apparatus can be used to move a driver roll, e.g., the driver roll 2 of FIG. 1.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic and specific aspects of my contribution to the art and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the appended claims.
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A suction head or a pick-up roll in a paper machine is mounted on a pivotable lever and is movable therewith between an operative position, an intermediate position at a short distance from the operative position, and a retracted position at a substantial distance from the operative position by two hydraulic cylinder and piston units whose cylinders are articulately connected to the frame and whose piston rods are articulately connected to the lever. The piston rods are rigid with first pistons, and each unit further comprises an annular second piston which surrounds the respective piston rod. Admission of pressurized fluid into a first chamber of each cylinder results in movement of the second pistons from first to second positions to thereby move the lever from operative to intermediate position through the medium of the first pistons and piston rods. The lever is pivoted to retracted position by admitting fluid into a second chamber of each cylinder to thus move the first pistons relative to the second pistons. The lever can be returned to operative position by admitting fluid into a third chamber of each cylinder and by relieving the pressure of fluid in the first chamber so that the first pistons first move relative to and thereupon together with the second pistons.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to devices for discreetly providing confidential combination lock information to screening authorities at airports and the like to provide the screening authorities with means for opening the luggage of a traveler without disclosing the information to other parties.
[0003] 2. Description of the Related Art
[0004] With heightened security measures presently taking place at airports and other travel terminals it has been necessary to subject travelers and their luggage to intense scrutiny and screening procedures. For example, air travelers departing from major airports often are subjected to screening and examination prior to being permitted to board on commercial aircraft, while their luggage is often subjected to internal examination either by X-ray scanners, computed tomography (CT) scanners, and/or computerized axial tomography (CAT) scanners by such authorities as the Travel Security Administration (TSA).
[0005] Several efforts have been made to date to equip luggage with combination locks having a key override whereby the lock may be opened by the TSA screening authority utilizing one of a limited number of keys which they are provided with to override the combination lock and provide access to the contents of the luggage for screening purposes.
[0006] Efforts have also been made to avoid the need to require travelers to purchase combination locks having dual key override for various reasons. For example, often combination locks having a key override are more bulky than ordinary combination locks. Secondly, such locks are more expensive. Finally, their use is limited in that the official screening authorities must be provided with a limited number of such keys and each lock must bear a number which corresponds to the key which overrides the combination such that the screening authorities must first initially make note of the number of the lock and thereafter locate the appropriate key to override the combination.
[0007] One suggested proposal to simplify the manner of screening luggage by the TSA has been made whereby an identification tag will be provided with the luggage and which will include a tray which includes a plurality of upstanding guides arranged to form three arrays of the well-known digital figure-eight symbol. The purchaser will be supplied with this device when purchasing the luggage, or it may be purchased separately. After purchase, the user inserts an appropriate number of metal pieces which depict three numbers which correspond to the combination of the lock associated with the luggage. Thereafter, the tray is placed inside the identification tag which is snapped shut and hung on the outside of the bag. The TSA screeners will then subject the tag to an X-ray or CT scan machine and the metal numbers will be revealed by blocking the rays, allowing the screener to enter the luggage to examine the contents.
[0008] The tag is relatively bulky and must be hung outside the luggage. If it were placed inside the luggage, the metal numbers, which appear black on the X-ray machine, will tend to be confused with other articles (i.e. metal objects) in the luggage and may not be read correctly.
[0009] While this device is somewhat effective in providing screeners with access to the inside contents of the luggage without having to utilize extra devices such as keys or the like, the technique and the procedure can be simplified further by the present invention.
[0010] I have invented a relatively lightweight and simple card-type device which can be placed inside an article of luggage and can relatively easily and simply provide access to the lock combination to a TSA screener utilizing X-ray or CT scanner techniques without confusion with other articles in the luggage.
BRIEF SUMMARY OF THE INVENTION
[0011] The present invention includes a security device having a card-shaped member composed of at least one layer of scanning-radiation-blocking material having a plurality of score-lines defining a section of the scanning-radiation-blocking material with at least one portion of the section capable of being readily and selectively removed by a user to form a user-customized aperture extending through the at least one layer of scanning-radiation-blocking material, with the user-customized aperture defining a user-selected numeral-shape, such that the card-shaped member, having the user-customized aperture therein, selectively blocks scanning radiation from a screening device to display the user-selected numeral-shape on a display of the screening device corresponding to a hidden combination code associated with a closable apparatus.
[0012] In one example embodiment, the closable apparatus is an article of luggage. The card-shaped member may be configured and dimensioned to be disposed within a pocket of the apparatus associated with the user. The pocket may be disposed within the interior of the closable apparatus. In another example embodiment, the at least one layer of scanning-radiation-blocking material includes zinc. Alternatively or in addition, the at least one layer of scanning-radiation-blocking material is capable of blocking X-rays and/or computed tomography (CT) radiation.
[0013] The plurality of score-lines may provide a plurality of removable sections arranged in at least one digital figure-eight pattern capable of forming any selected numerical digit after selective removal of at least one of the plurality of removable sections by the user. The card-shaped member may be associated with distinctive indicia viewable on an exterior surface of the closable apparatus, and such distinctive indicia may be a logo.
[0014] The present invention also includes an article of luggage, having an exterior surface; locking means for opening upon entry of a predetermined combination code; and a closable interior space accessible by the opening of the locking means, the interior space for receiving scanning radiation from a screening device, and the interior space including a pocket for receiving a card-shaped member, such that the card-shaped member is composed of at least one layer of scanning-radiation-blocking material having a plurality of score-lines defining a section of the scanning-radiation-blocking material with at least a portion of the section capable of being readily and selectively removed by a user to form a user-customized aperture extending through the at least one layer of scanning-radiation-blocking material, wherein the user-customized aperture defines a user-selected numeral-shape; and the card-shaped member, having the user-customized aperture therein, selectively blocks the scanning radiation from the screening device to display the user-selected numeral-shape on a display of the screening device corresponding to the predetermined combination code associated with the locking means.
[0015] The card-shaped member may be configured and dimensioned to be disposed within the pocket. The at least one layer of scanning-radiation-blocking material may include zinc. Alternatively or in addition, the at least one layer of scanning-radiation-blocking material is capable of blocking X-rays and/or computed tomography (CT) radiation. The plurality of score-lines may provide a plurality of removable sections arranged in at least one digital figure-eight pattern capable of forming any selected numerical digit after selective removal of at least one of the plurality of removable sections by the user. The card-shaped member may be associated with distinctive indicia viewable on an exterior surface of the apparatus, and such distinctive indicia may be a logo.
[0016] The present invention also includes a method of encoding a lock combination of a lock of a closable apparatus, with the method having the steps of: providing a card-shaped member associated with a closable apparatus and composed of at least one layer of scanning-radiation-blocking material; providing a plurality of score-lines in the at least one layer and defining a section of the scanning-radiation-blocking material; removing a selected portion of the section to form a user-customized aperture extending through the at least one layer of scanning-radiation-blocking material and defining a user-selected numeral-shape; directing scanning radiation from a screening device at the card-shaped member having the user-customized aperture; and selectively blocking the scanning radiation using the card-shaped member having the user-customized aperture, thereby causing the display of the user-selected numeral-shape on a display of the screening device corresponding to a hidden combination code associated with the closable apparatus. The at least one layer of scanning-radiation-blocking material may include zinc.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0017] Preferred embodiments of the invention are disclosed hereinbelow with reference to the drawings, wherein:
[0018] FIG. 1 is a front view of a card-type device according to the invention, incorporating three representations of digital “figure-eight” formed by score lines or otherwise weakening lines in an X-ray blocking material which score lines facilitate simply punching out the appropriate portions or sections to form the desired numeral in each of the three locations, the numerals representing a lock combination;
[0019] FIG. 2 is a perspective view of an article of luggage on a conveyor belt, having a built-in combination lock and an internal pocket which carries the card of FIG. 1 after the appropriate sections have been punched out to form an exemplary combination, “711”;
[0020] FIG. 3 is a cross-sectional view taken along lines 3 - 3 of FIG. 2 showing a pocket having an open top in which the card is slipped for containment;
[0021] FIG. 4 is a cross-sectional view taken along lines 4 - 4 of FIG. 2 wherein the pocket is provided with an open top to the customer, with additional means for sealing the open top after insertion of the combination card, as by adhesive cement, double sided tape, or the like; and
[0022] FIG. 5 is a perspective view of a piece of luggage on a conveyor belt, having a hang-type combination lock and an internal pocket which carries a card according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Referring initially to FIG. 1 there is disclosed a card-type device 10 which may be made of any X-ray or CT scan blocking material (i.e., cast zinc), or it may be layered and having at least one layer with such scanning-radiation blocking material. The scanning-radiation blocking material may be formed to have three spaced-apart sections or boxes 12 , 14 and 16 . The card-type device 10 may include any known chemical elements or compositions of scanning-radiation blocking material, such as cast zinc, lead amalgams, lead foil, and/or any combination thereof to form the sections 12 , 14 and 16 .
[0024] These sections 12 , 14 and 16 each include a plurality of score lines, for example, score lines 23 , 24 , 26 , 27 , 28 , and 30 for section 12 , which essentially weaken the material to facilitate the easy punching out of user-selected portions of the appropriate sections by the user to form the desired numerals of a lock combination for opening a combination lock 33 as an example of locking means for accessing an interior space of an apparatus or article of the user. For example, as shown in the example embodiments in FIGS. 2-5 , the apparatus may be an article of luggage 31 with which the user is traveling and which may be subject to screening by security personnel. Alternatively, the apparatus may be a knapsack, a duffel bag, a book bag, a briefcase, or other closable containers of the user traveling into a secured environment with screening equipment, such as an airport, a bus terminal, a courtroom or other government buildings, national monuments, a school or other educational buildings, large office buildings and skyscrapers, department stores and malls, etc. Accordingly, the apparatus having the combination lock 33 is not limited to an article of luggage for screening and examination.
[0025] The score lines 23 , 24 , 26 , 27 , 28 and 30 may be oriented in an array. The first array of score lines in box 12 will correspond to the first numeral of the combination of the lock 33 , whereas the second array of score lines in box 14 will be utilized to form the second numeral of the combination of the lock 33 , and the third array of score lines in box 16 will be utilized to form the third numeral of the combination of the lock 33 . If the card is made entirely of an X-ray blocking material, each section will be punched out completely by the user. If the card is only layered with an X-ray blocking material in boxes 12 , 14 and 16 , only the layer of X-ray blocking material will be removed by the user.
[0026] It is well known by individuals familiar with computers and calculators that certain of the figure-eight array of lines shown in FIG. 1 can be selectively eliminated to form an appropriate numeral. For example, in the first array in box 12 of score lines, the digital figure-seven can be formed by eliminating the sections identified as 26 , 28 and 18 thereby leaving spaces 23 , 24 , 27 and 30 to form the numeral “7”, as shown in FIG. 2 . On the other hand, the numeral “1” can be formed by eliminating the sections identified as 26 and 28 , thereby leaving spaces 18 , 23 , 24 , 27 and 30 , as shown in FIG. 2 . As a third example the number “3” can be formed by eliminating the sections identified as 24 , 26 , 28 , 18 and 30 , thereby leaving spaces 23 and 27 . It can be seen that by simply punching out the appropriate straight line sections defined by the appropriate score lines the card 10 will be left with spaces which actually form a number. The card can then be placed in a zippered pocket 36 inside the luggage and distinctive indicia, such as an appropriate label or logo, can be placed on the outside of the luggage to alert the screening authority, such as the TSA, that this luggage is equipped with such a card 10 . Upon subjecting the article of luggage to an X-ray or CT scanner machine 34 , the card 10 will either completely or partially block the rays (depending upon the material used), except where the spaces appear, so as to form the appropriate numerals visible on the display monitor of the screening terminal. By the presence of such spaces, the screener will be discreetly informed of the combination of the lock 33 attached to the outside of the luggage 31 .
[0027] As noted, the scanning radiation, such as, for example, X-rays, will be completely or partially blocked in dependence upon the density of the scanning-radiation blocking material which is utilized to form the card 10 . In other words the more dense the material is, the more blockage of X-rays which will occur. For example, one preferred embodiment will be in the form of a card 10 which can be made from an appropriate metal such as cast zinc with score lines being provided sufficient to enable the user to simply punch the appropriate sections out of the card 10 to form the correct number of the combination of the lock 33 . Any material which will completely block or partially block X-rays is contemplated. In fact, if an alternative material can be made of sufficient density to block or to partially block X-rays sufficient to provide a distinction between the blocked X-rays and the unblocked X-rays to identify it will be sufficient. It is only necessary that a sufficient contrast of shading shows up on the display of the screener's machine.
[0028] In use, the card 10 is enclosed in an internal pocket 36 of an article of luggage 31 , as shown in an example embodiment in FIGS. 2-3 , with the article of luggage 31 placed upon a conveyor belt 38 to be screened. In the example embodiment, the article of luggage 31 has a built-in combination lock 33 and the internal pocket 36 which carries the card 10 of FIG. 1 after the appropriate sections have been punched out to form an exemplary combination “711”. Although the card 10 is internally disposed in the article of luggage 31 , in response to scanning radiation from an X-ray or CT scanner machine 34 , the combination “711” encoded on the card 10 will be displayed on a display of the scanner machine 34 for viewing by the screener to discreetly reveal the combination only to the screener and so to allow the article of luggage 31 to be opened and examined by the screener. However, other parties such as passengers and fellow travelers will not be able to determine the hidden combination since the card 10 is internally disposed.
[0029] In one example embodiment, the pocket 36 may have an open top in which the card 10 is slipped for containment, and which open top may then be closed and optionally secured, for example, by known fasteners.
[0030] FIG. 4 is a cross-sectional view taken along lines 4 - 4 of FIG. 2 wherein the pocket 36 is provided with an open top to the customer, with additional means such as fasteners for sealing the open top after insertion of the combination card, as by adhesive cement, double sided tape, or the like.
[0031] In an alternative embodiment, the card of FIG. 1 can simply be placed in a zippered pocket 36 thereby avoiding the need to attract attention to others that the combination of the lock 33 on the outside of the luggage 31 is actually contained inside the luggage. By placing the card 10 inside the bag or luggage 31 , and by disclosing the numerals by the absence of X-ray blocking material, there will be no confusion between the numerals and items stored in the remaining contents of the luggage, as there may be in prior art devices.
[0032] As noted, the distinctive indicia 32 such as an identifying logo can be placed on an exterior surface, such as the outside of the bag 31 , to be viewable to screeners, with such distinctive indicia 32 being associated with the use of the card 10 to alert the TSA that the bag 31 is equipped with a means for disclosing the combination by X-rays or other known scanning techniques. For example, the well known logo promoted as a trademark by Travel Sentry, Inc., as shown as an example of the indicia 32 on the bag 31 in FIGS. 2 and 5 , can be placed on the bag 31 to identify the bag 31 as one having an internally placed combination source. Other suitable logos or indicia may be provided.
[0033] As an alternative embodiment, the card 10 of FIG. 1 can also be placed in an internal pocket of a piece of luggage which can be provided with the luggage as a pocket which is sealable by a zipper or permanently sealable, once the card is removed, altered to display the combination, and replaced into the pocket. The pocket can be provided with a super strength adhesive and release paper on each surface to permit permanently sealing the pocket, such that once the card is sealed into the pocket physical access to the card is not available without destruction of the bag. An appropriate adhesive might be contact cement, or double sided tape.
[0034] As noted, it is only necessary to provide a card of material having sufficient density to fully or partially block the X-rays or other scanning radiation of the TSA screening machines to permit passage therethrough to provide the screeners with the appropriate combination number or code of the combination lock 33 .
[0035] Referring to FIG. 5 there is shown an article of luggage 37 on a conveyor belt 38 having a padlock-type combination lock 40 as another embodiment of locking means of a closable portion of the luggage 37 , with an internal pocket 42 containing a card 10 according to the present invention, with the card 10 encoding the combination of the combination lock 40 . An X-ray or CT scanner machine 34 is also shown in FIG. 5 , such that the scanning radiation therefrom reveals the combination of “711” to the screener on the display of the scanner machine 34 for opening the lock 40 and examining the contents of the article of luggage 37 .
[0036] While the preferred embodiment of the present invention has been shown and described herein, it will be obvious that such embodiment is provided by way of example only. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the invention herein. Accordingly, it is intended that the invention be limited only by the spirit and scope of the appended claims.
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A security device for use with luggage or other closable apparatus includes a card-shaped member composed of at least one layer of scanning-radiation-blocking material having a plurality of score-lines defining a section of the scanning-radiation-blocking material with at least one portion of the section capable of being readily and selectively removed by a user to form a user-customized aperture extending through the at least one layer of scanning-radiation-blocking material, with the user-customized aperture defining a user-selected numeral-shape, such that the card-shaped member, having the user-customized aperture therein, selectively blocks scanning radiation from a screening device to display the user-selected numeral-shape on a display of the screening device corresponding to a hidden combination code associated with the closable apparatus.
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FIELD OF INVENTION
The present invention relates to compounds with activity as antagonists at metabotropic gluatmate receptors and more particularly to pyrazine and triazine derivatives of 1,2,4,5-tetrahydro-Benzo or Thieno [d]azepine that demonstrate activity as group I mGluR antagonists.
BACKGROUND
In the central nervous system (CNS) the transmission of stimuli takes place by the interaction of a neurotransmitter, which is sent out by a neuron, with a neuroreceptor. L-glutamic acid, the most commonly occurring neurotransmitter in the CNS, plays a critical role in a large number of physiological processes. The glutamate-dependent stimulus receptors are divided into two main groups. The first main group forms ligand-controlled ion channels. The metabotropic glutamate receptors (mGluR) belong to the second main group and, furthermore, belong to the family of G-protein-coupled receptors.
At present, eight different members of these mGluRs are known and of these some even have sub-types. On the basis of structural parameters, the different second messenger signaling pathways and the different affinity to low-molecular weight chemical compounds, these eight receptors can be sub-divided into three sub-groups: mGluR1 and mGluR5 belong to group I, mGluR2 and mGluR3 belong to group II and mGluR4, mGluR6, mGluR7 and mGluR8 belong to group III.
Ligands of metabotropic glutamate receptors belonging to the first group can be used for the treatment or prevention of acute and/or chronic neurological disorders such as epilepsy, stroke, chronic and acute pain, psychosis, schizophrenia, Alzheimer's disease, cognitive disorders and memory deficits. Other treatable indications in this connection are restricted brain function caused by bypass operations or transplants, poor blood supply to the brain, spinal cord injuries, head injuries, hypoxia caused by pregnancy, cardiac arrest and hypoglycaemia. Further treatable indications are Huntington's chorea, amyotrophic lateral sclerosis (ALS), dementia caused by AIDS, eye injuries, retinopathy, idiopathic parkinsonism or parkinsonism caused by pharmaceutical compositions as well as conditions which lead to glutamate-deficiency functions, such as e.g. muscle spasms, convulsions, migraine, urinary incontinence, nicotine addiction, opiate addiction, anxiety, vomiting, dyskinesia and depression.
SUMMARY
The present invention is a compound of the formula
wherein
R 1 is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, or unsubstituted phenyl or phenyl substituted in meta or para position with at least one substituents selected from the group consisting of lower alkyl, lower alkoxy or halogen, or is absent, in the case when X is —N═ or ═N—;
R 2 is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, ═O, —S-lower alkyl, —SO 2 -lower alkyl or —OR, —O(CHR a ) m+1 —OR b , NR c 2 , NHNR d 2 , —N(R e )(CHR f ) m+1 —OR g , —N(R h )(CHR i ) m -pyridino, —N(R j )(CHR k ) n —(C 3 -C 6 )cycloalkyl, —N(R l )(CHR m ) m (CR n 2 )—NR o 2 , or —N(R p )(CHR q ) m+1 —NH—C(O)—O-lower alkyl;
m is 1, 2, 3, 4, 5 or 6;
n is 0, 1, 2, 3, 4 or 5;
R and R a-q are independently selected from the group consisting of hydrogen, lower alkyl or lower alkenyl;
X is selected from the group consisting of —N═, ═N—, >C═ or ═C<; and, in the case where R 2 is ═O or alkenyl, the dotted line is a bond,
Y is selected from the group consisting of —CH═CH—, —CH═CR 3 —, —CR 3 ═CH—, —CR 3 —CR 4 — or s; and
R 3 , R 4 are selected, independently from each other, from the group consisting of hydrogen, lower alkyl, lower alkoxy or halogen with the proviso, that when Y represents a vinylene group, only one group R 3 and one group R 4 are present in the resultant benzene ring;
or a pharmaceutically acceptable salt thereof in racemic and optically active form.
It has surprisingly been found that the compounds of formula I are antagonists at metabotropic glutamate receptors.
Objects of the present invention are compounds of formula I and pharmaceutically acceptable salts thereof and their use as pharmaceutically active substances. Methods for the preparation of the above mentioned substances and pharmaceutical compositions based on compounds in accordance with the invention and their production are also objects of the present invention as well as the use of the compounds in accordance with the invention in the control or prevention of illnesses treated by modulation of metabotropic glutamate receptors, and, respectively, for the production of corresponding pharmaceutical compositions.
DETAILED DESCRIPTION
Preferred compounds of formula I within the scope of the present invention are those having the formula
wherein
R 1 is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, or unsubstituted phenyl or phenyl substituted in meta or para positions with at least one substituent selected from the group consisting of lower alkyl, lower alkoxy or halogen, or is absent, when X is —N═ or ═N—;
R 2 is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl, ═O, —S-lower alkyl,
—SO 2 -lower alkyl or
—OR, —O(CHR a ) m+1 —OR b , —NR c 2 , —NH—NR d 2 , —N(R e )(CHR f ) m+1 —OR g , —N(R h )(CHR i ) m -pyridino, N(R j )(CHR k ) n —(C 3 -C 6 )cycloalkyl, —N(R l )(CHR m ) m (CR n 2 )NR o 2 , or —N(R p )(CHR q ) m+1 —NH—C(O)—O-lower alkyl;
m is 1, 2, 3, 4, 5 or 6;
n is 0, 1, 2, 3, 4 or 5;
R and R a-q are independently selected from the group consisting of hydrogen, lower alkyl or lower alkenyl;
X is selected from the group consisiting of —N═, ═N—, >C═ or ═C<; the dotted line is a bond when R is ═O or lower alkenyl; and
a pharmaceutically acceptable salt thereof in racemic and optically active form.
Preferred compounds of formula I-A within the scope of the present invention are those, in which
R 1 is absent and X is —N═ or ═N—; and
R 2 is —NR c 2 , —NH—NR d 2 , —N(R e )(CHR f ) m+1 —OR g ,
—N(R h )(CHR l ) m -pyridino, —N(R j )(CHR k ) n —(C 3 -C 6 )cycloalkyl,
—N(R l )(CHR m ) m (CR n 2 )NR o 2 , or —N(R p )(CHR q ) m+1 —NH—C(O)—O-lower alkyl.
The following are examples of such compounds:
3-Amino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile,
3-(cyclopropylmethyl-amino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile,
3-(2-hydroxy-ethylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile,
(RS)-3-(2-hydroxy-propylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile,
3-hydrazino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile,
{2-[6-cyano-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazin-3-ylamino]-ethyl}-carbamic acid tert-butyl ester, or
3-(2-pyridin-3-yl-ethylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile.
Especially preferred are those compounds of formula I-A, in which
R 1 is absent and X is —N═ or ═N—; and
R 2 signifies —N(R e )(CHR f ) m+1 —OR g ,
—N(R h )(CHR i ) m -pyridino, or —N(R j )(CHR k ) n —(C 3 -C 6 )cycloalkyl.
Examples of such compounds are the following:
3-(cyclopropylmethyl-amino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile,
3-(2-hydroxy-ethylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile,
(RS)-3-(2-hydroxy-propylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile, or
3-(2-pyridin-3-yl-ethylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile.
Compounds of formula I, in which
X signifies >C═ or ═C< and R 1 and R 2 are lower alkyl, are also preferred.
The following are examples of such compounds:
5-ethyl-6-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile, or
6-ethyl-5-methyl -3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile.
Especially preferred are such compounds of formula I, in which
X signifies >C═ or ═C< and R 1 signifies ethyl.
6-Ethyl-5-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile is an example of such a compound.
Also preferred are compounds of formula I, in which
X signifies >C═ or ═C< and R 1 signifies unsubstituted phenyl or phenyl substituted in meta or para positions with one or more substituents selected from the group consisting of lower alkyl, lower alkoxy or halogen.
An example of such a compound is 5-methyl-6-phenyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile.
Further preferred compounds are those, in which
X signifies >C═ or ═C< and R 2 signifies —N(R e )(CHR f ) m+1 —OR g with R e,f,g signifying independently from each other hydrogen, lower alkyl or lower alkenyl.
5-(2-hydroxy-ethylamino)-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile is an example of such a compound.
The term “lower alkyl” used in the present description denotes straight-chain or branched saturated hydrocarbon residues with 1-7 carbon atoms, preferably with 1-4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl and the like.
The term “lower alkenyl” used in the present description denotes straight-chain or branched unsaturated hydrocarbon residues with 2-7 carbon atoms, preferably with 2-4 carbon atoms.
The term “lower alkoxy” denotes a lower alkyl group as defined above linked to an oxygen group. Preferred alkoxy groups are methoxy or ethoxy.
The term “cycloalkyl” denotes a saturated carbocyclic group containing from 3 to 6 carbon atoms, preferred are cyclopropyl, cyclopentyl or cyclohexyl.
The term “halogen” embraces fluorine, chlorine, bromine and iodine.
The term “phenyl substituted in meta or para position with at least one substituent selected from the group consisting of lower alkyl, lower alkoxy or halogen” means the homocyclic six membered aromatic ring which may be substituted by at least one substituent selected from the group consisting of lower alkyl, lower alkoxy or halogen in the para and/or meta positions, relative to the ring carbon that is attached to one of the carbons of the pyrazine ring of the compounds of formula I.
The compounds of formula I and their pharmaceutically acceptable salts can be manufactured by
reacting the compound of the formula
with nucleophiles to obtain a compound of formula
wherein R 21 signifies —OR, —O(CHR a ) m+1 —OR, —NR c 2 , —NH—NR dd′ 2 , —N(R e )(CHR f ) m+1 —OR g ,
—N(R h )(CHR i ) m -pyridino, —N(R j )(CHR k ) n —(C 3 -C 6 )cycloalkyl, —N(R l )(CHR m ) m (CR n 2 )—NR o 2 , or
—N(R p )(CHR q ) m+1 —NH—C(O)—O-lower alkyl as defined before, and, if desired,
converting a functional group of R 21 in a compound of formula I-1 into another functional group to obtain another compound of formula I-1, and, if desired,
converting a compound of formula I-1 into a pharmaceutically acceptable salt; or reacting a compound of the formula
wherein R 22 signifies alkyl, with the compound of formula
to obtain a compound of formula
and, if desired,
converting a compound of formula 1-3 into a pharmaceutically acceptable salt; or reacting a compound of the formula
wherein R 5 signifies halogen, with the compound of formula
to obtain a compound of formula
and, if desired,
converting a functional group of R 2 in a compound of formula 1-4 into another functional group to obtain another compound of formula I-4,
and, if desired,
converting a compound of formula I-4 into a pharmaceutically acceptable salt.
3-Methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo- or thieno-azepin-3-yl)-[1,2,4]triazine-6-carbonitriles (I-2) are prepared by reaction of 3-(methylthio)-5-chloro-6-cyano-1,2,4-triazine (J. J. Huang, J. Org. Chem. 1985, 50, 2293-2298) with tetrahydro-benzo- or thieno-azepine compounds III, e.g. 2,3,4,5-tetrahydro-1H-benzo[d]azepine hydrochloride (J. Heterocycl. Chem. 1971, 8(5), 779-83), in the presence of a base like triethylamine or ethyl-diisopropylamine in solvents like N,N-dimethylformamide, dimethylsulfoxide, methyl-ethylketone, ethanol, dioxane or tetrahydrofuran at temperatures between 10 and 50° C.
Substitution of the Me—S-group in compound I-2 by optionally substituted N-nucleophiles can be performed in water, ethanol, N,N-dimethylformamide, dimethylsulfoxide, 1,2-dimethoxyethane, preferentially in dioxane at elevated temperatures, preferentially 100° C to 160° C.
Substitution of the Me—S-group in compound I-2 by optionally substituted O-nucleophiles can be performed in an inert solvent as ethers, like 1,2-dimethoxyethane or dioxane at temperatures between room temperature and 120° C. after transformation of the corresponding alcohol into an alcoholate using a base like sodium hydride or potassium hydride.
The functionalization of the O- and N-nucleophiles can also serve as a protective function. Thus, modifications at the other part of the R 21 -substituent are allowed, e.g. removal of a N-protecting group, like the tert-butoxycarbonyl group, by methods well documented in the literature.
Compounds of formula I-1 can also be prepared by oxidation of the thioether I-2 to the corresponding sulfon according to known oxidative methods, e.g. by 3-chloroperbenzoic acid in dichloromethane, followed by treatment with thiolates, alcoholates, amines or aqueous base, e.g. like sodium carbonate or sodium hydrogencarbonate, thus yielding the group R 21 .
Compounds of formula I-3 wherein R 22 signifies lower alkyl can be prepared by reacting the intermediate II-1 with tetrahydro-benzo- or thieno-azepine compounds III, e.g. 2,3,4,5-tetrahydro-1H-benzo[d]azepine hydrochloride (J. Heterocycl. Chem. 1971, 8(5), 779-83), in the presence of a base like triethylamine or ethyl-diisopropylamine in solvents like N,N-dimethylformamide, dimethylsulfoxide, methyl-ethylketone, ethanol, dioxane or tetrahydrofuran at temperatures between 10 and 50° C.
The intermediate II-1 can be synthesized in analogy to the procedure as described in J. Org. Chem. 1972, 37 (24), 3958-3960, starting with the condensation of the corresponding amidrazones IV and methyl or ethyl oxomalonate V, followed by ammonolysis of the ester VI, and, finally, dehydration of the amide VII and substitution of the hydroxy group by chlorine (scheme 1).
Compounds of formula
are prepared by methods as shown in schemes 2, 3 and 4 and described in the following. 1,2-Dicarbonyl compounds VIII with R 6 and R 7 signifying both independently from each other hydrogen, optionally substituted phenyl, lower alkyl or lower alkenyl, react with 2-amino-malonic acid diamide IX as described in J. Amer. Chem. Soc. 1949,71,78-81, either in the presence of an aqueous base at temperatures between 0° C. and 60° C. or in the absence of a base in solvents like water or an alcohol at temperatures between room temperature and 120° C. to form the two 3-oxo-3,4-dihydro-pyrazine-2-carboxylic acid amides Xa and Xb. Treatment of Xa and Xb either separately or as a mixture with phosphorus oxychloride and optionally additional phosphorus pentachloride in the presence of triethylamine or diethylaniline at temperatures between 40° C. and 120° C. give 3-chloro-pyrazine-2-carbonitriles II-3a and II-3b (scheme 2).
3-Chloro-pyrazine-2-carbonitriles II-3a and II-3b react either separately or as a mixture with tetrahydro-benzo- or thieno-azepine compounds III or their hydrochlorides in solvents like N,N-dimethylformamide, acetonitrile, acetone or dimethylsulfoxide in the presence of a base like potassium carbonate or a tertiary amine as diisopropyl-ethylamine at temperatures between room temperature and 80° C. to form the desired 3-(tetrahydro-benzo- or thieno-azepine-3-yl)-pyrazine-2-carbonitriles I-5a and I-5b, which can be separated by known methods such as chromatography or crystallization.
In an alternative method (scheme 3), bromopyrazine derivatives of formula II-4 are prepared by reacting O-tosylisonitrosomalononitrile XI with morpholino-enamines of formula XII with R 11 signifying lower alkyl or lower alkenyl, in the presence of a base like pyridine, triethylamine or diisopropyl-ethylamine in aprotic solvents like ether, tetraydrofuran or N,N-dimethylformamide at temperatures between −20° C. and 60° C. to obtain (morpholino-alkenylimino)malononitriles XIII (Helv. Chim. Acta 1986, 69, 793-802). Treatment of the (morpholino-alkenylimino)malononitriles XIII with hydrobromic acid in acetic acid between room temperature and 80° C. induces a cyclisation reaction leading to the bromopyrazines II-4 (Helv. Chim. Acta 1990, 73,1210-1214).
Bromo-pyrazines II-4 react with tetrahydro-benzo or thieno-azepine compounds III or their hydrochlorides in solvents like N,N-dimethylformamide, acetonitrile, acetone or dimethylsulfoxide in the presence of a base like potassium carbonate or a tertiary amine like diisopropyl-ethylamine at temperatures between room temperature and 80° C. to form the desired 3-(tetrahydro-benzo- or thieno-azepine-3-yl)-pyrazine-2-carbonitriles I-6. 3-(Tetrahydro-benzo- or thieno-azepine-3-yl)-pyrazine-2-carbonitriles of formula I-7 can be prepared according to scheme 4.
Diazotization of the 3-amino-5-chloro-2-cyano-pyrazine XIV (J. Org. Chem. 1975, 40, 2341-2347) with t-butyl-nitrite in solvents like acetonitrile or N,N-dimethylformamide in the presence of copper-(II)-bromide at temperatures between room temperature and 95° C. gives the 3-bromo-5-chloro-2-cyano-pyrazine II-5. The 3-bromo-5-chloro-2-cyano-pyrazine II-5 reacts with one equivalent of a primary or secondary amine to two products, in which either the chloro-atom or the bromo-atom is replaced in the amine moiety. If the reaction is performed with a primary amine R 8 NH 2 in a solvent like dioxane or tetrahydrofuran in the presence of a base like triethylamine or diisopropylethylamine, preferentially at room temperature, then compound II-6 with replaced chloro-atom can be obtained with reasonable selectivity. In a second analogous reaction, tetrahydro-benzo- or thieno-azepine compounds III or their hydrochlorides can then be reacted with II-6 in solvents like N,N-dimethylformamide, tetrahydrofuran, dioxane, acetonitrile, acetone or dimethylsulfoxide and in the presence of a base like potassium carbonate or a tertiary amine like diisopropyl-ethylamine at temperatures between room temperature and 80° C. giving compounds I-7.
Optionally substituted 1,2,4,5-tetrahydro-benzo[d]azepine compounds III
are prepared as described in the Eur. Pat. Appl. EP 1 074 549 A2 (2001). The 5,6,7,8-tetrahydro-4H-thieno[2,3-d]azepine with R 3 and R 4 ═H is known (J. Heterocyclic Chem. 1985, 22, 1011). Analogous 5,6,7,8-tetrahydro-4H-thieno[2,3-d]azepine compounds bearing substituents in the thiophene ring can be prepared in close analogy as outlined in scheme 5. Precursor acid chlorides XV bearing preferentially a tosyloxy protective function at the secondary nitrogen atom are cyclized in an inert solvent like 1,2-dichloroethane, dichloromethane or nitrobenzene in the presence of a Lewis acid catalyst like aluminium trichloride, tin tetrachloride or phosphorous pentachloride at temperatures between −40° C. and 80° C. to yield the protected ketones XVI. Hydroxy thieno[2,3-d]azepines XVII can be obtained by simultaneous reduction of the ketone function and removal of the N-tosyl protective function by treatment with sodium bis(methoxyethoxy)aluminium-hydride in toluene at reflux. The hydroxy thieno[2,3-d]azepines XVII can be further reduced to 5,6,7,8-tetrahydro-4H-thieno[2,3-d]azepines XVIII with stannous chloride in acetic acid in the presence of hydrochloric acid at temperatures between room temperature and 100° C.
The methods for the preparation of compounds of formula I are described in more detail in examples 1 to 15.
The pharmaceutically acceptable salts can be manufactured readily according to methods known per se and taking into consideration the nature of the compound to be converted into a salt. Inorganic or organic acids such as, for example, hydrochloric acid, hydrobromic acid, sulphuric acid, nitric acid, phosphoric acid or citric acid, formic acid, fumaric acid, maleic acid, acetic acid, succinic acid, tartaric acid, methanesulphonic acid, p-toluenesulphonic acid and the like are suitable for the formation of pharmaceutically acceptable salts of basic compounds of formula I. Compounds which contain the alkali metals or alkaline earth metals, for example sodium, potassium, calcium, magnesium or the like, basic amines or basic amino acids are suitable for the formation or pharmaceutically acceptable salts of acidic compounds of formula I.
The compounds of formula I and their pharmaceutically acceptable salts are, as already mentioned above, metabotropic glutamate receptor antagonists and are therefore useful in the treatment or prevention of diseases which are mediated by metabotropic glutamate receptor antagonists. The compounds of formula I can be used for the treatment or prevention of acute and/or chronic neurological disorders, such as epilepsy, stroke, chronic and acute pain, psychosis, schizophrenia, Alzheimer's disease, cognitive disorders, memory deficits and psychosis. Other treatable indications are restricted brain function caused by bypass operations or transplants, poor blood supply to the brain, spinal cord injuries, head injuries, hypoxia caused by pregnancy, cardiac arrest and hypoglycaemia. Further treatable indications are Huntington's chorea, ALS, dementia caused by AIDS, eye injuries, retinopathy, idiopathic parkinsonism or parkinsonism caused by pharmaceutical compositions as well as conditions which lead to glutamate-deficient functions, such as e.g. muscle spasms, convulsions, migraine, urinary incontinence, nicotine addiction, psychoses, opiate addiction, anxiety, vomiting, dyskinesia and depression. The compounds are especially useful for the treatment of pain and migraine.
The compounds of the present invention are group I mGluR antagonists. Their pharmacological activity was tested using the following method:
Binding Assay for the Characterization of mGluR 1 Antagonistic Properties
Binding assay with tritiated 1-ethyl-2-methyl-6-oxo-4-(1,1,2-tritritio-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-1,6-dihydro-pyrimidine-5-carbonitrile (Eur. Pat. Appl. EP 1 074 549 A2): HEK 293 cells were transiently transfected with the rat mGluR1a receptor. The cells were collected and washed 3 times with PBS. The cell pellets were frozen at −80° C. Membranes were prepared from HEK 293 cells transfected with the rat mGluR1a receptor and used in the binding experiments at 10 μg proteins per assay after resuspension in a HEPES NaOH 20 mM, pH=7.4 binding buffer. 1-Ethyl-2-methyl-6-oxo-4-(1,1,2-tritritio-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-1,6-dihydro-pyrimidine-5-carbonitrile (S.A 33.4 Ci/mmol) was used at 3 nM final concentration. The incubation with variable concentrations of potential inhibitors was performed for 1 hour at room temperature, the incubate was then filtered onto GF/B glass fiber filter preincubated 1 hour in PEI 0,1% and washed 3 times with 1 ml of cold binding buffer. The radioactivity retained on the unifilter 96 was counted using a Topcount β counter. After correction for non specific binding the data were normalized and the IC 50 value calculated using a 4 parameters logistic equation which was fitted to the inhibition curve.
The preferred compounds have an IC 50 range of 0.001-10.0 μmol/l (B-IC 50 ).
In the table below are shown some specific activity data of preferred compounds:
Example No.
B-IC 50 (□M)
3-(2-methoxy-ethoxy)-5-(1,2,4,5-tetrahydro-
1
3.0
benzo[d]azepin-3-yl)-[1,2,4]triazine-6-
carbonitrile
3-amino-5-(1,2,4,5-tetrahydro-benzo[d]-
2
0.027
azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
3-dimethylamino-5-(1,2,4,5-tetrahydro-
3
1.38
benzo[d]azepin-3-yl)-[1,2,4]triazine-6-
carbonitrile
3-(cyclopropylmethyl-amino)-5-(1,2,4,5-
4
0.005
tetrahydro-benzo[d]azepin-3-yl)-
[1,2,4]triazine-6-carbonitrile
3-(2-hydroxy-ethylamino)-5-(1,2,4,5-
5
0.031
tetrahydro-benzo[d]azepin-3-yl)-
[1,2,4]triazine-6-carbonitrile
(RS)-3-(2-hydroxy-propylamino)-5-(1,2,4,5-
6
0.027
tetrahydro-benzo[d]azepin-3-yl)-
[1,2,4]triazine-6-carbonitrile
3-hydrazino-5-(1,2,4,5-tetrahydro-
7
0.37
benzo[d]azepin-3-yl)-[1,2,4]triazine-6-
carbonitrile
{2-[6-cyano-5-(1,2,4,5-tetrahydro-
8
0.027
benzo[d]azepin-3-yl)-[1,2,4]triazin-3-
ylamino]-ethyl}-carbamic acid tert-butyl
ester
3-(2-pyridin-3-yl-ethylamino)-5-(1,2,4,5-
9
0.029
tetrahydro-benzo[d]azepin-3-yl)-
[1,2,4]triazine-6-carbonitrile
6-ethyl-5-methyl-3-(1,2,4,5-tetrahydro-
12
0.006
benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
5-ethyl-6-methyl-3-(1,2,4,5-tetrahydro-
12
0.103
benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-
13
0.47
pyrazine-2-carbonitrile
5-methyl-6-phenyl-3-(1,2,4,5-tetrahydro-
14
0.045
benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
5-(2-hydroxy-ethylamino)-3-(1,2,4,5-
15
0.5
tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-
carbonitrile
The compounds of formula I and pharmaceutically acceptable salts thereof can be used as pharmaceutical compositions, e.g. in the form of pharmaceutical preparations. The pharmaceutical preparations can be administered orally, e.g. in the form of tablets, coated tablets, dragees, hard and soft gelatine capsules, solutions, emulsions or suspensions. However, the administration can also be effected rectally, e.g. in the form of suppositories, or parenterally, e.g. in the form of injection solutions.
The compounds of formula I and pharmaceutically acceptable salts thereof can be processed with pharmaceutically inert, inorganic or organic carriers for the production of pharmaceutical preparations. Lactose, corn starch or derivatives thereof, talc, stearic acid or its salts and the like can be used, for example, as such carriers for tablets, coated tablets, dragees and hard gelatine capsules. Suitable carriers for soft gelatine capsules are, for example, vegetable oils, waxes, fats, semi-solid and liquid polyols and the like; depending on the nature of the active substance no carriers are, however, usually required in the case of soft gelatine capsules. Suitable carriers for the production of solutions and syrups are, for example, water, polyols, sucrose, invert sugar, glucose and the like. Adjuvants, such as alcohols, polyols, glycerol, vegetable oils and the like, can be used for aqueous injection solutions of water-soluble salts of compounds of formula I, but as a rule are not necessary. Suitable carriers for suppositories are, for example, natural or hardened oils, waxes, fats, semi-liquid or liquid polyols and the like.
In addition, the pharmaceutical preparations can contain preservatives, solubilizers, stabilizers, wetting agents, emulsifiers, sweeteners, colorants, flavorants, salts for varying the osmotic pressure, buffers, masking agents or antioxidants. They can also contain still other therapeutically valuable substances.
As mentioned earlier, pharmaceutical compositions containing a compound of formula I or a pharmaceutically acceptable salt thereof and a therapeutically inert excipient are also an object of the present invention, as is a process for the production of such pharmaceutical compositions which comprises bringing one or more compounds of formula I or pharmaceutically acceptable salts thereof and, if desired, one or more other therapeutically valuable substances into a galenical dosage form together with one or more therapeutically inert carriers.
The dosage can vary within wide limits and will, of course, be fitted to the individual requirements in each particular case. In general, the effective dosage for oral or parenteral administration is between 0.01-20 mg/kg/day, with a dosage of 0.1-10 mg/kg/day being preferred for all of the indications described. The daily dosage for an adult human being weighing 70 kg accordingly lies between 0.7-1400 mg per day, preferably between 7 and 700 mg per day.
Finally, as mentioned earlier, the use of compounds of formula I and of pharmaceutically acceptable salts thereof for the production of pharmaceutical compositions, especially for the control or prevention of acute and/or chronic neurological disorders of the aforementioned kind, is also an object of the invention.
The following examples are provided for illustration of the invention. They should not be considered as limiting the scope of the invention, but merely as being representative thereof.
EXAMPLE 1
3-(2-Methoxy-ethoxy)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
a) 5-Chloro-3-methylsulfanyl-[1,2,4]triazine-6-carbonitrile
A solution of 500 mg (2.7 mmol) of 3-methylsulfanyl-5-oxo-4,5-dihydro-[1,2,4]triazine-6-carboxylic acid amide (J. J. Huang, J. Org. Chem. 1985, 50, 2293-2298; H. Wang et al., Hua Hsueh Hsueh Pao 1964, 30(2), 183-192; CA Vol. 61, 8311b) in 38 ml (408 mmol) of phosphorus oxychloride was heated to reflux during 1.5 h. After cooling of the dark brown reaction mixture, the excess of phosphorus oxychloride was evaporated under reduced pressure. To destroy residues of phosphorus oxychloride and to neutralize the reaction mixture, the resulting red-brown oily residue was dissolved in 15 ml of toluene and the solution added to an ice-cold saturated aqueous solution of sodium hydrogencarbonate. The organic phase was diluted with 100 ml of dichloromethane, separated from the aqueous phase, dried over sodium sulfate, and evaporated under reduced pressure. The resulting 5-chloro-3-methylsulfanyl-[1,2,4]triazine-6-carbonitrile was obtained as a brown oil and was used in the following reactions without further purification.
b) 3-Methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
A solution of 395 mg (2.7 mmol) of 2,3,4,5-tetrahydro-1H-3-benzazepine hydrochloride [J. Heterocycl. Chem. 1971, 8(5), 779-83] in 5 ml of ethanol was treated at room temperature with 0.92 ml (5.4 mmol) of Huenig's base and, thereupon, with a solution of 501 mg (2.7 mmol) of crude 5-chloro-3-methylsulfanyl-[1,2,4]triazine-6-carbonitrile in 5 ml of ethanol. The dark brown reaction mixture was stirred during 18 h at room temperature. For the working-up, the product, partially precipitated in pure form, was filtered and the resulting mother liquor evaporated under reduced pressure. The residue was chromatographed on silica gel with a 2:1 v/v mixture of hexane and ethylacetate as the eluent. In total, 470 mg (58.5% of theory) of 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile were obtained in the form of a beige powder; MS: 298 (M+H) + .
c)3-(2-Methoxy-ethoxy)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
Under an argon atmosphere at 0° C., a solution of 25.6 mg (0.34 mmol) of 2-methoxy-ethanol in 2 ml of tetrahydrofurane was treated with 15 mg (0.34 mmol) of sodium hydride (55% dispersion in refined oil) and stirred during 15 min. To this mixture, a solution of 100 mg (0.34 mmol) of 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile in 3 ml of tetrahydrofurane was added and stirring continued for 18 h at 40° C. The yellow solution was evaporated under reduced pressure and the residue (141 mg) was chromatographed on silica gel with a 99:1 v/v mixture of dichloromethane and methanol as eluent. Thus were obtained 10 mg (9% of theory) of 3-(2-methoxy-ethoxy)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a light yellow solid; MS: 326 (M+H) + .
EXAMPLE 2
3-Amino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
A dispersion of 200 mg (0.67 mmol) of 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile, which was obtained according to the method as described in example 1b, and 1.0 ml of ammonium hydroxide (1.34 M) was heated under stirring in a sealed tube at 140° C. overnight. To complete the reaction, another 1.0 ml of ammonium hydroxide (1.34 M) was added. Heating was continued under the aforementioned conditions for 18 h. The limpid solution was evaporated under reduced pressure and the residue was chromatographed on silica gel with a 95:5 v/v mixture of dichloromethane and methanol as the eluent. There were obtained 40 mg (22% of theory) of 3-amino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a light yellow solid; MS: 267 (M+H) + .
EXAMPLE 3
3-Dimethylamino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
In an analogous manner as described in example 2, reaction of 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile with dimethylamine (33% solution in absolute ethanol) in a sealed tube at 110° C. yielded 3-dimethylamino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a light brown amorphous solid; MS: 295 (M+H) + .
EXAMPLE 4
3-(Cyclopropylmethyl-amino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
A mixture of 150 mg (0.50 mmol) of 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as prepared in example 1b and 74 mg (1.0 mmol) of aminomethyl-cyclopropane in 5 ml of dioxane was stirred at 120° C. overnight. The solution was evaporated under reduced pressure and the residue was chromatographed on silica gel with a 98:2 v/v mixture of dichloromethane and methanol as the eluent. There were obtained 57 mg (35% of theory) of 3-(cyclopropylmethyl-amino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a white solid; MS: 321 (M+H) + .
EXAMPLE 5
3-(2-Hydroxy-ethylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
In analogy to the procedure as described in example 4 the 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile was reacted with ethanolamine in dioxane at 140° C. overnight to give 3-(2-hydroxy-ethylamino)-5 -(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a light yellow solid; MS: 311 (M+H) + .
EXAMPLE 6
(RS)-3-(2-Hydroxy-propylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
In analogy to the procedure as described in example 4 the 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile was reacted with (RS)-1-amino-2-propanol in dioxane at 120° C. overnight to give (RS)-3-(2-hydroxy-propylamino)-5-(1,2,4,5 -tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a white solid; MS: 325 (M+H) + .
EXAMPLE 7
3-Hydrazino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
In analogy to the procedure as described in example 4 the 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4] triazine-6-carbonitrile was reacted with hydrazine hydrate in dioxane at 140° C. during 3 hours to give 3-hydrazino-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a yellow amorphous powder; MS: 282 (M+H) + .
EXAMPLE 8
{2-[6-Cyano-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazin-3-ylamino]-ethyl}-Carbamic Acid Tert-Butyl Ester
In analogy to the procedure described in example 4 the 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile was reacted with (2-aminoethyl)-carbamic acid tert-butyl ester in dioxane at 120° C. overnight to give {2-[6-cyano-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazin-3-ylamino]-ethyl}-carbamic acid tert-butyl ester as a white solid; MS: 410 (M+H) + .
EXAMPLE 9
3-(2-Pyridin-3-yl-ethylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
A solution of 120 mg (0.40 mmol) of 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile in 5 ml of dichloromethane was treated at room temperature with 109 mg (0.44 mmol) of 3-chloro-perbenzoic acid (70%). After 2 hours the reaction mixture was evaporated under reduced pressure, and, without working-up and characterization, the resulting crude 3-methanesulfonyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile was directly treated with a solution of 108 mg (0.88 mmol) of 3-(2-aminoethyl)pyridine in 10 ml of dioxane. The reaction mixture was then stirred at 80° C. overnight. The reaction mixture was then evaporated under reduced pressure and the residue obtained directly chromatographed on silica gel with a 95:5:0.1 v/v/v mixture of dichloromethane, methanol and ammonium hydroxide as the eluent. There were obtained 55 mg (37% of theory) of 3-(2-pyridin-3-yl-ethylamino)-5 -(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a white amorphous solid; MS: 372 (M+H) + .
EXAMPLE 10
3-Hydroxy-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile
A solution of 200 mg (0.67 mmol) of 3-methylsulfanyl-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile in 10 ml of dichloromethane was cooled to 0° C. and treated with 332 mg (1.35 mmol) of 3-chloro-perbenzoic acid (70%). The reaction mixture was warmed up to room temperature and stirred overnight. For the working-up, the reaction mixture was diluted with 10 ml of dichloromethane and extracted twice with 10 ml of a saturated solution of sodium hydrogencarbonate. The combined organic phases were dried over sodium sulfate, and evaporated under reduced pressure. The resulting residue, 170 mg of a yellow powder, was purified by chromatograhy on silica gel with a 98:2 mixture of dichloromethane and methanol as eluent. There were obtained 154 mg (86% of theory) of 3-hydroxy-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile as a yellowish solid; MS: 266 (M−H).
EXAMPLE 11
3-(2-Amino-ethylamino)-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile trifluoro-acetate
To a solution of 60 mg (0.15 mmol) of {2-[6-cyano-5-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazin-3-ylamino]-ethyl}-carbamic acid tert-butyl ester as prepared in example 8 in 2 ml of dichloromethane were added 0.2 ml of trifluoroacetic acid. The reaction mixture was stirred at room temperature for one hour and then evaporated under reduced pressure. The solid residue was dispersed in ether. The resulting solid was filtered and gave 30 mg (47% of theory) of 3-(2-amino-ethylamino)-5 -(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-[1,2,4]triazine-6-carbonitrile trifluoro-acetate as an off-white solid; MS: 310 (M+H) + .
EXAMPLE 12
12-1) 5-Ethyl-6-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile and
12-2) 6-Ethyl-5-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
a) 5-Ethyl-6-methyl-3-oxo-3,4-dihydro-pyrazine-2-carboxylic acid amide and 6-ethyl-5-methyl-3 -oxo-3,4-dihydro-pyrazine-2-carboxylic Acid Amide
A solution of 8.32 g (80.61 mmol) 2-amino-malonic acid diamide and 9.75 g (83.26 mmol) of 2,3-pentanedione in 60 ml of water was heated under reflux for 18 hours. After cooling to room temperature the crystals formed were collected by filtration and dried in vacuo. There were thus obtained 9.52 g (52.54 mmol, 65.2% of theory) of a 3:2 or a 2:3 mixture of the 6-ethyl-5-methyl-3-oxo-3,4-dihydro-pyrazine-2-carboxylic acid amide and the
5-ethyl-6-methyl-3-oxo-3,4-dihydro-pyrazine-2-carboxylic acid amide as yellow solid; MS: 181 (M) + .
b) 3-Chloro-6-ethyl-5-methyl-pyrazine-2-carbonitrile and 3-chloro-5-ethyl-6-methyl-pyrazine-2-carbonitrile (1:1 Mixture of the Two Isomers)
1.81 g (10.0 mmol) of the 3:2 or 2:3 mixture of the 6-ethyl-5-methyl-3-oxo-3,4-dihydro-pyrazine-2 -carboxylic acid amide and the 5-ethyl-6-methyl-3-oxo-3,4-dihydro-pyrazine-2 -carboxylic acid amide were suspended in 4.2 ml (30 mmol) of triethylamine. Then, 30 ml of phosphorus oxychloride were slowly added between 0° C. and 5° C. and the reaction mixture heated under reflux for 3 hours. It was then cooled to 20° C., 5.3 g (25 mmol) of phosphorus pentachloride were added and the reaction mixture heated again under reflux for 3 hours. It was then added to water while maintaining a temperature of 20° C. to 25° C. The aqueous phase was subsequently extracted 5 times with 100 ml of ether and the combined ether phases washed with saturated sodium hydrogen carbonate solution, dried over magnesium sulfate and evaporated under reduced pressure. The residue formed was chromatographed on silica gel using a 1:1 v/v mixture of dichloromethane and hexane as eluent giving 1.0 g (5.5 mmol, 55% of theory) of a 1:1 mixture of the 3-chloro-6-ethyl-5-methyl-pyrazine-2-carbonitrile and the 3-chloro-5-ethyl-6-methyl-pyrazine-2-carbonitrile in form of an orange red oil; MS: 181 (M) + .
c) 5-Ethyl-6-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile and 6-ethyl-5-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
A solution of 0.300 g (1.65 mmol) of the 1:1 mixture of the 3-chloro-6-ethyl-5-methyl-pyrazine-2 -carbonitrile and the 3-chloro-5-ethyl-6-methyl-pyrazine-2-carbonitrile, of 0.395 g (1.30 mmol) of 2,3,4,5-tetrahydro-1H-benzo[d]azepine hydrochloride (J. Heterocycl. Chem. 1971, 8(5), 779-83) and of 0.566 g (2.60 mmol) of N-ethyl-diisopropylamine in 1.0 ml of N,N-dimethylformamide was stirred at room temperature for 60 hours and then at 60° C. for 18 hours. The reaction mixture was subsequently poured into 50 ml of an ice/water mixture and extracted 3 times with 50 ml of ethylacetate. The combined ethylacetate phases were dried over magnesium sulfate and evaporated under reduced pressure. The residue formed was then chromatographed on silica gel using dichloromethane as eluent giving 0.086 g (0.29 mmol, 18% of theory) of the 6-ethyl-5-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile as yellowish solid after crystallization from dichlormethane/pentane; MS: 293 (M+H) + ; and 0.074 g (0.25 mmol, 15% of theory) of the 5-ethyl-6-methyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile as yellowish solid; MS: 293 (M+H) + .
EXAMPLE 13
3-(1,2,4,5-Tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
In analogy to the procedure as described in example 12 the 2-chloro-3-cyanopyrazine (J. Chem. Soc., Perkin Trans. 1 1991, 11, 2877-81) was treated with 2,3,4,5-tetrahydro-1 H-benzo[d]azepine hydrochloride (J. Heterocycl. Chem. 1971, 8(5), 779-83) and N-ethyl-diisopropylamine in N,N-dimethylformamide at room temperature followed by 60° C. to yield the 3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile as light yellow solid; MS: 251 (M+H) + .
EXAMPLE 14
5-Methyl-6-phenyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
In analogy to the procedure described in example 12 1-phenyl-1,2-propanedione and 2-aminomalonamide were heated in an aqueous solution to give 5-methyl-3-oxo-6-phenyl-3,4 -dihydro-pyrazine-2-carboxylic acid amide. Then, the 5-methyl-3-oxo-6-phenyl-3,4-dihydro-pyrazine-2-carboxylic acid amide was treated with triethylamine and phosphorus pentachloride in phosphorus oxychloride at reflux to give the 3-chloro-5-methyl-6-phenyl-pyrazine-2-carbonitrile. The 3-chloro-5-methyl-6-phenyl-pyrazine-2-carbonitrile was finally treated with 2,3,4,5-tetrahydro-1H-benzo[d]azepine hydrochloride (J. Heterocycl. Chem. 1971, 8(5), 779-83) and N-ethyldiisopropylamine in N,N-dimethylformamide at room temperature to yield the 5-methyl-6-phenyl-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile as yellow amorphous solid; MS: 341 (M+H) + .
EXAMPLE 15
5-(2-Hydroxy-ethylamino)-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
a) 3-Bromo-5-chloro-pyrazine-2-carbonitrile
A solution of 0.309 g (2.00 mmol) of the 3-amino-5-chloro-pyrazine-2-carbonitrile (J. Org. Chem. 1975, 40, 2341-2347) in 5.0 ml of acetonitrile was slowly added at a temperature of 65° C. to a suspension of 0.903 g (4.0 mmol) of copper(II)bromide and 0.344 g (3.0 mmol) of tert.-butyl nitrite in 20.0 ml of acetonitrile. The reaction mixture was stirred at 65° C. for 1 hour, then cooled to room temperature. It was subsequently poured into 50 ml of an ice/water mixture and extracted 3 times with 50 ml of dichloromethane. The combined dichloromethane phases were dried over magnesium sulfate and evaporated under reduced pressure. The residue formed was chromatographed on silica gel with a 4:1 to 0:10 v/v gradient of hexane and dichloromethane as the eluent giving 0.333 g (1.53 mmol, 76.2% of theory) of the 3-bromo-5-chloro-pyrazine-2-carbonitrile as light yellow amorphous solid; MS: 218 (M) + .
b) 3-Bromo-5-(2-hydroxy-ethylamino)-pyrazine-2-carbonitrile
0.061 g (1.00 mmol) of ethanolamine were added slowly at room temperature to a solution of 0.218 g (1.0 mmol) of the 3-bromo-5-chloro-pyrazine-2-carbonitrile and 0.264 g (2.0 mmol) of N-ethyldiisopropylamine in 15.0 ml of dioxane. The reaction mixture was stirred at room temperature for 18 hours. It was subsequently poured into 50 ml of an ice/water/sodium hydrogen carbonate mixture and extracted 3 times with 50 ml of ethylacetate. The combined ethylacetate phases were dried over magnesium sulfate and evaporated under reduced pressure. The residue formed was chromatographed on silica gel with a 100:0 to 95:5 v/v gradient of dichloromethane and methanol as the eluent giving 0.131 g (0.539 mmol, 53.9% of theory) of the 3-bromo-5-(2-hydroxy-ethylamino)-pyrazine-2-carbonitrile as yellow amorphous solid; MS: 243 (M) + .
c) 5-(2-Hydroxy-ethylamino)-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile
0.415 g (3.00 mmol) of potassium carbonate were added slowly at room temperature to a solution of 0.243 g (1.0 mmol) of the 3-bromo-5-(2-hydroxy-ethylamino)-pyrazine-2-carbonitrile and 0.220 g (1.2 mmol) of the 2,3,4,5-tetrahydro-1H-benzo[d]azepine hydrochloride (J. Heterocycl. Chem. 1971, 8(5), 779-83) in 10.0 ml of N,N-dimethyl-formamide. The reaction mixture was stirred at room temperature for 64 hours and at 80° C. for 5 hours. It was subsequently poured into 50 ml of an ice/water mixture and extracted 3 times with 50 ml of dichloromethane. The combined dichloromethane phases were dried over magnesium sulfate and evaporated under reduced pressure. The residue formed was chromatographed on silica gel with a 9:1 to 0:10 v/v gradient of hexane and ethylacetate as the eluent giving 0.308 g (1.0 mmol, 100% of theory) of the 5-(2-hydroxy-ethylamino)-3-(1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-pyrazine-2-carbonitrile as light yellow amorphous solid; MS: 310 (M+H) + .
EXAMPLE A
Tablets of the following composition are produced in a conventional manner:
mg/Tablet
Active ingredient
100
Powdered lactose
95
White corn starch
35
Polyvinylpyrrolidone
8
Na carboxymethylstarch
10
Magnesium stearate
2
Tablet weight
250
EXAMPLE B
Tablets of the following composition are produced in a conventional manner:
mg/Tablet
Active ingredient
200
Powdered lactose
100
White corn starch
64
Polyvinylpyrrolidone
12
Na carboxymethylstarch
20
Magnesium stearate
4
Tablet weight
400
EXAMPLE C
Capsules of the following composition are produced:
mg/Capsule
Active ingredient
50
Crystalline lactose
60
Microcrystalline cellulose
34
Talc
5
Magnesium stearate
1
Capsule fill weight
150
The active ingredient having a suitable particle size, the crystalline lactose and the microcrystalline cellulose are homogeneously mixed with one another, sieved and thereafter talc and magnesium stearate are admixed. The final mixture is filled into hard gelatine capsules of suitable size.
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The invention relates to compounds which are represented by the formula
wherein R 1 , R 2 , R 3 , R 4 , X and Y are as defined in the specification, as well as pharmaceutically acceptable salts thereof. The invention further relates to pharmaceutical compositions containing these compounds and to a process for their preparation. The compounds possess affinity towards metabotropic glutamate receptors and are therefore useful in the treatment or prevention of acute and/or chronic neurological disorders.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to devices designed to separate clear stock from fats, oils, and meat solids derived from cooking meat or fowl.
2. Description of the Prior Art
Prior art separating systems generally do not use a screen filter to separate out small particles of meat from the stock. Where a screen filter is applied, it is often inconvenient to use. For example in U.S. Pat. No. 4,934,420 the screen is simply placed over the top of the collection vessel. The edge of the screen filter has nothing to prevent particles of meat from falling over the edge of the collection vessel and on to the counter below.
U.S. Pat. No. 5,297,476 also uses a screen filter with only a slight depression for holding the meat particles from pouring over the side. Although the depression is an improvement over the flat screen filter of U.S. Pat. No. 4,934,420 described above, it is not enough to assure that larger sections of meat will not fall over the sides when poured into the filter.
Another problem area found in prior an separators often involves the flow valve used to control the flow of liquid from the collection vessel. The valve is often difficult to operate and difficult to clean. For example, in U.S. Pat. No. 3,713,788 the control rod for the valve extends up through the stock and fat layer. The control rod is an extra component which must be cleaned because of its position in the stock and fat. Actuation of the control rod requires the operator's hand to be on top of the separator while the operators head must be to the side to see where the fat layer is located.
Yet another problem area with prior art separators is controlling the point at which the flow valve is shut off to prevent fat from being added to the clear stock as it is drained from the collection vessel. This is due to a funnel-like collection vessel used in many prior art devices such as those shown in U.S. Pat. Nos. 3,865,023, 4,331,189, 4,389,926, 4,460,185, 4,464,265, 4,934,420, and 5,297,476. In these inventions, the rate at which the liquid drops in the collection vessel is relatively slow when the liquid is in the wide upper area of the collection vessel. However, as the fluid drops in the collection vessel, the rate at which it drops increases because of the smaller cross section of the collection vessel at lower levels. Finally when the fluid is near the neck at the bottom of the vessel, the rate of drop can be ten times as fast as when the fluid was near the top of the vessel. It becomes especially difficult to control the valve at such times because it must be shut off quickly to prevent fat from mixing with the clear stock When there is only a small mount of stock initially available, this problem is important because all the stock resides in the lower levels of the funnel-like collection vessel and the rate of drop of the fluid in the collection vessel starts out fast and gets faster, making accurate control of the flow valve extremely difficult.
The needed improvements in separators pointed out in the above discussion of the prior art have been incorporated in the present invention, and are described m the following specifications.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a convenient means of separating oil and fat from stock, from both small and large quantities of stock.
An object of the present invention is to provide a means of deriving fat free stock in a single operation even when there is a relatively large quantity of stock available, as would be produced from cooking a large portion of meat or a complete large fowl, such as a large turkey.
An object of the present invention is to provide a means of separating and retaining large as well as small pieces of meat or foul from the stock.
An object of the present invention is to provide a separator flow valve that can be easily operated, disassembled and cleaned and for which replacement parts can be readily obtained at low cost.
The present invention comprises a colander, a transparent hopper vessel with a trap, a support base and a flow valve connected to the trap for draining fluid from the hopper vessel. The hopper vessel receives the stock. After a period of standing, the fat in the stock floats to the top and forms a clearly discernible layer. The clear stock is drained from the bottom of the hopper vessel through the trap and flow valve to an external collection vessel. As the clear stock is drawn off, the layer of fat at the top is clearly visible through the transparent walls of the hopper. The flow valve is shut off before the fat layer reaches the entrance to the flow valve in the trap, thereby preventing fat from mixing with the clear stock that has been drown off.
If only a small mount of stock is available initially, the clear stock can still be separated from the fat. The trap covers a portion of the bottom of the hopper vessel, but is still relatively large as compared to the narrow funnel necks found at the bottom of many prior art separators. For example, it occupies typically not less than 10% of the floor area of the hopper vessel. The width and breath of the trap is essentially maintained down to its bottom, providing a constant and relatively slow rate of decent of the fat layer during the period when the clear stock is being drawn off. This design thereby permits a precise cut off of the flow of stock in time to prevent mixing fat and clear stock even when only a small mount of stock is initially available.
The flow valve is designed to use a standard and readily available "O"-ring as the sealing element, which is the component most subject to ware in the valve. The "O"-ring is easily replaced at low cost, making repair of the flow valve quick and economical.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective drawing of a colander which forms the uppermost portion of the present invention.
FIG. 2A is a perspective view of a hopper vessel which forms the middle portion of the invention.
FIG. 2B is a perspective view of a trap that forms a part of the hopper vessel.
FIG. 3 is a perspective view of the base of the present invention.
FIG. 4A is a plan view of a flow valve used with the hopper vessel of the present invention.
FIG. 4B is a front view of the control lever for the flow valve.
FIG. 4C is a side view of the flow valve.
DETAILED DESCRIPTION OF THE INVENTION
As shown m FIGS. 1 through 4, the invention is comprised of four principal components, a colander 1, a hopper vessel 5, a base 12, and a flow valve 15. In particular, FIG. 1 shows the colander 1 to include four generally vertical sides walls 3A, two horizontally positioned handles 3B extending outwardly from the top portion of the front and rear side walls. A horizontally positioned strainer 2, which forms the bottom of the colander and is joined about its periphery to the inside lower edges of the side walls 3A. The lower outside edge of the side walls 3A are indented to form a recessed area 4. This recessed area is used to slide the bottom portion of the colandar into the top of the hopper vessel where the colander is held in its working position to strain the stock before it is received by the hopper vessel.
In order to facilitate the production of clear stock by requiring only one operation with the fact/stock stock separator after cooking a large portion of meat or foul such as a large turkey, the colander typically has a minimum volume of 144 cubic inches.
FIG. 2A shows the hopper vessel 5 to be comprised of four generally vertical side walls 5A joined together along their side vertical edges to form an enclosure with a generally rectangular cross section that is open at its bottom and at its top. Mounted on the outside left and right walls are handles 6A and 6B, respectively. Handle 6A is not visible, but is located on the left side wall symmetrically with respect to handle 6B on the right side wall. This Figure also shows a base 12 located immediately below the hopper vessel that is used to support the hopper vessel at a convenient working height, which is typically five inches above a working surface, such as a counter top. The base is similar in construction and cross sectional dimensions to the hopper vessel. It comprises four generally vertical walls 12A joined along their vertical edges to produce an enclosure with a generally rectangular cross section that is open at its bottom and at its top. On the top outside portion of the walls 12A is an indentation 13, which permits this portion of the base to fit inside and lock itself in its working position in the bottom of the hopper vessel. The hopper vessel includes a plurality of holes 11 in its vertical side walls below a platform 7. These holes are used for quickly draining water from the hopper vessel to facilitate the washing and clean up process. Only one hole is shown in the drawing, but these holes are generally located near the comer of the vertical walls.
FIG. 2A also shows the inside of the hopper vessel including the platform 7. FIG. 2B is a detailed drawing of this platform which is located inside and approximately midway down inside the hopper vessel. The platform is joined about its periphery to the inside walls of the hopper vessel, sealing off the inside of the hopper vessel to prevent any flow of liquid below the level of the platform. The platform includes an area 7A that slopes generally downward from its periphery at its sides and rear towards the front of the platform where a trap 8 is located. This is shown by the directional arrows 7B which point in the downward direction of the flow. The trap is typically positioned in the front, central area of the platform. The trap is in the form of a generally cubic shaped depression that is open at its top, with its top edges joined to the platform and with its forward side edges joined to the inside front wall of the hopper vessel.
As can be seen in FIG. 2A, them is a threaded port 9, referred to as the drain pipe port, which passes through the front wall of the hopper vessel and enters into the lower portion of the trap. Through this port is threaded a dram pipe D that is a part of the flow valve 15 which is shown in detail in FIGS. 4A, 4B and 4C. In particular, it can be seen from the plan view of this flow valve, shown in FIG. 4A, that the flow valve comprises a control lever 16, depressible bearing shafts 17A and 17B located on opposite sides of the valve control lever, brackets 21A and 21B, each bracket having bearing ports 18A and 18B, respectively, a mounting pin 25, a spring 22, and a drain pipe 23.
On the right end of the drain pipe, as can be seen in FIG. 4A, there are external threads 23A that are threaded into port 9 to secure the valve to the hopper vessel and to make a connection to the trap to pass clear stock to an external collection vessel. The brackets 22A and 22B are positioned parallel to one another and are spaced apart to accept the placement of the control lever 16 between then; however, in FIG. 4A, the control lever is shown removed from the valve to make it possible to view components that lie below the control lever. To place the control lever between the brackets, the bearing shafts 17A and 17B, which are internally spring loaded within the control lever, are pressed inwardly towards the control lever, and the control lever is then inserted between the brackets. The control lever is positioned between the brackets in such a way as to align the bearing shafts 17A and 17B with the bearing holes 18A and 18B, respectively. Once aligned, the bearing shafts under the pressure of the internal spring loading, automatically extend outwardly from the control lever and into the bearing ports, thereby providing a pivot joint for the control lever about the bearing shafts.
The brackets are oriented vertically and are parallel to one another. They are secured in position by attachment to the drain pipe at their lower edges. The pin 25 is passes through ports 25A and 25B in the brackets 21A and 21B respectively in a direction generally orthogonal to the face of the brackets in an area near the right end of the brackets, as shown in FIG. 4A. The pin 25 spans the spacing between the brackets and is held in position by attachment means to the brackets at ports 25A and 25B.
As is known to those skilled in the art, the pin may be secured in this position by a number of methods, as for example a press fit or brazing to ports 25A and 25B in the brackets, or the pin and ports may be threaded. Similarly, the bearing shafts may be spring loaded by a number of methods, as for example placing a spring or other resilient device between the shafts within the control lever. One end of each bearing shaft is retained within the control lever by any one of several possible methods including collars about the retained end, or attachment to an internal spring, which is itself secured internally to the control lever.
In FIG. 4C, which is a side view of the flow valve, it can be seen that the valve further comprises a stopper 20 and an "O"-ring 19. The stopper typically has a circular cross section and is a part of the lower end 16C of the control lever. The lower end of the control lever shown in FIG. 4B, is flared outwardly to accommodate the size of the stopper which is typically larger than the width of the control lever. This greater width of the control lever at this point also provides mechanical support for the stopper. As shown in FIG. 4C, the stopper is positioned to be aligned with and fit into the inside of the drain pipe at its left end. When the stopper is placed inside the end of the drain pipe, it blocks the drain pipe, cutting off the flow of fluid through the pipe. The "O"-ring is fitted over the stopper. When the stopper is positioned inside the pipe, the "O"-ring is compressed between the control lever and the collection pipe, allowing it to function as a valve gasket that insures that any fluid leaking past the stopper does not pass beyond the "O"-ring.
FIG. 4C also shows that port 9 in the hopper vessel is oriented to have a slightly downward slope of approximately 15 degrees with respect to the horizontal. This slope is automatically transferred to the drain pipe when the pipe is threaded into port 9. The slope is incorporated into the design to use gravity to assist the flow of fluid from the trap through the pipe.
The side view of bracket 21B, as seen in FIG. 4C shows it to be attached at its lower edges to the top of the dram pipe 23. The top left portion of the bracket is shown to include bearing port 18B through which bearing shaft 17B extends. The control lever 16 can be seen to have an upper half 16A and a lower half 16B with the upper and lower halves joining at the middle 16C of the control lever where they form an angle of approximately 120 degrees with one another. Both the lower half and the upper half of the control lever have a longitudinal axis. The control lever also has a left and a right side These sides are parallel to one another and and are also parallel to the longitudinal axis which both lie in the same plane. The bearing shafts extend outward from their respective sides in a direction orthogonal to their respective side of the control lever.
The lower half of the control lever extends downward from the middle and is positioned generally vertically while the upper half extends to the right from its middle at an angle of approximately 30 degrees above the horizontal plane. The spring 22 is connected between the mounting pin 25 and the lower half of the control lever 16B, causing the stopper 20 to be pressed inside the collection pipe, closing the pipe and shutting off the flow of fluids through the valve until the valve is actuated. The flow valve is actuated when pressure is applied in a downward direction on the upper half of the control lever 16A. When the valve is actuated, the control lever rotates about bearing shafts 17A and 17B which are located at the middle of the control lever. This rotation, causes the stopper to be withdrawn from the collection pipe and permits fluid to flow through the valve.
The downward pitch of port 9 helps to drain fluid by gravity and thereby automatically avoids the trapping of fluids in the valve or trap. This feature alone aids in keeping the fat/stock separator clean. Also aiding in the cleaning operation is the ability of the bearing shafts to be depressed, which permits the control lever, to be removed. It is then an easy matter to clean the area normally below the control lever. The control lever contains the stopper which is easy to clean when the lever is removed from the valve. The valve gasket is a standard "O"-ring part which is simply rolled on or off the stopper, facilitate cleaning and replacement.
As is known to those skilled in the art, many variations of the present invention may be made without departing from the spirit or scope of the invention. One primary example is the hopper vessel and the trap may have round or oval walls rather than generally rectangular wall recited above in connection with the preferred embodiment The invention is limited only by the following claims.
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A fat/stock separator comprising a colander, a transparent hopper vessel with a trap, a support base and a flow valve mounted to and connected through the wall of the hopper vessel to the trap for draining fluid from the hopper vessel. The colander in a preferred embodiment is sufficiently large to accept the stock and meat parts produced from cooking a large portion of meat or fowl, such as a complete turkey. The oil and fat contained within the stock separates and floats to the top after standing for a period of time. It is then possible to draw off through the flow valve fat free stock from beneath the layer of oil. The contours of the trap and the transparency of the hopper vessel facilitate determining accurately where the fat free stock ends, thereby making it possible to draw off fat free stock, whether there is a large or a small amount of liquid in the hopper vessel.
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BACKGROUND OF THE DISCLOSURE
The present invention is generally directed to a method for treating a doped amorphous silicon surface to enhance electrical contact. The method is applicable to the production of microelectronic circuit devices, and more particularly, is more applicable to the production of thin film amorphous silicon semiconductors, particularly those employed in liquid crystal display matrix addressed systems.
A liquid crystal display device typically comprises a pair of flat panels sealed at their outer edges and containing a quantity of liquid crystal material. The flat panels generally possess transparent electrode material disposed on the inner surfaces in predetermined patterns. One panel is often covered completely by a single transparent ground plane electrode. The opposite panel is configured with an array of transparent electrodes, referred to herein as pixel (picture element) electrodes. Thus a typical cell in a liquid crystal display includes liquid crystal material disposed between a pixel electrode and a ground electrode forming, in effect, a capacitor-like structure disposed between transparent front and back panels. In general, however, transparency is required for only one of the two panels and the electrodes disposed thereon.
In operation, the orientation of liquid crystal material is effected by voltages applied across the electrodes on either side of the liquid crystal material. Typically, voltage applied at the pixel electrode effects a change in the optical properties of the liquid crystal material. This optical change causes the display of information on the display screen. In conventional digital watch displays and in new LCD displays, screens used in some miniature television receivers, the visual effect is typically produced by variations in reflected light. However, the utilization of transparent front and back panels and transparent electrodes also the permits the visual effects to be produced by transmissive effects. These transmissive effects may be facilitated by subsequently powered light sources for the display including fluorescent type devices. This is typically referred to as back lighting. Various electrical mechanisms are employed to sequentially turn on and off individual pixel elements in an LCD display. Most relevantly, the switch element of the present invention comprises a thin film field effect transistor employing a layer of amorphous silicon. These devices are preferred in many LCD devices because of their potentially small size, low power consumption, switching speed, ease of fabrication, and compatibility with conventional LCD structures.
Thin film field effect transistors made from plasma enhanced chemically vapor deposited (PECVD) amorphous silicon (a-Si) and silicon nitride are ideal for matrix addressing of liquid crystal displays. They are fabricated on glass substrates with high picture element density using methods and equipment employed in conventional integrated circuit fabrication. In one process for FET fabrication and LCD displays, a molybdenum contact is made to N + amorphous silicon using two masking steps. After a deposition of an insulative material such as silicon nitride, a layer of intrinsic amorphous silicon and the doping of the upper portions of the amorphous silicon layer, a thin layer of molybdenum is sputter deposited. This film is patterned back into small regions called mesas. Then the silicon nitride/silicon layers are patterned into regions somewhat larger than the mesas and referred to herein as islands. Subsequently, thick molybdenum is deposited on the wafer and patterned into source/drain and data line electrodes. The deposition of the thin molybdenum before subsequent processing into islands has been found to be necessary to ensure reliable contact of molybdenum to the N + silicon. Hence, it is seen that two masking steps are required to form the contact: the mesa and mask and the island mask. Reducing the number of masking steps is desirable because it reduces processing time and in general, increases device yield.
SUMMARY OF THE INVENTION
In accordance with a preferred embodiment of the present invention, a thin layer of molybdenum, about 50 nanometers in thickness, is sputter deposited on the N + silicon. This molybdenum layer is then removed by etching without any patterning required. The silicon/silicon nitride layer is then patterned into islands as before. Then molybdenum source/drain metal is deposited, patterned and etched and the process is completed. It is the deposition of this thin molybdenum layer and its subsequent removal which is believed responsible for the improvements in electrical contact between the molybdenum source/drain electrodes and the N + amorphous silicon material.
It is noted that the present method of processing eliminates the need to form molybdenum mesas prior to formation of the source/drain contacts. Thus one masking step is eliminated. It is also noted that, without the present invention, the mesa/island structure is generally required since the overhang problem due to undercutting of the silicon/silicon nitride layers can develop and cause step coverage problems for the source/drain metallization.
Accordingly, it is an object of the present invention to provide a method for improving electrical contact to amorphous silicon materials. It is also an object of the present invention to reduce the number of masking steps required in the formation of amorphous silicon thin film transistors.
It is yet another object of the present invention to increase the yield of thin film field effect transistor devices employed in microcircuit applications.
It is yet another object of the present invention to reduce the number of masking steps and improve the yield in the manufacture of matrix addressed liquid crystal displays.
Lastly, but not limited hereto, it is an object of the present invention to provide a method for treating an amorphous silicon surface, particularly an N + doped amorphous silicon surface, to enhance electrical contact with said surface, particularly when the subsequent contacting material is molybdenum.
DESCRIPTION OF THE FIGURES
The subject matter which is regarded as the invention is particularly pointed out and distinctly claimed in the concluding portion of the specification. The invention, however, both as to organization and method of practice, together with further objects and advantages thereof, may best be understood by reference to the following description taken in connection with the accompanying drawings in which:
FIG. 1A is a cross-sectional side elevation view illustrating the mesa and island structures present at one stage in thin film FET fabrication;
FIG. 1B is a cross-sectional side elevation view similar to FIG. 1A, but more particularly illustrating the deposition of source/drain contact material and the etching of a gap therein to form an inverted field effect transistor device;
FIG. 2A is a cross-sectional side elevation view illustrating an initial process step in accordance with the present invention;
FIG. 2B is similar to FIG. 2A, but more particularly illustrates the removal of the thin layer of deposited molybdenum resulting in permanent alternation of the N + amorphous silicon surface;
FIG. 2C is similar to FIG. 2B, but more particularly illustrates patterning via a mask step to form islands and particularly illustrating the absence of mesa structures;
FIG. 2D is similar to FIG. 2C, but more particularly indicating the deposition and patterning of source/drain metallization.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1A and 1B are provided to particularly illustrate the fact that the present invention utilizes one less masking step than is provided by other processing methods. In particular, FIG. 1A illustrates one stage in the fabrication of an inverted, thin film field effect transistor. FIG. 1B illustrates a completed FET structure produced in accordance a process which is different than the present invention. The transistor structures shown in FIG. 1 are seen as being disposed upon a glass substrate 10. This is the typical situation in which these transistors are employed in liquid crystal display devices. However, in general, any insulative substrate material which is thermally compatible and non-reactive with other materials employed in the transistor is suitable for use as a substrate. It is also noted that the transistor structures as illustrated in the figures herein are referred to as inverted since the gate electrode is deposited at a lower point in the transistor structure.
In particular, FIG. 1A illustrates gate electrode 12 disposed on substrate 10. The disposition of gate electrode materials and conductive leads typically requires a separate masking and patterning step which is not specifically relevant to the practice of the present invention. However, following formation of metallic gate electrode patterns 12, insulative layer 14, typically comprising silicon nitride is deposited over the substrate. In a similar fashion, a layer of amorphous silicon material 16 is then deposited over insulative layer 14. Doped amorphous silicon layer 15 is then deposited in a conventional fashion using well known methods to produce layer 15 of doped N + amorphous silicon. Next, a layer of metallic material 18 such as molybdenum is employed. Molybdenum layer 18 is employed for the purpose of enhancing electrical contact to the doped N + amorphous silicon material 15. It is the improvement of this electrical contact to which the present invention is specifically addressed. In accordance with the process illustrated in FIGS. 1A and 1B, layer 18 is subject to a masking and patterning operation resulting in the formation of a mesa structure 18 shown in FIG. 1A. It is noted that this particular masking step is the one which is eliminated by the practice of the present invention. Nonetheless, in the process illustrated, a subsequent patterning and masking operation removes portions of layers 14, 15 and 16 so as to form island structures beneath the mesa structure shown. It is noted that if layer 18 is not removed or cut back into mesas prior to deposition and etching of source and drain electrode material, an overhang due to undercutting of the silicon/silicon nitride material is apt to develop and to cause step coverage problems for the source/drain metallization layer. Thus, the separate masking operations for mesa and island structures have been found to be highly desirable to prevent step coverage problems from occurring.
FIG. 1B illustrates the completion of a process for forming a thin film field effect transistor from the structure seen in FIG. 1A. In particular, a layer of conductive material 19, preferably comprising molybdenum is deposited and patterned as shown. In particular, patterning of the molybdenum material results in the formation of an aperture or gap which separates source and drain portions of the field effect transistor. It is noted that contact improvement layer 18 is divided into portions 18' as shown. While typically comprising the same material, preferably molybdenum, structures 18' and 19 are shown as distinct in FIG. 1B since the structures actually perform somewhat different functions. In particular, as noted above, molybdenum layer 18 (also designated as 18' after patterning) is relatively thin, namely approximately 50 nm, and serves solely to improve electrical contact to the doped amorphous silicon layer 15. However, a much thicker metallization layer 19 is actually employed to provide source and drain metallization patterning and connection of these device elements to the rest of the circuit. In general, in a liquid crystal display type device as described above, each pixel element is associated with a single FET device such as that shown in FIG. 1B (or in FIG. 2D as is more particularly discussed below with reference to the process of the present invention). It is also noted that the figures of the present invention are not shown to scale and, in particular, the dimensions in the vertical direction have been exaggerated so as to more readily provide a pictorial illustration of the invention and also to provide drawings which are more readily understood by those skilled in the microelectronic fabrication arts.
A process for carrying out the present invention is particularly illustrated in FIGS. 2A-2D. The processing required to produce the cross-section in FIG. 2A is typically the same processing that is employed in the construction of the device stage shown in FIG. 1A, as discussed above, up to and including the formation of doped amorphous silicon layer 15. In this regard, it is noted that while the doped region herein is referred to as a separate layer 15, it is nonetheless understood by those skilled in that art that this layer is actually formed by doping a portion of amorphous silicon layer 16 and as such, layers 15 and 16 essentially form a single structure with the exception that the uppermost regions of the amorphous silicon material are doped with a particular polarity dopant such as phosphorus.
However, FIG. 2A illustrates the deposition of a thin layer of molybdenum which is preferably sputtered onto the N + doped amorphous silicon. This layer of molybdenum 21 is preferably approximately 50 nanometers in thickness, but may range from about 10 to about 100 nanometers in thickness. It is preferably deposited by sputtering, Also, in marked contrast to other processes, thin molybdenum layer 21 is removed. It is preferably removed by etching with a mixture of phosphoric, acetic, and nitric acids in an aqueous solution. This is typically referred to as a PAWN etch. Most importantly, it is noted that molybdenum layer 21 is removed without any patterning step being employed. This is in marked contrast to the process illustrated in FIGS. 1A and 1B. As a result of the deposition and removal of molybdenum layer 21, it is believed that a permanent alteration of N - doped amorphous silicon layer 15 is produced. This alteration is illustrated by heavy line 20 seen in FIGS. 2B, 2C and 2D. It is this permanent alteration which appears to produce the desirable characteristics of the present invention. In accordance with preferred embodiments of the present invention for forming thin film field effect transistors, the silicon/silicon nitride layer is then patterned into islands as described above. A typical resulting island is shown in FIG. 2C. It is particularly noted that mesa structures are absent in FIGS. 2C and 2D and that no problem of undercutting, overhanging or step coverage is present. Nonetheless, the alteration of the surface of N + doped amorphous silicon 15 renders that surface much more susceptible to electrical contact with subsequently deposited molybdenum material 19 which is patterned as described above to produce source and drain metallization. The resulting structure is seen in FIG. 2D. It has been found that if the deposition of molybdenum layer 21 is omitted from the process, the yield of good electrical contacts is significantly reduced. It is also noted that experiments conducted clearly indicate that it is the deposition and subsequent removal of molybdenum layer 21 which results in the beneficial effects provided by the process of the present invention. In particular, it has been determined by electrical measurements that there is an alteration of the N + silicon surface due to the deposition and removal of the molybdenum. Even after long etching in a PAWN etch to remove the molybdenum, the electrical conductivity of the N + silicon is much higher than for untreated N + silicon. Furthermore, sputter etching of the surface, followed by plasma etching sufficient to remove a small fraction of the N + material, results in a dramatic reduction of the N + conductivity in comparison with that observed from material exposed to molybdenum deposition and removal. This indicates that a permanent alteration of the N + surface has occurred. This alteration persists even through multiple resist processing steps including cleaning steps and oxygen ashing. This altered surface is important for producing a good bond and contact between the thick molybdenum layer 19 which is deposited and patterned into source and drain metallization after formation of the islands.
In an alternate embodiment the first molybdenum cap is not removed until just prior to deposition of the source-drain metalization. This molybdenum cap protects the surface from contamination during intermediate processing steps such as ITO deposition and patterning. Subsequent etching of the molybdenum cap is also advantageous in that it strips the Si surface of the contaminants.
Accordingly, from the above, it should be appreciated that the process of the present invention significantly improves contact to doped amorphous silicon surfaces. It is further seen that the process of the present invention reduces the number of masking steps employed in the fabrication of thin film amorphous transistors. It is also seen that the process described herein is particularly advantageous for forming FET control device in matrix addressed liquid crystal displays. It is also seen that the processing time and the device yield associated with fabrication of such transistors is also improved by the process of the present invention.
While the invention has been described in detail herein in accord with certain preferred embodiments thereof, many modifications and changes therein may be effected by those skilled in the art. Accordingly, it is intended by the appended claims to cover all such modifications and changes as fall within the true spirit and scope of the invention.
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Electrical contact to doped amorphous silicon material is enhanced by depositing a thin layer of molybdenum on the amorphous silicon surface and subsequently removing it. This treatment is found to permanently alter the silicon surface so as to facilitate and improve electrical contact to the silicon material by subsequently deposited metallization layers for source and drain electrode attachment. The layer of molybdenum which is deposited and removed need only be approximately 50 nanometers in thickness to produce desirable results. The method is particularly useful in the fabrication of thin film, inverted, amorphous silicon field effect transistors. Furthermore, such devices are particularly useful in the fabrication of liquid crystal display systems employing such field effect transistors in matrix addressed arrays used for switching individually selected pixel elements.
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BACKGROUND OF THE INVENTION
The invention relates to an electric contact for liquid crystal display cells. The contact arrangement described in German Pat. No. 2,910,779 consists of part mounts comprising a bottom part and side walls, from the upper ends of which two mutually parallel strips (projections) begin which reach over the display device. A display cell representing a single digit is pushed into the clamping seat thus formed. A fluorescence plate can then be provided between the holder bottom and the display cell. In the holder bottom, an integrated electronic circuit is embedded which is electrically connected to the terminal pins protruding from the holder bottom and to the contact pins located in the side walls. The contact pins are curved towards the display cell and, with connection surfaces extending across the end face of the display cell, form a spring-loaded electric contact for the electrodes. If the contact is unsatisfactory, the contact pins can be soldered to the connection surfaces. For the representation of several display symbols, a corresponding number of part holders is connected by means of snap closures.
The known contact arrangement can be exchanged only with great difficulty, even if the contact pins are not soldered to the connection surfaces. The display device to be provided with contacts cannot be operated in transmitted light. With the exception of a fluorescence plate, artificial illumination is difficult. In addition, the number of terminal pins for the representation of many display symbols is considerable. Using this contact arrangement, it is difficult to provide large display cells with contacts.
It is one of the objects of invention to provide an electric contact arrangement for liquid crystal display cells, which is suitable for both transmissive and reflective displays, which can easily be exchanged, and which allows good electrical contacting of the display cell. It is a further object to provide a device which is also suitable for display cells of any desired shape, and which has few external electrical terminals and is of space-saving design.
The advantages obtained by the invention are essentially that the electric contact arrangement, due to the counter-contacts, represents a good and stable electrical connection to the display cell and nevertheless, for example in the event of a malfunction of the integrated circuit, can readily be exchanged. Since the contact arrangement is located outside the display and illumination zone, it is particularly suitable for displays which are operated in transmitted light. Moreover, the outlay on connections, which is otherwise conisderable, using auxiliary prints, part holders and "chip-on-glass" technology is minimised.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is explained below in more detail by reference to examples illustrated in the drawing in which:
FIG. 1 shows a liquid crystal display cell with an electrical contact arrangement according to the invention;
FIG. 2 shows another liquid crystal display cell with another electric contact arrangement according to the invention;
FIG. 3 shows a section of the contact arrangement according to FIG. 2 along the line A--A';
FIG. 4 shows a liquid crystal display cell with another electric contact arrangement according to the invention;
FIG. 5 shows a section of the contact arrangement according to FIG. 4 along the line B--B', and
FIG. 6 shows a cascade connection of two integrated circuits.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Two contact arrangements according to the invention with L-shaped multi-point connectors 1 are shown in FIG. 1. The counter-contacts held in the multi-point connector 1 and the external terminals are formed by contact tabs 2 and contact pins 3. The two contact arrangements are plugged into the side of a liquid crystal display cell 4 which has electrode segments 5 for digits and decimal points. The contact arrangement is mounted on a print plate 6 by means of soldering the contact pins 3.
Two further electric contact arrangements according to the invention with L-shaped multi-point connectors 1 are shown in FIG. 2. The designation is here the same as in FIG. 1. In this case, the two contact arrangements are plugged into the same side of a large-area liquid crystal display cell 4. The cell forms a speedometer display for cars, and it has digits and other display symbols. The contact pins 3 are arranged in the center of the multi-point connector 1 and are pushed into a plug 7. The socket in turn is connected via a flat band cable 8 to a voltage supply and control electronics (not shown).
FIG. 3 shows a section along the line A--A' of FIG. 2. Contact tabs 2 which are connected via tracks 5' to the electrode segments 5 (not shown here) are provided on the display cell 4 in contact with contact surfaces 2'. The contact tabs 2 and the contact pins 3 are connected via electric lines 9', 9" (gold or aluminium wires) to an integrated electronic circuit 10 embedded in the multi-point connector 1. The electric lines 9', 9" are likewise located within the multi-point connector 1. Since the integrated circuit is in the immediate vicinity of the counter-contact, namely the contact tabs 2, the electric lines 9', 9" are very short. The electrical losses and hence also the outlay on connections are thus substantially reduced. At the upper end of the multi-point connector 1, a projection 11 is provided opposite the contact tabs 2 with the display cell 4 resting on the projection 11 and being laterally adjusted by guides provided therein. As shown in broken lines, the contact pins can also protrude laterally from the contact arrangement.
In FIG. 4, another embodiment of the invention is shown. The contact arrangement here consists of an essentially cuboid multi-point connector 1, into which the liquid crystal display cell 4, namely a matrix display with punctiform electrode segments 5, is plugged in.
FIG. 5 is a section along the line B--B' of FIG. 4. On its upper surface, the multi-point connector 1 has a U-shaped slot with a row of spring contacts 12 (counter-contacts) on both sides. The ends of the slot are surrounded by the multi-point connector 1, so that the plugged-in display cell 4 is adjusted. The spring contacts 12 here form a regular grid. On the lower surface of the cuboid multi-point connector 1, a (narrower) U-shaped slot surrounded by the multi-point connector is likewise provided, wherein a row of contact bushes 13 (external terminals) is arranged. The integrated circuit 10 is again embedded in the multi-point connector 1 and is connected via electric lines 9', 9" located within the multi-point connector 1 to the spring contacts 12 and to the contact bushes 13. The plugs 14 which are plugged into the contact bushes 13 are in turn located on a multi-point connector. On the display cell 4, contact surfaces 2' are provided on both sides, in order to enlarge the number of contacts. The contact surfaces 2' located on the outer side of the display cell 4 are here connected via the end face to the corresponding tracks 5'.
When two integrated circuits 10 are provided in one multi-point connector 1, a cascade arrangement according to FIG. 6 is particularly suitable. The part located in the multi-point connector 1 is indicated in broken lines. In this way, the number of external connections 3 is minimised. The two integrated circuits 10 form a so-called "master-slave" relationship, in which the left-hand circuit represents the master and the right-hand circuit represents the slave. This arrangement is excellently suitable for both symbol displays and point-matrix displays. The electrical connections between the two integrated circuits 10, the counter-contacts 2 and the external terminals 3 are made without cross-overs or by means of a film which is coated on both sides with metal tracks and which is anyway required for making the contacts with the integrated circuits 10.
The conventional display cells have a standardised length. The following four standard lengths are most suitable for use with the contact arrangement according to the invention: ##EQU1##
The smallest standard length given is, due to the conventional grid for the contact tabs 2 (FIG. 3) or spring contacts 12 (FIG. 5), still just technically feasible. The largest standard length given is limited due to the number of terminals of the integrated circuit 10. As a standard grid for the contact tabs 2 or spring contacts 12, there are the following possibilities: 2.54 mm (0.1 inch), 1.905 mm (0.075 inch), 1.27 mm (0.02 inch) and 1.00 mm. The standard grid here gives the distance between the center lines of two adjacent contact tabs 2 or spring contacts 12. For the contact tabs 2 or spring contacts 12 made as metal springs, the smallest indicated grid of 1.00 mm cannot be further reduced because of the width of the contact tabs or spring contacts.
In Table 1, examples of integrated circuits as drivers for the display cells are listed; these are particularly suitable for the contact arrangements according to the invention. The number, the manufacturer, the type designation, the number of selectable segments Z seg , the selection type A and the number of counter-contacts Z int and external terminals Z ext are listed.
TABLE 1______________________________________No. Manufacturer Type Z.sub.seg A Z.sub.int Z.sub.ext______________________________________1 Philips PCE 2100 40 duplex 22 62 Philips PCE 2110 60 duplex 32 83 Philips PCE 2111 64 duplex 34 64 Philips PCE 2112 32 parallel 33 65 Siemens SM 804 45 parallel 46 186 National MM 5452 32 parallel 33 77 NEC uPD 7225 32-128 parallel 36 15 to 1:4 multiplex______________________________________
In Table 2, the most favourable combinations of integrated circuits, length of the display cell L in mm, number of counter-contacts Z int , grid constant of the counter-contacts R int in mm, segment number Z seg and selection type A are indicated.
TABLE 2______________________________________No. L Z.sub.int R.sub.int Z.sub.seg + A______________________________________1 23.9 22 1.00 40 duplex1 50.7 20 2.54 36 duplex2,3,4,6,7 38.0 32 to 36 1.00 32 parallel up to 128 at 1:4 multiplex2,3,4,6,7 50.7 32 to 36 1.27 32 parallel up to 128 at 1:4 multiplex2,3,4,6,7 69.8 32 to 36 1.905 32 parallel up to 128 at 1:4 multiplex5 50.7 46 1.00 45 parallel up to 350 at 1:10 multiplex5 69.8 46 1.27 45 parallel up to 350 at 1:10 multiplex______________________________________
In the illustrative embodiment described in FIG. 1, two integrated circuits of type PCE 2100 from Philips have been used. The display cell 4 is 51 mm long and 22 mm wide. The number of contact tabs 2 is 20 on each side, with a grid constant of 2.54 mm. The number of contact pins 3 is 6 on each side, the grid constant being 2.54 mm for each group of three. The contact pins 3 are soldered to the print plate 6, so that a very stable electrical and mechanical connection to the contact arrangements and hence also to the display cell 4 is formed. The total number of the selected electrode segments 5 is 72.
In the illustrative embodiment indicated in FIG. 2, two integrated circuits of the type PCE 2111 from Philips have been used. The large-area display cell 4 is 70 mm long and 70 mm wide. The number of the contact tabs 2 of one contact arrangement is 34, with a grid constant of 1.00 mm. The number of the contact pins 3 of each contact arrangement is 6, with a grid constant of 2.54 mm, and they are connected via the plug 7 to the flat band cable 8. The number of the selectable electrode segments 5 is 128 in this case. The display cell 4 is mounted in a frame (not drawn), in order to ensure good mechanical stability.
The manufacture of the contact arrangements, according to the invention, with multi-point connectors 1 is similar to the production of integrated circuits with plastic housings. For this purpose, the track pattern is stamped from a metal web (copper) and glued to a flexible film. When two integrated circuits 10 have been arranged in cascade, a second track pattern is stamped and glued to the other side of the film. The conventional margin around the track pattern is then stamped out and the integrated circuit or circuits 10 and, for example, the contact tabs 2 and the contact pins 3 are bonded to the tracks by means of gold or silver wires. The housing is then fitted around this structure by means of an appropriate process, such as transfer moulding, that is to say two multi-point connector halves are locally heated and the flexible film with the integrated circuit 10, the contact tabs 2 and the contact pins 3 is pressed in between the two halves.
For the contact tabs 2, the contact pins 3, the spring contacts 12 and the contact bushes 13, preferably nickel-silver, beryllium or--and this is particularly economical--brass is selected. The sheet thickness is between 0.1 and 0.3 mm, and is preferably 0.2 mm. The outer parts are provided with superficial copper-plating or tin-plating.
It is to be understood that the counter-contacts and the external terminals can be formed by any desired plug systems. The contact arrangements according to the invention are also applicable with particular advantage for a modular plug-in system.
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An electric contact arrangement for liquid crystal display cells is disclosed which consists of a multi-point connector having an internal embedded integrated circuit. The contact arrangement contains contacts to a liquid crystal display cell, and external terminals to appropriate circuitry. The contact arrangement can be plugged into the side of the liquid crystal display cell in order to remain outside the display or illumination zone. The embedded integrated circuit is located in the immediate vicinity of the contacts from the liquid crystal cell inserted into the multi-point connector. By this means the electrical losses and outlay on the connections are considerably reduced.
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RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Ser. No. 60/969,221 filed on Aug. 31, 2007, the entire content of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to internal combustion engines, and more particularly to fuel systems for internal combustion engines.
BACKGROUND OF THE INVENTION
[0003] Fuel systems for internal combustion engines often include a canister containing activated carbon that is connected to a fuel tank by a tube. Vapor vented from the fuel tank is routed to the canister to remove or adsorb hydrocarbons and other vapor emissions from the vapor before the vapor is vented to the atmosphere.
[0004] However, during operation of the engine or the equipment with which the engine is utilized, vibration of the engine or movement of the vehicle may cause fuel in the fuel tank to splash or slosh against the walls of the fuel tank. Excessive splashing or sloshing of fuel in the fuel tank may cause some fuel in the fuel tank to pass through the tube and leak into the canister. Once saturated with liquid fuel, activated carbon may become less efficient in removing or adsorbing hydrocarbons from the vapor vented from the fuel tank. Liquid in the venting system or carbon canister can adversely affect the operation of the fuel tank ventilation system.
SUMMARY OF THE INVENTION
[0005] The present invention provides, in one aspect, a baffle or liquid fuel barrier device configured for use with a fuel tank. The device substantially prevents liquid fuel from entering a carbon canister that absorbs fuel vapor.
[0006] The present invention provides, in one aspect, a baffle device configured to be disposed near an outlet of a fuel tank. The baffle device includes a fitting having an aperture therethrough and a first baffle. The first baffle includes a passageway in fluid communication with the aperture and at least one first baffle aperture configured to permit entry of fuel vapor into the passageway and exit of fuel vapor from the passageway. The baffle device also includes a second baffle overlying at least a portion of the first baffle aperture. The second baffle preferably includes a second baffle aperture that is misaligned with the first baffle aperture.
[0007] The present invention provides, in another aspect, a fuel tank assembly including a fuel tank having a wall at least partially defining a fuel-containing space, a fitting coupled to the wall, the fitting having an aperture therethrough, and a first baffle. The first baffle includes a passageway in fluid communication with the aperture and at least one first baffle aperture configured to permit entry of fuel vapor into the passageway and exit of fuel vapor from the passageway. The fuel tank assembly also includes a second baffle overlying at least a portion of the first baffle aperture.
[0008] The present invention provides, in yet another aspect, a baffle device including a fitting with an aperture therethrough. The aperture has an inlet end and an outlet end. The baffle device also includes a first baffle coupled to the fitting. The first baffle defines a first passageway in fluid communication with the inlet end of the aperture in the fitting. The first baffle includes a longitudinal slot. The baffle device further includes a second baffle coupled to the fitting. The second baffle defines a second passageway receiving at least a portion of the first baffle. The second baffle includes a longitudinal slot misaligned with the longitudinal slot in the first baffle. It is understood that the fitting, the aperture, and the baffles may be molded integrally as one piece with the wall of a plastic fuel tank. Alternatively, other constructions of the baffle device may incorporate both plastic and metal components that are separate from one another.
[0009] In each of the embodiments, the baffles preferably comprise one or more concentric, curved or arc-shaped members having slots in them or gaps between them to reduce the splashing of liquid fuel into or near the inlet end of the aperture in the fitting.
[0010] Other features and aspects of the invention will become apparent by consideration of the following detailed description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a cross-sectional view of a portion of a fuel tank assembly including a fuel tank, and a baffle device of the present invention coupled to the fuel tank.
[0012] FIG. 2 is a cross-sectional view of the baffle device of FIG. 1
[0013] FIG. 3 is an exploded view of the baffle device of FIG. 1 .
[0014] FIG. 4 is an assembled, end perspective view of the baffle device of FIG. 1 .
[0015] FIG. 5 is an assembled side view of the baffle device of FIG. 1 .
[0016] FIG. 6 is an assembled side view of the baffle device of FIG. 1 .
[0017] FIG. 7 is an assembled side view of the baffle device of FIG. 1 .
[0018] FIG. 8 is an assembled end view of the baffle device of FIG. 1 .
[0019] FIG. 9 is a cross-sectional view of the baffle device of FIG. 1 , taken along line 9 - 9 in FIG. 8 .
[0020] FIG. 10 is a side perspective view of a second construction of a baffle device of the present invention.
[0021] FIG. 11 is a side perspective view of the baffle device of FIG. 10 .
[0022] FIG. 12 is an exploded, end perspective view of the baffle device of FIG. 10 .
[0023] FIG. 13 is an end perspective view of the baffle device of FIG. 10 .
[0024] FIG. 14 is a side view of the baffle device of FIG. 10 .
[0025] FIG. 15 is an end view of the baffle device of FIG. 10 .
[0026] FIG. 16 is an exploded, end perspective view of a third construction of a baffle device of the present invention.
[0027] FIG. 17 is an assembled, end perspective view of the baffle device of FIG. 16 .
[0028] FIG. 18 is a cross-sectional view of the baffle device of FIG. 16 , taken along line 18 - 18 in FIG. 17 .
[0029] FIG. 19 is a side view of the baffle device of FIG. 16 .
[0030] FIG. 20 is an end view of the baffle device of FIG. 16 .
[0031] FIG. 21 is a cross-sectional view of the baffle device of FIG. 16 , taken along line 21 - 21 in FIG. 20 .
[0032] Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. Unless specified or limited otherwise, the terms “mounted,” “connected,” “supported,” and “coupled” and variations thereof are used broadly and encompass both direct and indirect mountings, connections, supports, and couplings. Further, “connected” and “coupled” are not restricted to physical or mechanical connections or couplings.
DETAILED DESCRIPTION
[0033] FIG. 1 illustrates a fuel system 10 including a fuel tank assembly having a fuel tank 14 and a baffle device 18 coupled to the tank 14 . The fuel system 10 also includes a canister 22 containing activated carbon and a tube 26 fluidly connecting the canister 22 and the baffle device 18 . The canister 22 may be similar to the canister shown and described in U.S. Pat. No. 7,159,577, the entire content of which is incorporated herein by reference. The fuel system 10 may be used to provide fuel for internal combustion engines incorporated in outdoor power equipment (e.g., walk-behind lawn mowers, lawn tractors, generators, snow-throwers, and other non-hand held or hand-held outdoor power equipment).
[0034] With reference to FIGS. 1-9 , the baffle device 18 includes a fitting 30 having an aperture 34 defining a central axis 36 . In the illustrated construction of the baffle device 18 , the aperture 34 is configured as a stepped aperture 34 , including an inlet end 38 and an outlet end 42 having different diameters. Specifically, the inlet end 38 of the aperture 34 has a diameter that is less than the diameter of the outlet end 42 of the aperture 34 to reduce the amount of liquid fuel that could flow through the aperture 34 and control the amount of vapor allowed to exit the tank 14 during refueling. In alternative constructions of the baffle device 18 , the inlet end 38 of the aperture 34 may have a diameter that is greater than the diameter of the outlet end 42 of the aperture 34 . Alternatively, the aperture 34 may have a substantially constant diameter from the inlet end 38 to the outlet end 42 . The fitting 30 preferably also includes a barb 46 configured to be inserted into the tube 26 that fluidly interconnects the baffle device 18 and the canister 22 or other ventilation system components. As shown in FIGS. 1 , 2 , and 9 , the aperture 34 passes through the barb 46 .
[0035] With reference to FIGS. 1-9 , the baffle device 18 also includes nested baffles 50 a, 50 b, each having a longitudinal axis coaxial with the central axis 36 , coupled to the fitting 30 . Alternatively, one or both of the nested baffles 50 a, 50 b may be non-collinear with the central axis 36 . As shown in FIGS. 1-3 and 9 , the baffle 50 a includes respective ends 54 , 58 and defines a passageway 62 between the respective ends 54 , 58 of the baffle 50 a. Likewise, the baffle 50 b includes respective ends 66 , 70 and defines a passageway 74 between the respective ends 66 , 70 of the baffle 50 b. The fitting 30 includes a cylindrical groove 78 , at least partially defined by an inner peripheral wall 82 , that is concentric with the aperture 34 (see FIG. 3 ). The baffle 50 a is received within the groove 78 to fluidly communicate the passageway 62 and the aperture 34 in the fitting 30 . In the illustrated construction of the baffle device 18 , the outer diameter OD a of the baffle 50 a and the outer diameter of the groove 78 are sized to provide an interference fit between the end 58 of the baffle 50 a and the inner peripheral wall 82 (see FIG. 7 ). In alternative constructions of the baffle device 18 , the baffle 50 a may be coupled to the fitting 30 in any of a number of different ways to fluidly communicate the passageway 62 of the baffle 50 a and the aperture 34 in the fitting 30 . In yet other alternative constructions of the baffle device 18 , the baffle 50 a may be integrally formed as a single piece with the fitting 30 .
[0036] With continued reference to FIGS. 1-3 and 9 , the fitting 30 also includes a second groove 86 , at least partially defined by an inner peripheral wall 94 , that is concentric with the first groove 78 and the aperture 34 (see FIG. 3 ). The baffle 50 b is received within the groove 86 , and at least a portion of the baffle 50 a is positioned within the passageway 74 of the baffle 50 b. In the illustrated construction of the baffle device 18 , the outer diameter ODb of the baffle 50 b (see FIG. 5 ) and the outer diameter of the groove 86 are sized to provide an interference fit between the end 70 of the baffle 50 b and the inner peripheral wall 94 . In alternative constructions of the baffle device 18 , the baffle 50 b may be coupled to the fitting 30 in any of a number of different ways to receive at least a portion of the baffle 50 a within the passageway 74 of the baffle 50 b. In yet other alternative constructions of the baffle device 18 , the baffle 50 b may be integrally formed as a single piece with the fitting 30 . Further, the baffle 50 a may be coupled to the fitting 30 in any manner described above, and the baffle 50 b may be directly coupled to the baffle 50 a in any number of different ways (e.g., fastening, welding, using adhesives, integrally forming, etc.). Likewise, the baffle 50 b may be coupled to the fitting 30 in any manner described above, and the baffle 50 a may be directly coupled to the baffle 50 b in any number of different ways (e.g., fastening, welding, using adhesives, integrally forming, etc.).
[0037] With reference to FIGS. 1-9 , the fitting 30 further includes a cylindrical outer portion 90 sized to provide an interference fit with a peripheral surface defining an aperture 92 in the fuel tank 14 (see FIG. 1 ). The fitting 30 may also be welded to the fuel tank 14 or adhesives may be utilized to further secure the baffle device 18 to the fuel tank 14 . Alternatively, at least a portion of the baffle device 18 (e.g., the fitting 30 ) may be integrally formed with a portion of the fuel tank 14 (e.g., a wall of the fuel tank 14 that at least partially defines a fuel-containing space). Further, the respective baffles 50 a, 50 b may be integrally formed as a single piece with the fitting 30 , or the baffles 50 a, 50 b may be integrally formed as a single piece with the fitting 30 and a portion of the fuel tank 14 . As a further alternative, other structure (e.g., a grommet) may be utilized to secure the baffle device 18 to the fuel tank 14 .
[0038] With reference to FIG. 2 , the baffle 50 a is sized such that a ratio of the length La of the baffle 50 a to the inner diameter IDa of the baffle 50 a is at least about 3:1. Generally, increasing the ratio of the length La of the baffle 50 a to the inner diameter IDa of the baffle 50 a also steepens the angle at which fuel within the baffle 50 a or fuel below the baffle 50 a must splash to reach the aperture 34 through the passageway 62 . With continued reference to FIG. 2 , the baffle 50 b is sized such that a ratio of the length Lb of the baffle 50 b to the inner diameter IDb of the baffle 50 b is at least about 2:1.
[0039] With reference to FIGS. 3 and 4 , the baffle 50 a includes a first baffle aperture preferably configured as a longitudinal slot 98 extending between the respective ends 54 , 58 of the baffle 50 a. In the illustrated construction of the baffle device 18 , the width Wa of the slot 98 is between about one-fourth of an inch and about one-sixteenth of an inch (see FIG. 7 ). The baffle 50 b also includes a second baffle aperture preferably configured as a longitudinal slot 102 extending between the respective ends 66 , 70 of the baffle 50 b. In the illustrated construction of the baffle device 18 , the width Wb of the slot 102 is at least about one-sixteenth of an inch (see FIG. 5 ), and is about equal to the width Wa of the slot 98 . The widths Wa,Wb of the respective slots 98 , 102 are sized small enough to reduce the amount of liquid fuel entering the passageway 62 through the baffles 50 a, 50 b in a direction substantially transverse to the central axis 36 of the aperture 34 , yet large enough to allow sufficient vapor venting from the fuel tank 14 at high fill levels and tilt angles of fuel in the fuel tank 14 . The widths Wa,Wb of the respective slots 98 , 102 are also sized large enough to allow substantially uninhibited movement of air through the slots 98 , 102 to allow replacement air to enter the fuel tank 14 when the fill level in the tank 14 decreases. Further, the widths Wa,Wb of the respective slots 98 , 102 are sized large enough to substantially prevent liquid fuel in the fuel tank 14 from coalescing or bridging the widths Wa,Wb of the respective slots 98 , 102 due to the effects of surface tension, viscosity, and surface energy that may otherwise inhibit the flow of vapor through the slots 98 , 102 . Alternatively, each of the baffles 50 a, 50 b may include one or more longitudinally-spaced apertures rather than the slots 98 , 102 .
[0040] With reference to FIGS. 3 , 4 , and 8 , the respective slots 98 , 102 of the baffles 50 a, 50 b are misaligned with one another such that the slot 98 in the baffle 50 a is not in facing relationship with the slot 102 in the baffle 50 b to provide a straight-line path through the baffles 50 a, 50 b in a direction substantially transverse to the central axis 36 of the aperture 34 . Specifically, in the illustrated construction of the baffle device 18 , the slot 98 in the baffle 50 a is misaligned with the slot 102 in the baffle 50 b by about 180 degrees. In alternative constructions of the baffle device 18 , the slot 98 in the baffle 50 a may be misaligned with the slot 102 in the baffle 50 b by at least about 30 degrees. In yet other alternative constructions of the baffle device 18 , the baffle 50 b need not comprise a complete cylinder, but rather may comprise a portion of a cylinder (i.e., a curved or an arc-shaped portion) that is sufficiently long enough (e.g., about 60 or more degrees) to at least partially shield the slot 98 in the baffle 50 a.
[0041] With reference to FIG. 2 , the fitting 30 provides a gap G between the outer diameter ODa of the baffle 50 a and the inner diameter IDb of the baffle 50 b through which fuel vapor must flow to reach the passageway 62 of the baffle 50 a and the aperture 34 in the fitting 30 . The gap G is sized large enough for the same reasons as discussed above with respect to the widths Wa,Wb of the respective slots 98 , 102 , i.e., to substantially prevent liquid fuel from adhering or coalescing between the outer wall of the baffle 50 a and the inner wall of the baffle 50 b due to the effects of surface tension, viscosity, and surface energy that may otherwise inhibit the flow of vapor through the gap G.
[0042] With continued reference to FIG. 2 , the end 54 of the baffle 50 a is spaced from the end 66 of the baffle 50 b by a length dimension ΔL along the central axis 36 . Spacing the respective ends 54 , 66 of the baffles 50 a, 50 b in this manner substantially reduces coalescence of fuel between the ends 54 , 66 of the respective baffles 50 a, 50 b. The length dimension ΔL is sized large enough for the same reasons as discussed above with respect to the widths Wa,Wb of the respective slots 98 , 102 , i.e., to substantially prevent liquid fuel from adhering or coalescing between the ends 54 , 66 of the respective baffles 50 a, 50 b due to the effects of surface tension, viscosity, and surface energy that may otherwise inhibit the flow of vapor between the baffles 50 a, 50 b and through the gap G. In the illustrated construction of the baffle device 18 , the length dimension ΔL is greater than the gap G. Alternative constructions of the baffle device 18 in which the length dimension ΔL is decreased may also include an increased gap G to provide sufficient spacing between the ends 54 , 66 of the respective baffles 50 a, 50 b to substantially prevent liquid fuel from coalescing between the ends 54 , 66 of the respective baffles 50 a, 50 b. Alternative constructions of the baffle device 18 in which the gap G is decreased may also include an increased length dimension ΔL to provide sufficient spacing between the ends 54 , 66 of the respective baffles 50 a, 50 b to substantially prevent liquid fuel from coalescing between the ends 54 , 66 of the respective baffles 50 a, 50 b. In yet other alternative constructions, the baffle device 18 may, however, incorporate a length dimension ΔL at least as large as the gap G.
[0043] With reference to FIG. 1 , assuming the level of fuel within the tank 14 is below the end 54 of the baffle 50 a, fuel vapor in the tank 14 may exit the tank 14 by flowing directly through the passageway 62 of the baffle 50 a (upwardly as shown in FIG. 1 ) and through the aperture 34 in the fitting 30 to reach the canister 22 via the tube 26 . The nested baffles 50 a, 50 b, however, reduce the amount of liquid fuel, as it is splashed or sloshed against the walls of the fuel tank 14 , that reaches the aperture 34 in the fitting 30 and the canister 22 . Specifically, the misaligned slots 98 , 102 in the baffles 50 a, 50 b provide a tortuous path that reduces the amount of liquid fuel that splashes through the baffles 50 a, 50 b, in a direction substantially transverse to the central axis 36 , and into the passageway 62 of the baffle 50 a or the aperture 34 in the fitting 30 .
[0044] Should the fuel tank 14 be filled such that the fuel level is above the lower ends 54 , 66 of the respective baffles 50 a, 50 b, fuel vapor in the tank 14 may exit the tank 14 by flowing through the tortuous path created by the misaligned slots 98 , 102 in the baffles 50 a, 50 b, in a direction substantially transverse to the central axis 36 . Upon reaching the passageway 62 of the baffle 50 a, the fuel vapor may flow through the aperture 34 in the fitting 30 to reach the canister 22 via the tube 26 . However, the nested baffles 50 a, 50 b reduce the amount of liquid fuel, as it is splashed or sloshed against the walls of the fuel tank 14 , that reaches the aperture 34 in the fitting 30 in substantially the same manner as described above when the level of fuel in the fuel tank 14 is below the respective lower ends 54 , 66 of the baffles 50 a, 50 b.
[0045] FIGS. 10-15 illustrate a second construction of a baffle device 106 configured for use with the fuel tank 14 , the tube 26 , and the canister 22 of FIG. 1 . Like the baffle device 18 , the baffle device 106 includes a fitting 108 having an aperture 112 therethrough and a cylindrical outer portion 113 . With reference to FIGS. 10-12 , the baffle device 106 also includes a spiraled baffle 110 having respective ends 114 , 118 and defining a passageway 122 between the respective ends 114 , 118 of the baffle 110 . The spiraled baffle 110 includes nested windings 126 a, 126 b that define a spiraled tortuous path about a central axis 120 of the aperture 112 (see FIG. 12 ). In the illustrated construction of the baffle device 106 , the interior winding 126 a is engaged with the cylindrical outer portion 113 of the fitting 108 by an interference fit to secure the baffle 110 to the fitting 108 (see FIG. 13 ). In alternative constructions of the baffle device 106 , the baffle 110 may be coupled to the fitting 108 in any of a number of different ways to fluidly communicate the passageway 122 of the baffle 110 and the aperture 112 in the fitting 106 .
[0046] As previously stated, the baffle device 106 may be utilized with the fuel tank 14 , the tube 26 , and the canister 22 of FIG. 1 . Assuming the level of fuel within the tank 14 is below the end 114 of the baffle 110 , fuel vapor in the tank 14 may exit the tank 14 by flowing directly through the passageway 122 of the baffle 110 and through the aperture 112 in the fitting 108 to reach the canister 22 via the tube 26 . The nested windings 126 a, 126 b, however, reduce the amount of liquid fuel, as it is splashed or sloshed against the walls of the fuel tank 14 , that reaches the aperture 112 in the fitting 108 and the canister 22 . Specifically, the nested windings 126 a, 126 b provide a tortuous path that reduces the amount of liquid fuel that splashes through the nested windings 126 a, 126 b of the baffle 110 , in a direction substantially transverse to the central axis 120 , and reaches the passageway 122 of the baffle 110 or the aperture 112 in the fitting 108 .
[0047] Should the fuel tank 14 be filled such that the fuel level is above the lower end 114 of the baffle 110 , fuel vapor in the tank 14 may exit the tank 14 by flowing through the tortuous path created by the nested windings 126 a, 126 b along a path spiraled about the central axis 120 . Upon reaching the passageway 122 of the baffle 110 , the fuel vapor may flow through the aperture 112 in the fitting 108 to reach the canister 22 via the tube 26 . However, the nested windings 126 a, 126 b reduce the amount of liquid fuel, as it is splashed or sloshed against the walls of the fuel tank 14 , that reaches the aperture 112 in the fitting 108 in substantially the same manner as described above when the level of fuel in the fuel tank 14 is below the lower end 114 of the baffle 110 .
[0048] FIGS. 16-21 illustrate a third construction of a baffle device 130 configured for use with the fuel tank 14 , the tube 26 , and the canister 22 of FIG. 1 . Like the baffle device 18 , the baffle device 130 includes a fitting 132 having a stepped aperture 133 therethrough, with an inlet end 135 and an outlet end 136 , and a cylindrical outer portion 137 (see FIG. 18 ). With reference to FIGS. 16 , 17 , and 20 , the baffle device 130 includes a two-piece baffle 134 including opposed J-shaped baffles 138 defining a passageway 142 between the respective baffles 138 . Each J-shaped or other curved baffle 138 includes a substantially curved or cylindrical portion 146 and a straight portion 150 extending from the curved or cylindrical portion 146 . In the illustrated construction of the baffle device 130 , the respective arced, curved, or cylindrical portions 146 of the J-shaped baffles 138 engage the cylindrical outer portion 137 of the fitting 132 by an interference fit to secure the respective baffles 138 to the fitting 132 (see FIG. 20 ). In alternative constructions of the baffle device 130 , the two-piece baffle 134 may be coupled to the fitting 132 in any of a number of different ways to fluidly communicate the passageway 142 defined by the baffles 138 and the aperture 133 in the fitting 132 .
[0049] As previously stated, the baffle device 130 may be utilized with the fuel tank 14 , the tube 26 , and the canister 22 of FIG. 1 . Assuming the level of fuel within the tank 14 is below the lower end of the two-piece baffle 134 , fuel vapor in the tank 14 may exit the tank 14 by flowing directly through the passageway 142 defined between the baffles 138 and through the aperture 133 in the fitting 132 to reach the canister 22 via the tube 26 . The curved or cylindrical portions 146 of the baffles 138 and the straight portions 150 of the baffles 138 , however, reduce the amount of liquid fuel, as it is splashed or sloshed against the walls of the fuel tank 14 , that reaches the aperture 133 in the fitting 132 and the canister 22 . Specifically, the J-shaped baffles 138 provide tortuous paths between the curved or cylindrical portion 146 of one baffle 138 and the straight portion 150 of the other baffle 138 to reduce the amount of liquid fuel that splashes through the two-piece baffle 134 , in a direction substantially transverse to a central axis 140 of the aperture 133 (see FIG. 16 ), and reaches the passageway 142 defined between the baffles 138 or the aperture 133 in the fitting 132 .
[0050] Should the fuel tank 14 be filled such that the fuel level is above the lower end of the two-piece baffle 134 , fuel vapor in the tank 14 may exit the tank 14 by flowing through the tortuous paths created between the curved or cylindrical portion 146 of one baffle 138 and the straight portion 150 of the other baffle 138 . Upon reaching the passageway 142 defined between the respective baffles 138 , the fuel vapor may flow through the aperture 133 in the fitting 132 to reach the canister 22 via the tube 26 . However, the two-piece baffle 134 reduces the amount of liquid fuel, as it is splashed or sloshed against the walls of the fuel tank 14 , that reaches the aperture 133 in the fitting 132 in substantially the same manner as described above when the level of fuel in the fuel tank 14 is below the lower end of the two-piece baffle 134 .
[0051] Various features of the invention are set forth in the following claims.
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A baffle device, configured to be disposed near an outlet of a fuel tank, includes a fitting having an aperture therethrough and a first baffle. The first baffle includes a passageway in fluid communication with the aperture and a first baffle aperture configured to permit entry of fuel vapor into the passageway and exit of fuel vapor from the passageway. The baffle device also includes a second baffle overlying at least a portion of the first baffle aperture.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 12/995,437, filed Nov. 30, 2010, which is a continuation of International Application No. PCT/US2009/045737, filed May 29, 2009, which claims priority to U.S. Provisional Patent Application No. 61/057,282, filed May 30, 2008, the entire disclosures of which are hereby incorporated by reference in their entirety.
GOVERNMENT INTERESTS
[0002] This invention was made with government support under Grant No. R01 AI 054193 awarded by the National Institutes of Health. The United States Government has certain rights in the invention.
TECHNICAL FIELD
[0003] Embodiments herein relate to anti-bacterial agents, and, more specifically, to anti-bacterial agents from benzo[d]heterocyclic scaffolds for prevention and treatment of multidrug resistant bacteria.
BACKGROUND
[0004] In 2004, the IDSA (Infectious Disease Society of America) reported that each year 90,000 of the 2 million people who acquire a hospital bacterial infection will die. That is a 4.5% mortality rate arising from just being within the hospital. Multi-drug resistance bacterial strains are a major problem and one that has been increasing very rapidly every year during the last few decades. In brief, from its discovery in 1968 multi-drug resistant Staphylococcus aureus (MRSA) had already accounted for greater than 50% of S. aureus patient isolates by 1999 in ICUs (intensive care units) within the National Nosocomial Infection Surveillance (NNIS) System. Then by 2003, 59.5% of isolates were from MRSA. Vancomycin resistant enterocci (VRE) has had a similar rapid rise in hospital isolates increasing from its 1990 discovery to 25% of all enterococal isolates in 1999 and then increasing further to 28.3% by 2003 in NNIS surveyed ICUs. Without the immediate discovery of new antibiotics, this rise in multi-drug resistant strains will continue to grow thereby putting everyone treated within hospitals at undue risk of infection and possible death.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] Embodiments will be readily understood by the following detailed description in conjunction with the accompanying drawings. Embodiments are illustrated by way of example and not by way of limitation in the figures of the accompanying drawings.
[0006] FIG. 1 illustrates a general scheme for the synthesis of various benzo[d]heterocyclic compounds for the treatment of multidrug resistant bacteria in accordance with various embodiments.
[0007] FIG. 2 is a flowchart of initial analogs generated to explore the effects on antibacterial potency and selectivity of nitrofuran replacement with nitrothiophene in accordance with embodiments herein.
[0008] FIG. 3 illustrates specific examples of the syntheses used to make benzimidazoles from aldehydes, benzthiazoles from nitriles, and benzoxazoles from acid chlorides in accordance with embodiments.
[0009] FIG. 4 illustrates selectivity and potency of various benzimidazoles, benzthiazoles, and benzoxazoles against a panel of microorganisms including gram-positive bacteria, gram-negative bacteria, fungi, yeast, and mycobacteria.
[0010] FIG. 5 illustrate the chemical structure, molecular weight, and chemical formula of most of the compounds of FIG. 4 .
[0011] FIG. 6 illustrates the potency of various benzo[d]heterocyclic compounds against methicillin-resistant Staphylococcus aureus (MRSA) in micromolar concentration.
[0012] FIG. 7 illustrates the potency of various imidazopyridine compounds against MRSA in micromolar concentration.
[0013] FIG. 8 illustrates the potency and selectivity of an exemplary compound against a panel of MRSA clinical isolates compared to a Vancomycin standard in micrograms per milliliter.
[0014] FIG. 9 illustrates the potency and selectivity of an exemplary compound against a panel of Gram-positive clinical isolate strains compared to a Ciprofloxacin standard in micrograms per milliliter.
[0015] FIG. 10 illustrates the potency and selectivity of an exemplary compound against a panel of Gram-negative clinical isolate strains compared to a Ciprofloxacin standard in micrograms per milliliter.
[0016] FIG. 11 illustrates the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) determinations of an exemplary compound to various Gram-positive strains.
[0017] FIG. 12 illustrates results of a time-kill assay of an exemplary compound against a methicillin-sensitive S. aureus strain (MSSA).
[0018] FIG. 13 illustrates a mutational analysis of an exemplary compound by growth of S. aureus strains.
[0019] FIG. 14 illustrates the mutational analysis of an exemplary compound by serial transfer experiments.
DETAILED DESCRIPTION
[0020] In the following detailed description, reference is made to the accompanying drawings which form a part hereof, and in which are shown by way of illustration embodiments that may be practiced. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope. Therefore, the following detailed description is not to be taken in a limiting sense, and the scope of embodiments is defined by the appended claims and their equivalents.
[0021] Various operations may be described as multiple discrete operations in turn, in a manner that may be helpful in understanding embodiments; however, the order of description should not be construed to imply that these operations are order dependent.
[0022] For the purposes of the description, a phrase in the form “A/B” or in the form “A and/or B” means (A), (B), or (A and B). For the purposes of the description, a phrase in the form “at least one of A, B, and C” means (A), (B), (C), (A and B), (A and C), (B and C), or (A, B and C). For the purposes of the description, a phrase in the form “(A)B” means (B) or (AB) that is, A is an optional element.
[0023] The description may use the terms “embodiment” or “embodiments,” which may each refer to one or more of the same or different embodiments. Furthermore, the terms “comprising,” “including,” “having,” and the like, as used with respect to embodiments, are synonymous.
[0024] Embodiments herein provide compounds and methods of making and using such compounds for prevention and treatment of multidrug resistant bacteria.
[0025] In embodiments, the aryl or heteroaryl[d]heterocyclic derived compounds show impressive activity against multidrug resistant strains of bacteria including Methicillin-resistant Staphylococcus aureus (Methicillin-RSA), Vancomycin-Resistant Enterococcus (VRE), and Linezolid-Resistant Enterococcus (LRE) infections with potencies near or beyond that of current clinical treatments. In embodiments, these compounds are also effective against Bacillus subtilis, Escherichia coli, Pseudmonadas aeruginosa, Mycobacterium vaccae, Sporobolomyces salmonicolor, Candida albicans, Penicilluum notatum and Mycobacterium tuberculosis to various extents. Thus, in embodiments, methods of using one or more compounds described herein may be provided for the prevention and/or treatment of multidrug resistant bacteria.
[0026] In accordance with an embodiment, exemplary compounds may be prepared by the scheme in FIG. 1 , which illustrates a general scheme for the synthesis of various benzo[d]heterocyclic compounds for the treatment of multidrug resistant bacteria.
[0027] In FIG. 1 , reagents include: a) Oxalyl chloride, CH 2 Cl 2 , catalytic N,N-dimethylforamide; b) N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride, Et 3 N, CH 3 CN; c) Et 3 N, CH 2 Cl 2 , reflux; d) Acetic acid, reflux; e) (Diethylamino)sulfur trifluoride, K 2 CO 3 , CH 2 Cl 2, −78 ° C. to room temp.; and f) p-toluenesulfonic acid, toluene, reflux.
[0028] In an embodiment, these compounds may be prepared by an EDC-mediated coupling of 1 or displacement of an acid chloride 2 with 3, base and proper solvent to give an amide 4. Cyclization of the amide 4 with one of the above conditions (depending on Y substituent) results in heterocyclic products 5.
[0029] In FIG. 1 , compound 3, Y is H, O, SH, SR 1 , NH 2 , NHR 1 , CH 2 NH 2 , CH 2 SH, CH 2 OH, CH 2 NHR 1 , CH 2 SR 1 . In FIG. 1 , compound 5 may comprise the following: R 1 is H, alkyl, substituted alkyl, including halogenated alkyl such as CF 3 , aryl and substituted aryl, halogen, cycloheteroalkyl (such as morpholine, thiomorpholine, piperazine, piperidine), aryl, heteroaryl, substituted heteroaryl, nitro, sulfone, sulfoxide, sulfamide, phosphate, alkylphosphate (such as PO(CH 3 ) 2 , PO(OCH 3 ) 2 ) boronic acid, or boronic ester; X is O, S, N, or CH 2 ; n=0-8, saturated or unsaturated; Y is O, S, N, or CH 2 ; m=0-3; R 2 is H, OH, halogen, amine, COOH, NHR 1 (wherein R 1 is as previously defined), NR 1 R 1 , alkyl, substituted alkyl, cycloalkyl, or functionalized alkyl (including alkenes, alkynes, alcohols, epoxides, ketones, esters, ethers, aldehydes, nitriles, nitros, thiols, thioesters, sulfides, disulfide, sulfones, sulfoxides, amines, amides, ureas, carbamates), cycloheteroalkyl (such as morpholine, thiomorpholine, piperazine, piperidine), acyl, halogenated acyl, substituted acyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, heterocylic (such as furan, nitrofuran, thiophene, nitrothiophene, imidazole, oxazole, oxazoline, thiazole, thiazoline, triazole, pyridine, pyrazine, naphthalene, diketopiperazine, quinoline, isoquinoline, imidazopyridines, oxazolidinone, and all substitutions upon), wherein R 2 may be monosubstituted or polysubstituted; and Z is N in the 2, 3, 4, or 5-positions of the phenyl ring and any combination therein (with the 2-position being exemplified by the structure shown).
[0030] In embodiments, compounds may be formed as a prodrug to enhance the delivery of the compound, such as enhancing absorption, distribution, metabolism, excretion, etc. Suitable groups to provide a prodrug may, for example, entail modifying an OH group to form an O-prodrug group, wherein the prodrug group is one of acyl, ester, carbamate, urea, sugar, or amino acid.
[0031] In embodiments, various molecules as described herein have surprising activity against MRSA. One exemplary compound tested (nitrofuran benzimidazole), showed results against MRSA of (MIC=8 μM) and against VRE (MIC=16 μM). While this particular molecule has been tested previously, the present application is the first disclosure of this compound having activity against multi-drug resistant “super bug” strains. In addition, in accordance with an embodiment described herein, this compound and analogs thereof may be synthesized in high yields in just a single step. Further embodiments herein provide analogs of the afore-mentioned compounds and methods of making and using such compounds.
[0032] In a time of rapid and increasing resistance toward the last line antibacterial agents like Vancomycin and Linezolid, it is prudent that investigation of all new leads undertaken. In an embodiment, a set of analogs (see FIG. 2 ) were produced in order to explore potency and antimicrobial selectivity. The next generation of benzoxazole and benzthiazole derivatives, as well as the effects of substitution of the benzimidazole core on antibacterial potency and selectivity, were explored.
[0033] Synthesis of analogs was accomplished in a simple straightforward manner as shown in FIG. 3 . FIG. 3 illustrates specific examples of the syntheses used to make benzimidazoles from aldehydes, benzthiazoles from nitriles, and benzoxazoles from acid chlorides. Fortuitously, many compounds may be made in a just one step. For instance, condensation of 5-nitro-2-furaldehyde 1 (where X is O) or 5-nitro-2-thiophenealdehyde 1 (where X is S) with various diamines, 2, followed by oxidation with potassium ferricyanide results in a panel of substituted benzimidazoles, 3a to 3g. Next, the benzthiazoles (6a and 6b) may be easily prepared by an acid catalyzed cyclization of nitrile, 4, and 2-aminothiophenol (5). Finally, benzoxazoles (11a and 11b) may be prepared in a two step process involving coupling of easily prepared acid chloride, 8, with 2-aminophenol (9) to give intermediate amide (10) which may then be cyclized with p-toluenesulfonic acid in refluxing toluene.
[0034] In FIG. 3 , the reagents include: (a) KFe(CN) 6 , CH 3 OH, water, reflux, 2 h-16 h; (b) p-TSOH, ethanol, reflux, 16 h; (c) Oxalyl chloride, CH 2 Cl 2 , DMF (drop), 4 h; (d) Et 3 N, CH 2 Cl 2 , reflux, 16 h; and (e) p-TSOH, toluene, reflux, 16 h.
[0035] In accordance with an embodiment, in order to first broadly screen these compounds, an agar diffusion assay was employed to determine whether these compounds have any activity against a diverse array of organisms which include MRSA and VRE. Then to follow up, if a compound showed promise (by having a large zone of inhibition) its minimum inhibition concentration at 90% (MIC) would be determined for that specific organism ( FIG. 4 ). FIG. 4 illustrates selectivity and potency of various benzimidazoles, benzthiazoles, and benzoxazoles against a panel of microorganisms including gram-positive bacteria, gram-negative bacteria, fungi, yeast, and mycobacteria. The minimum inhibition concentration at 90% is shown in micromolar concentration. In an embodiment, the initial agar diffusion assay screen was encouraging as it hinted that many of these compounds have a broad spectrum of activity while others showed some specificity towards specific organisms. Therefore many of the compounds had their MICs determined which reflected many of the findings of the diffusion assay. FIG. 5 illustrates the chemical structure, molecular weight, and chemical formula of most of the compounds of FIG. 4 .
[0036] FIG. 6 illustrates the potency of various benzo[d]heterocyclic compounds against methicillin-resistant Staphylococcus aureus (MRSA) in micromolar concentration. FIG. 7 illustrates the potency of various imidazopyridine compounds against MRSA in micromolar concentration.
[0037] All the anhydrous solvents, reagent grade solvents for chromatography and starting materials were purchased from either Aldrich Chemical Co. (Milwaukee, Wis.) or Fisher Scientific (Suwanee, Ga.). General methods of purification of compounds involved the use of silica cartridges purchased from AnaLogix, Inc. (Burlington, Wis.; www.ana-logix.com) and/or recrystallization. The reactions were monitored by thin-layer chromatography (TLC) on precoated Merck 60 F 254 silica gel plates and visualized using UV light (254 nm).
[0038] All compounds were analyzed for purity and characterized by 1 H and 13 C NMR using a Varian 300 MHz NMR and Varian 500 MHz NMR spectrometer. Chemical shifts are reported in ppm (δ) relative to the residual solvent peak and coupling constants (J) are reported in hertz (Hz) (s=singlet, bs=broad singlet, d=doublet, dd=double doublet, bd=broad doublet, ddd=double doublet of dublet, t=triplet, tt=triple triplet, q=quartet, and m=multiplet) and analyzed using MestReC NMR data processing.
[0039] Mass Spectra values are reported as m/z. All reactions were conducted under Argon unless otherwise noted. Solvents were removed in vacuo on a rotary evaporator. The LC/MS analyses were carried out on Waters ZQ instrument consisting of chromatography module Alliance HT, photodiode array detector 2996, and mass spectrometer Micromass ZQ, using a 3×50 mm Pro C18 YMC reverse phase column. Mobile phases: 10 mM ammonium acetate in HPLC grade water (A) and HPLC grade acetonitrile (B). A gradient was formed from 5% to 80% of B in 10 minutes at 0.7 mL/min. The MS electrospray source operated at capillary voltage 3.5 kV and a desolvation temperature 300° C. Elemental analyses were performed by Midwest Microlabs, LLC (Indianapolis, Ind.). Yields quoted are unoptimized.
[0040] Abbreviations: DCM=dichloromethane; DMF=dimethylformamide; ACN=acetonitrile; EtOAc=ethyl acetate; HOAc=acetic acid; EDCI═N-(3-Dimethylaminopropyl)-N 1 -ethylcarbodiimide hydrochloride; DMAP=4-dimethylaminopyridine; Et 3 N=triethylamine; and EtOH=ethanol.
[0041] The synthesis and testing of an exemplary compound (ND-7901) are detailed below.
[0000]
[0042] 5-Nitro-2-furaldehyde (1a, 401 mg, 2.8 mmol) and 2,3-diaminophenol (2 g, 300 mg, 2.4 mmol) were dissolved in 10 mL of methanol. Next, a 5 mL aqueous solution of potassium ferricyanide (1.7 g, 5.1 mmol) was added and the reaction was heated to reflux for 16 hours while being exposed to air. Then the reaction was cooled, filtered and the filter pad was washed with ethanol. The filtrate liquor and washings were combined and concentrated in vacuo and the residue was recrystallized from EtOH:H 2 O (80/20 to give 180 mg of 3g as a dark solid (26%) after filtration. 1 H NMR (300 MHz, DMSO) δ 7.90 (1H, m), 7.42 (1H, m), 7.06 (2H, m), 6.59 (1H, m); HRMS calcd. for C 11 H 7 N 3 O 4 , 246.0515 found 246.0504. LC/MS Retention time 4.73 min (>95%), FABMS 246.4 (M+1).
[0043] FIG. 8 illustrates the potency and selectivity of ND-7901 against a panel of MRSA clinical isolates compared to a Vancomycin standard in micrograms per milliliter.
[0044] FIG. 9 illustrates the potency and selectivity of ND-7901 against a panel of Gram-positive clinical isolate strains compared to a Ciprofloxacin standard in micrograms per milliliter. ND-7901 exhibits good activity against Gram-positive isolates. FIG. 10 illustrates the potency and selectivity of ND-7901 against a panel of Gram-negative clinical isolate strains compared to a Ciprofloxacin standard in micrograms per milliliter. ND-7901 has limited activity against Gram-negative isolates.
[0045] FIG. 11 illustrates the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) determinations of ND-7901 to various Gram-positive strains. A series of broths were mixed with solutions of diluted drug an inoculum was applied. After incubation, the MIC was determined as the first concentration in which the growth of the organism has been inhibited. In contrast, the MBC was measured by inoculating the series of broths used for the MIC determination onto drug-free medium. The MBC is the first dilution at which growth is not observed. ND-7901 is bactericidal against most Gram-positive isolates.
[0046] FIG. 12 illustrates results of a time-kill assay of ND-7901 against methicillin-sensitive S. aureus (MSSA), ATCC 29213, showing the rapid kinetics of bacteria death when treated with drug at various concentrations with Vancomycin as the control.
[0047] FIG. 13 illustrates a mutational analysis of ND-701 by growth of S. aureus strains overnight with no selection and recovery of resistant colonies on drug plates at 2-4 times the MIC value. ND-7901 shows very low mutation such that no spontaneous mutants were recovered.
[0048] FIG. 14 illustrates the mutational analysis of ND-7901 by serial transfer experiments. As such, the S. aureus strains were grown with ND-7901 (0.5-2 times the MIC) added and passed serially until resistance was found. ND-7901 shows a very low level of resistance after 8 passages.
[0049] The synthesis and testing of various related compounds are detailed below.
[0000]
[0050] 5-Nitro-2-furaldehyde (1a, 1.0 g, 7.0 mmol) and 1,2-phenylenediamine (2a, 658 mg, 6.0 mmol) were dissolved in 15 mL of methanol. Next, an 8 mL aqueous solution of potassium ferricyanide (4.2 g, 12.6 mmol) was added and the reaction was heated to reflux for 3 hours while exposed to air. The reaction was cooled, then filtered and the filter pad was washed with ethanol. The filtrate liquor and washings were combined, concentrated in vacuo and the residue was recrystallized with EtOH:H 2 O (80/20) to give 1.34 g of 3a as a red-tan solid (83%) after filtration. Mp 225-226° C.; 1 H NMR (300 MHz, DMSO) δ 7.91 (1H, d, J=3.9 Hz), 7.66 (2H, m), 7.48 (1H, d, J=3.7 Hz), 7.30 (2H, m); HRMS calcd. For C 11 H 7 N 3 O 3 , 230.0566 found 230.0561. LC/MS Retention time 5.55 min (>95%), FABMS 230.3 (M+1).
[0000]
[0051] 5-Nitro-2-thiophenecarboxyaldehyde (1b, 500 mg, 3.1 mmol) and 1,2-phenylendiamine (2a, 286 mg, 2.6 mmol) were dissolved in 10 mL of methanol. Next, a 5 mL aqueous solution of 1.57 grams of potassium ferricyanide was added and the mixture was heated to reflux for two hours. Then the reaction was cooled, filtered and filter pad was washed with ethanol. The filtrate liquor and washings were combined and concentrated in vacuo and the residue was recrystallized from EtOH:H 2 O (80/20). A dark tan solid of 3b was collected by filtration, 180 mg (28%). 1 H NMR (300 MHz, DMSO) δ 8.24 (1H, d, J=4.4 Hz), 7.84 (1H, d, J=4.4 Hz), 7.65 (2H, m), 7.29 (2H, m); HRMS calcd. for C 11 H 7 N 3 O 2 S, 246.0337 found 246.0324. LC/MS Retention time 6.53 min (<95%), FABMS 244.4 (M−1).
[0000]
[0052] 5-Nitro-2-furaldehyde (1a, 304 mg, 2.1 mmol) and 4-chloro-1,2-phenylyenediamine (2c, 253 mg, 1.8 mmol) were dissolved in 10 mL of methanol. Next, a 10 mL aqueous solution of potassium ferricyanide (821 mg, 3.2 mmol) was added and the reaction was heated to reflux for 16 hours with exposure to air. The reaction was cooled, then filtered and the filter pad was washed with ethanol. The filtrate liquor and washings were combined and concentrated in vacuo and the residue was recrystallized from EtOH:H 2 O (80/20) to give 257 mg of 3c as a dark green solid (55%) after filtration. Mp 230-235° C.; 1 H NMR (300 MHz, DMSO) δ 7.96-7.82 (1H, bs), 7.76-7.57 (2H, bs), 7.55-7.43 (1H, bs), 7.37-7.23 (1H, bs); HRMS calcd. for C 11 H 6 ClN 3 O 3 , 264.0176 found 264.0189. LC/MS Retention time 7.03 min (>95%), FABMS 264.2 (M+1).
[0000]
[0053] 5-Nitro-2-furaldehyde (1a, 310 mg, 2.2 mmol) and 4-fluoro-1,2-phenylyenediamine (2d, 230 mg, 1.8 mmol) were dissolved in 10 mL of methanol. Next, a 10 mL aqueous solution of potassium ferricyanide (837 mg, 3.2 mmol) was added and the reaction was heated to reflux for 3 hours with exposure to air. Then the reaction was cooled, filtered and the filter pad was washed with ethanol. The filtrate liquor and washings were combined and concentrated in vacuo and the residue was recrystallized from EtOH:H 2 O (80/20) to give 111 mg of 3d as a yellow-green solid (25%) after filtration. Mp 235-240° C.; 1 H NMR (300 MHz, DMSO) δ 7.96-7.84 (1H, bs), 7.75-7.60 (1H, bs), 7.58-7.38 (2H, bs), 7.27-7.08 (1H, bs); HRMS calcd. for C 11 H 6 FN 3 O 3 , 248.0471 found 248.0474 found. LC/MS Retention time 6.07 min (>95%), FABMS 248.3 (M+1).
[0000]
[0054] 5-Nitro-2-furaldehyde (1a, 306 mg, 2.1 mmol) and 2,3-diaminobenzoic acid (2e, 281 mg, 1.8 mmol) were dissolved in 10 mL of methanol. Next, a 5 mL aqueous solution of potassium ferricyanide (1.3 g, 3.8 mmol) was added and the reaction was heated to reflux for 16 hours while exposed to air. Then the reaction was cooled, filtered and the filter pad was washed with ethanol. The filtrate liquor and washings were combined and concentrated in vacuo and the residue was recrystallized from EtOH:H 2 O (80/20) to give 512 mg of 3e as a brown solid (88%) after filtration. 1 H NMR (300 MHz, DMSO) δ 8.22 (1H, s), 7.88 (1H, d, J=3.9 Hz), 7.82 (1H, d, J=8.2 Hz), 7.63 (1H, d, J=3.9 Hz), 7.56 (1H, d, J=8.5 Hz); HRMS calcd. for C 12 H 7 N 3 O 5 , 274.0464 found 274.0446. LC/MS Retention time 3.05 min (>95%), FABMS 274.3 (M+1).
[0000]
[0055] 5-Nitro-2-furaldehyde (1a, 407 mg, 2.8 mmol) and 2,3-diaminotoluene (2f, 300 mg, 2.4 mmol) were dissolved in 10 mL of methanol. Next, a 5 mL aqueous solution of potassium ferricyanide (1.7 g, 5.1 mmol) was added and the reaction was heated to reflux for 3 hours while exposed to air. The reaction was cooled, then filtered and the filter pad was washed with ethanol. The filtrate liquor and washings were combined and concentrated in vacuo and the residue was recrystallized from EtOH:H 2 O (80/20) to give 519 mg of 3f as a brown solid (75%) after filtration. 1 H NMR (300 MHz, DMSO) δ 7.82 (1H, d, J=3.9 Hz), 7.40 (2H, m), 7.11 (1H, t, J=7.6, 7.6 Hz), 7.01 (1H, d, J=6.8 Hz); HRMS calcd. for C 12 H 9 N 3 O 3 , 244.0722 found 244.0729. LC/MS Retention time 6.32 min (>95%), FABMS 244.4 (M+1).
[0000]
[0056] 5-Nitro-2-furonitrile (4a, 185 mg, 1.3 mmol) was dissolved in 10 mL of ethanol and then the 2-aminothiophenol (5, 0.15 mL, 1.4 mmol) and p-toluenesulfonic acid, monohydrate (240 mg, 1.3 mmol) were added and the reaction was heated to 80° C. overnight. The reaction was concentrated to dryness in vacuo and then the residue was dissolved in EtOAc and washed with 10% sodium bicarbonate (2×), 0.5 N citric acid (2×) and then satd. brine solution. The organic phase was collected and dried over sodium sulfate, filtered and then concentrated in vacuo to give a dark oil. The material was purified through a silica gel column eluting with 100% DCM and product 6a was collected as a yellow-tan solid, 75 mg (24%). 1 H NMR (300 MHz, DMSO) δ 8.31-8.12 (1H, m), 7.82 (1H, dd, J=66.5, 4.0 Hz), 7.69-7.53 (1H, m), 7.48 (1H, d, J=8.0 Hz), 7.14-7.08 (2H, m); HRMS calcd. for C 11 H 6 N 2 O 3 S, 247.0177, found 247.0171. LC/MS Retention time 8.07 min (<95%), FABMS 247.2 (M+1).
[0000]
[0057] 5-Nitro-2-thiophenecarbonitrile (4b, 206 mg, 1.3 mmol) was dissolved in 10 mL of ethanol and then the 2-aminothiophenol (5, 0.15 mL, 1.4 mmol) and p-toluenesulfonic acid, monohydrate (243 mg, 1.3 mmol) were added and the reaction was heated to 80° C. overnight. The reaction was concentrated to dryness in vacuo and the residue was dissolved in EtOAc and washed with 10% sodium bicarbonate (2×), 0.5 N citric acid (2×) and then satd. brine solution. The organic phase was collected, dried over sodium sulfate, filtered and then concentrated in vacuo to give a red oil. The residual material was triturated with dichloromethane and 6b was obtained as red solid after filtration, 125 mg (37%). 1 H NMR (300 MHz, DMSO) δ 8.22 (1H, dd, J=2.3, 0.8 Hz), 8.20 (1H, s), 8.14-8.08 (1H, m), 7.95 (1H, dd, J=4.4, 0.8 Hz), 7.64-7.50 (2H, m); HRMS calcd. for C 11 H 6 N 2 O 2 S 2 , 263.9949, found 263.9953. LC/MS Retention time 9.55 min (<95%), FABMS 263.3 (M+1).
[0000]
[0058] 5-Nitro-2-furoic acid (7a, 1.5 g, 9.4 mmol) was partly dissolved in 20 mL of dry dichloromethane. Oxayl chloride (1.8 mL, 21.3 mmol) was added followed by a few drops of DMF. The reaction was stirred for 4 hours then concentrated to dryness in vacuo to give intermediate acid chloride, 8a, as yellow oil which became solid upon standing, 1.0 g (99%). 5-Nitrofuran-2-carbonyl chloride (8a, 624 mg, 3.5 mmol) was dissolved in 10 mL of anhydrous dichloromethane and the solution was cooled to 0° C. 2-Aminophenol (9, 460 mg, 4.2 mmol) was added followed by Et 3 N (1.4 mL, 10.5 mmol) and the reaction was then allowed to warm to room temperature and stirred overnight. The reaction was concentrated to dryness in vacuo then diluted with EtOAc (75 mL) and washed with 0.5 N citric acid (2×), 10% sodium bicarbonate soln. (2×) and then satd. brine. The organic phase was dried over sodium sulfate and concentrated in vacuo to give a yellow film. The residual material was triturated with dichloromethane and upon cooling a yellow solid of N-(2-hydroxyphenyl)-5-nitrofuran-2-carboxamide, 10a, was collected, 631 mg (73%). HRMS calcd. for C 11 H 8 N 2 O 5 , 249.0511 found 249.0517. N-(2-Hydroxyphenyl)-5-nitrofuran-2-carboxamide (10a, 151 mg, 0.6 mmol) was dissolved in 6 mL of toluene containing p-toluenesulfonic acid, monohydrate (700 mg, 3.7 mmol) and the reaction was heated to reflux overnight. The reaction was concentrated in vacuo then purified through a silica gel column eluting with dichloromethane and increasing polarity to 10% EtOAc:dichloromethane to collect product 11a as a yellow-green solid, 62 mg (44%). 1 H NMR (300 MHz, CDCl 3 ) δ 7.87-7.81 (1H, m), 7.67-7.62 (1H, m), 7.46 (4H, m); HRMS calcd. for C 11 H 6 N 2 O 4 , 231.0406 found 231.0423. LC/MS Retention time 7.53 min (<95%), FABMS 231.3 (M+1).
[0000]
[0059] 2-Nitrothiophene-4-carboxylic acid (7b, 200 mg, 1.1 mmol) was dissolved in 5 mL of dry acetonitrile and then the EDCI (434 mg, 2.2 mmol), DMAP (414 mg, 3.4 mmol) and 2-aminophenol (9, 137 mg, 1.2 mmol) was added. The reaction was stirred at room temperature overnight under argon. The reaction was concentrated in vacuo to dryness then diluted with EtOAc (75 mL) and then the organic phase was washed 2× with 0.5 N citric acid, 2× with aqueous 10% sodium bicarbonate and satd. brine solution. The organic phase was dried over sodium sulfate and concentrated to give a red solid. The residue was triturated with dichloromethane to give product 10b which was collected by filtration, 219 mg (73%). The crude N-(2-hydroxyphenyl)-5-nitrothiophene-2-carboxamide (10b, 219 mg, 0.83 mmol) was dissolved in 6 mL of toluene containing p-toluenesulfonic acid, monohydrate (788 mg, 4.14 mmol) and the reaction was heated to reflux overnight. The reaction was concentrated in vacuo then purified through a silica gel column eluting with a gradient from pure dichloromethane to 5% EtOAc:dichloromethane to give product 11b as an off white solid, 99 mg (49%) after evaporation of the solvent. 1 H NMR (300 MHz, CDCl 3 ) δ 8.58-8.55 (1H, m), 8.31 (1H, d, J=1.78 Hz), 7.80-7.75 (1H, m), 7.63-7.56 (1H, m), 7.45-7.36 (2H, m); 13 C NMR (126 MHz, CDCl 3 ) δ 157.26, 150.41, 141.47, 132.12, 127.02, 125.97, 125.15, 120.37, 110.75; HRMS calcd. for C 11 H 6 N 2 O 3 S, 247.0177, found 247.0177. LC/MS Retention time 8.35 min (<95%), FABMS 247.3 (M+1).
[0060] Although certain embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a wide variety of alternate and/or equivalent embodiments or implementations calculated to achieve the same purposes may be substituted for the embodiments shown and described without departing from the scope. Those with skill in the art will readily appreciate that embodiments may be implemented in a very wide variety of ways. This application is intended to cover any adaptations or variations of the embodiments discussed herein. Therefore, it is manifestly intended that embodiments be limited only by the claims and the equivalents thereof.
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Embodiments herein provide compounds and methods of making and using such compounds for prevention and treatment of multidrug resistant bacteria. In particular, embodiments are directed to anti-bacterial agents from benzo[d]heterocyclic scaffolds for prevention and treatment of multidrug resistant bacteria.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to integrated circuit (IC) devices, and particularly to a semiconductor device suitable for application in high-voltage operation and a method for fabricating the same.
[0003] 2. Description of the Related Art
[0004] Recently, as fabrication techniques for semiconductor integrated circuits (ICs) develop, the demands on elements such as controllers, memory, low-voltage operation circuits and high-voltage operation circuits formed over a single chip are also increasing to form a single-chip system with increased integration.
[0005] In a single-chip system, a high-voltage device such as an insulated gate bipolar transistor (IGBT) is usually used to improve the power conversion efficiency and reduce electricity loss. The IGBT has the advantages of, for example, high current gain, high operating voltage, and low on-state resistance, and is useful in high-voltage operation applications.
[0006] However, with the ongoing trend of size reduction of the single-chip system, an IGBT is needed to comply with the trend of size reduction and maintain predetermined or increased current densities and on-state resistances.
BRIEF SUMMARY OF THE INVENTION
[0007] An exemplary semiconductor device comprises a semiconductor, first, second, and third isolations, a first doped well region, a first doped region, a second doped well region, second, third, and fourth doped regions, a first gate structure, and a second gate structure. The semiconductor layer has a first conductivity type. The first, second, and third isolations are formed separately over a portion of the semiconductor layer, thereby defining a first region between the first and second isolations, and a second region between the second and third isolations. The first doped well region is disposed in a portion of the semiconductor layer in the first region and has the first conductivity type. The first doped region is disposed in the first doped well region and has a second conductivity type opposite to the first conductivity type. The second doped well region is disposed in a portion of the semiconductor layer in the second region and has the second conductivity type and an asymmetric cross-sectional profile. The second, third, and fourth doped regions are proximately disposed in the second doped well region, wherein the second and fourth doped regions have dopants of the first conductivity type, and the third doped region has dopants of the second conductivity type. The first gate structure is disposed in a portion of the semiconductor layer in the second region to partially cover the second doped well region. A second gate structure is embedded in a portion of the semiconductor layer in the second region and penetrates a portion of the second doped well region.
[0008] An exemplary method for fabricating a semiconductor device comprises providing a semiconductor layer, having dopants of a first conductivity type. A first doped well region and a second doped well region are formed in a portion of the semiconductor layer, wherein the first doped well region has dopants of the first conductivity type, and the second doped well region has dopants of a second conductivity type opposite to the first conductivity type and a symmetric cross-sectional profile. First, second and third isolations are formed over the semiconductor layer, wherein the first and second isolations partially cover a portion of the first doped well region and defines a first region between the first and second isolation, and the third isolation is adjacent to the second doped well region and defines a second region between the second and third isolations. A patterned mask layer having an opening therein is formed over the semiconductor layer, herein the opening exposes a portion of the second doped well region. A trench is funned through the portion of the second doped well region exposed by the opening and a first doped region in a portion of the second doped well region exposed by the trench and a portion of the semiconductor layer under the second doped well region, wherein the first doped region has dopants of the first conductivity type. The patterned mask layer is removed. A thermal diffusion process is performed to diffuse the dopants of the first conductivity type of the first doped region into the second doped well region adjacent thereto, and makes the symmetric cross-sectional profile into an asymmetric cross-sectional profile, wherein a bottom surface of a portion of the second doped web region adjacent to the trench is closer to a top surface of the semiconductor layer than other portions of the second doped well region. A first gate structure is formed over a portion of the semiconductor layer in the second region and a second gate structure in the trench, wherein the first gate structure partially covers the second isolation and the second doped web region. Second, third, fourth and fifth doped regions are formed, wherein the second doped region is formed in a portion of the first doped well region and has dopants of the second conductivity type, and the third and fifth doped regions are formed in a portion of the second doped well region and has dopants of the first conductivity type, and the fourth doped region is formed in a portion of the second doped well region and is between the third and fifth doped regions and has dopants of the second conductivity type.
[0009] A detailed description is given in the following embodiments with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The invention can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
[0011] FIG. 1 is schematic cross-sectional view showing a semiconductor device according to an embodiment of the invention; and
[0012] FIGS. 2-9 are schematic cross-sectional views showing a method for fabricating a semiconductor device according to an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The following description is of the best-contemplated mode of carrying out the invention. This description is made for the purpose of illustrating the general principles of the invention and should not be taken in a limiting sense. The scope of the invention is best determined by reference to the appended claims.
[0014] FIG. 1 is a schematic cross-sectional view showing an exemplary semiconductor device 10 comprising an insulated gate bipolar transistor (IGBT) known by the inventor. The semiconductor device 10 is suitable for high-voltage operation applications.
[0015] Herein, the semiconductor device 10 is used as a comparative embodiment, and only one insulated gate bipolar transistor (IGBT) in the semiconductor device 10 is partially illustrated in FIG. 1 to describe issues such as the driving current reduction of the semiconductor device 10 which happens currently with the trend of size reduction.
[0016] As shown in FIG. 1 , the semiconductor device 10 comprises a semiconductor-on-insulator (SOI) substrate 12 . The SOI substrate 12 comprises a bulk semiconductor layer 14 , and a buried insulating layer 16 and a semiconductor layer 18 sequentially stacked thereover. The bulk semiconductor layer 14 and the semiconductor layer 18 may comprise semiconductor materials such as silicon, and the buried insulating layer 16 may comprise insulating materials such as silicon dioxide. The semiconductor layer 18 may comprise dopants of a first conductivity type, for example n-type. In the semiconductor device 10 , a deep trench isolation 20 is formed in a portion of the semiconductor layer 18 , and the deep trench isolation 20 penetrates the semiconductor layer 18 and arrives the buried insulating layer 16 , thereby defining an active region (not shown) for disposing the IGBT. The deep trench isolation 20 may comprise insulating materials such as silicon dioxide.
[0017] In addition, three isolations 22 , 24 and 26 are formed separately over the semiconductor layer 18 , and a source region 28 and a drain region 30 are thus defined over the surface of the semiconductor layer 18 . Herein, the isolations 22 , 24 and 26 are illustrated as field oxides (FOXs) formed over a portion over the surface of the semiconductor layer 18 . The source region 28 is a region substantially between the isolations 22 and 24 , and the drain region 30 is a region substantially between the isolations 24 and 26 . In addition, a gate structure 32 is further formed over the semiconductor layer 18 . The gate structure 32 is formed over a portion of the semiconductor layer 18 in the source region 28 and extends over a portion of the isolation 24 adjacent to the source region 28 . Herein, the gate structure 32 comprises a gate dielectric layer 34 and a gate electrode 36 . The gate dielectric layer 34 is only formed over the surface of the semiconductor layer 18 , and the gate electrode 36 is formed over the gate dielectric layer 34 and further extends to cover a portion of the isolation 24 adjacent thereto.
[0018] Moreover, a doped well region 38 is formed in a portion of the semiconductor layer 18 in the drain region 30 , having dopants of the first conductivity type the same as that of the semiconductor layer 18 . The dopant concentration in the doped well region 38 is greater than that of the semiconductor layer 18 . A doped region 40 is further formed in the doped well region 38 , having dopants of a second conductivity type, for example p-type, opposite to the first conductivity type of the doped well region 38 and the semiconductor layer 18 . Herein, the dopant concentration in the doped region 40 is greater than the dopant concentration in the doped well region 38 . In addition, a doped well region 42 is formed in a portion of the semiconductor layer 18 in the source region 28 , having dopants of the second conductivity type, for example p-type, opposite to that of the semiconductor layer 18 . Two adjacent doped regions 46 and 44 are formed in the doped well region 42 and the doped regions 46 and 44 are surrounded by the doped well region 42 . The doped region 46 comprises dopants of the second conductivity type opposite to that of the semiconductor layer 18 , and the doped region 44 comprises dopants of the first conductivity type the same as that of the semiconductor layer 18 . Dopant concentrations of the doped regions 44 and 46 are greater than the dopant concentration of the doped well region 42 . Herein, the gate structure 32 covers a portion of the doped well region 42 and the doped region 44 .
[0019] In one embodiment, the first conductivity type in the semiconductor device 10 is n-type and the second conductivity type in the semiconductor device 10 is p-type. Thus, the doped region 40 may function as an emitter of a PNP bipolar transistor, and the semiconductor layer 18 may function as a base of the PNP bipolar transistor, and the doped region 46 may function as a collector of the PNP bipolar transistor. In addition, the doped layer 40 may also function as a drain of an N-type high voltage metal-oxide-semiconductor (MOS) transistor, and the doped region 44 may function as a source of the N-type HV MOS transistor, and the gate structure 32 may function as a gate of the N-type HV MOS transistor. The portion of the gate structure 32 covering the doped region 42 may function as a channel of the N-type HV MOS transistor.
[0020] During operation of the semiconductor device 10 comprising the IGBT shown in FIG. 1 , a positive emitter voltage relative to the collector (i.e. the doped region 46 ) is applied to the doped region 40 , and a gate voltage greater than the threshold voltage of the N-type HV MOS transistor allows currents to pass through the N-type HV MOS transistor, thereby modulating the base currents which are connected to the collector and formed between the emitter and the collector. In addition, due to formation of the N-type HV MOS transistor, more base currents can be provided to the PNP bipolar transistor. Moreover, due to formation of the n-type semiconductor layer 18 , the voltage drop of the base currents in the base can be reduced.
[0021] However, since the IGBT in the semiconductor device 10 comprise a planar type gate (i.e. the gate structure 32 ), aspects of electrical performances such as driving current and the on-state resistance thereof cannot be improved any further currently with the size reduction of the semiconductor device 10 and the region of the IGBT in the semiconductor device 10 .
[0022] Accordingly, a semiconductor device comprising an insulated gate bipolar transistor IGBT) suitable for high-voltage operation applications and a method for fabricating the same are thus provided. The semiconductor device comprising the IGBT may maintain or improve electrical performance such as driving current and on-state resistance currently with the trend of size reduction.
[0023] FIGS. 2-9 are schematic views showing an exemplary method for fabricating a semiconductor device 100 comprising an IGBT. Herein, FIGS. 2-9 respectively show fabrication in an intermediate stage of the method for fabricating the semiconductor device 100 .
[0024] In FIG. 2 , a semiconductor substrate 102 is first provided. Herein, the semiconductor substrate 102 can be, for example, a semiconductor-on-insulator (SOI) substrate. The SOI substrate comprises a bulk semiconductor layer 104 , and a buried insulating layer 106 and a semiconductor layer 108 sequentially stacked over the hulk semiconductor layer 104 , The bulk semiconductor layer 104 and the semiconductor layer 108 may comprise semiconductor materials such as silicon, and the buried insulating layer 106 may comprise insulating materials such as silicon dioxide. The semiconductor layer 108 may comprise dopants of a first conductivity type, for example n-type.
[0025] Next, implantation processes (not shown) such as ion implantation processes are performed using suitable implantation masks (not shown) to form a doped well region 112 in a portion of the semiconductor layer 108 in a source region 116 for defining an IGBT of the semiconductor device 100 , and a doped well region 110 in a portion of the semiconductor layer 108 in a drain region 114 for defining the IGBT of the semiconductor device 100 . Herein, the doped well region 112 has dopants of a second conductivity type, for example p-type, opposite to the first conductivity type of the semiconductor layer 108 and a symmetric cross-sectional profile, and the doped well region 110 as dopants of the first conductivity type the same with that of the semiconductor layer 108 .
[0026] In FIG. 3 , a deep trench isolation 118 and at least three isolations 120 . 122 , and 124 are next formed in and over the semiconductor layer 108 . Herein, the deep trench isolation 118 is formed in a portion of the semiconductor layer 108 adjacent to a side of the doped well region 112 and extends downward to reach the buried insulating layer 106 . The deep trench isolation 118 can be formed by etching a portion of the semiconductor layer 108 to first form a deep trench (not shown) exposing a portion of the buried insulating layer 106 and then filling the deep trench with insulating materials such as silicon dioxide. The isolations 120 , 122 , and 124 can be formed by, for example, thermal oxidation by using suitable patterned masks, and thus are separately formed over various portions of the semiconductor layer 108 . Herein, the isolations 120 , 122 , and 124 are field oxides of silicon dioxide which are formed by thermal oxidation. The isolation 120 is disposed over the semiconductor layer 108 between the doped well region 112 and the deep trench isolation 118 , and the isolations 122 and 124 are formed over the semiconductor layer 108 at opposite sides of the doped well region 110 and partially cover the doped well region 110 .
[0027] In FIG. 4 , a patterned mask layer 125 is next formed over the surface of the semiconductor layer 108 and covers the deep trench isolation 118 and the isolations 120 , 122 , and 124 . An opening 126 is formed in the patterned mask layer 125 to expose a portion of the doped well region 112 . In one embodiment, the patterned mask layer 125 is a photoresist layer, and the opening 126 can thus he formed by processes such as photolithography and etching processes. Next, an ion implantation process 127 is performed, using the patterned mask layer 125 as an implantation mask, to implant dopants of the first conductivity type into a portion of the lower portion of the doped well region 112 exposed by the opening 126 and a portion of the semiconductor layer 108 thereunder, thereby forgoing a doped region 132 . Dosages and energies used in the ion implantation process 127 can be properly adjusted to control the location of the formed doped region 132 .
[0028] In FIG. 5 , an etching process (not shown) is performed next, using the patterned mask layer 125 as an etching mask, to remove the portion of the doped well region 112 exposed by the opening 126 , and form a trench 130 in the portion of the doped region exposed by the opening 126 . The trench 130 partially penetrates the doped well region 112 and exposes a top surface of the doped region 132 . In the above etching process, a portion of the doped region 132 (not shown) may be also etched and removed.
[0029] In another embodiment, the sequence of the ion implantation process and the etching process performed in FIGS. 4-5 may be reversed. As shown in FIG. 6 , after forming the patterned mask layer 125 having the opening 126 over the semiconductor layer 108 , an etching process 128 is first performed, using the patterned mask layer 125 as an etching mask, to remove a portion of the doped well region 112 exposed by the opening 126 , and a trench 130 is formed in a portion of the doped well region 112 exposed by the opening 126 . The trench 130 partially penetrates the doped well region 112 .
[0030] In FIG. 7 , an ion implantation process (not shown) is performed, using the patterned mask layer 125 as an implant mask, to implant dopants of the first conductivity type to a portion of the doped well region 112 exposed by the trench 130 and a portion of the semiconductor layer 108 thereunder, thereby forming a doped region 132 under the trench 130 and a portion of the semiconductor layer 108 exposed by the trench 130 , and the trench 130 partially exposes the surface of the doped region 132 .
[0031] In FIG. 8 , after removal of the patterned mask layer 125 shown FIGS. 4-7 , a thermal diffusion process (not shown), for example an annealing process, is then performed to diffuse the dopants of the first conductivity type in the doped region 132 into the adjacent doped well region 112 (see FIGS. 5 and 7 ) and changes the symmetric cross-sectional profile of the doped well region 112 . The change to the cross-sectional profile is illustrated as the doped dwell region 112 ′ shown in FIG. 8 . Herein, the doped dwell region 112 ′ no longer has a symmetric cross-sectional profile as that shown in FIGS. 2-7 but an asymmetric cross-sectional profile. After the thermal diffusion process, the profile of the doped region 132 is also changed and identified with the reference number 132 ′ in FIG. 8 . The diffused doped region 132 ′ covers a lower portion of the trench 130 .
[0032] Next, two gate structures 140 and 150 are separately formed over the semiconductor layer 108 . The gate structure 140 is formed over the semiconductor layer 108 between the doped well region 112 and the isolation 122 , and the gate structure 150 is formed in the trench 130 and fills the same. Herein, the gate structures 140 and 150 respectively comprise a gate dielectric layer 134 and a gate electrode layer 136 . The gate dielectric layer 134 and a gate electrode layer 136 in gate structure 140 and 150 can be formed in the same processes, and the fabrication and materials thereof can be the same as those of the conventional gate dielectric layer and gate electrode layer, and are not described herein.
[0033] In FIG. 9 , through the usage of suitable imp an masks (not shown) and operations of several implantation processes such as ion implantation processes, a doped region 152 is formed in a portion of the doped dwell region 1110 , and a plurality of adjacent doped regions 154 , 156 , 158 , and 160 are formed in the doped well region 112 ′. Herein, the doped regions 152 , 154 , and 158 have dopants of the second conductivity type opposite to the first conductivity type of the semiconductor layer 108 , and the doped regions 156 and 160 have dopants of the first conductivity type the same as that of the semiconductor layer 108 . The concentration of the doped regions 152 , 154 , 156 , 158 , and 160 are greater than the doped well region 110 or 112 ′ adjacent thereto.
[0034] As shown in FIG. 9 , a method for fabricating the semiconductor device 100 comprising an IGBT device is substantially completed. Additional contacts, interconnects, and insulating layers can be sequentially formed in the sequential processes to form related connection circuits, and the fabrication of these components is not described here for simplicity.
[0035] In one embodiment, the first conductivity type in the semiconductor device 100 shown in FIG. 9 is n-type and the second conductivity type in the semiconductor device 100 is p-type. Thus, the doped region 152 may function as an emitter of a PNP bipolar transistor, and the semiconductor layer 108 may function as a base of the PNP bipolar transistor, and the doped region 158 may function as a collector of the PNP bipolar transistor.
[0036] In addition, the doped region 152 may also function as a drain of an N-type high voltage metal-oxide-semiconductor (MOS) transistor comprising the gate structure 140 , and the doped region 160 may function as a source of the N-type HV MOS transistor comprising the gate structure 140 , and the gate structure 140 may function as a gate of the N-type HV MOS transistor. The portion of the gate structure 140 covering the doped region 112 ′ may function as a channel of the N-type HV MOS transistor.
[0037] Moreover, another N-type metal-oxide-semiconductor (MOS) transistor is disposed in the semiconductor device 100 , comprising the gate structure 150 . The doped region 152 may also function as a drain of an N-type metal-oxide-semiconductor (MOS) transistor comprising the gate structure 150 , and the doped region 156 may function as a source of the N-type MOS transistor comprising the gate structure 150 , and the gate structure 150 may function as a gate of the N-type MOS transistor. The portion of the doped region 112 ′ covered by the gate structure 150 may function as a channel of the N-type MOS transistor, which is entitled as C 1 in FIG. 9 . A bottom surface of the portion of the doped well region 112 ′ adjacent to the doped regions 156 and 154 is closer to the top surface of the semiconductor layer 108 than other portions of the doped well region 112 ′. Compared with another channel C 2 of an imaginary N-type MOS transistor comprising the gate structure 150 and the original doped well region 112 (illustrated with dotted line here, see FIG. 2-7 ) which is not formed with the doped region 132 ′ and is not affected by diffusion of the doped region 132 ′, having the original cross-sectional profile, the asymmetric cross-sectional profile of the doped well region 112 ′ adjacent to the gate structure 150 caused due to formation and diffusion of the doped region 132 ′ may reduce the length of the channel C 1 , thereby improving driving currents of the N-type MOS transistor comprising the gate structure 150 .
[0038] Moreover, during operation of the semiconductor device 100 comprising the IGBT shown in FIG. 9 , a positive emitter voltage relative to the collector (i.e. the doped region 158 ) is applied to the doped region 152 , and a gate voltage greater than the threshold voltage of the N-type MOS transistor and the N-type HV MOS transistor of the semiconductor device 100 allows currents to pass through the N-type MOS transistor and the N-type HV MOS transistor, thereby modulating the base currents which are connected to the collector and firmed between the emitter and the collector. In addition, due to formation of the N-type MOS transistor and the N-type HV MOS transistor, more base currents can be provided to the PNP bipolar transistor. Moreover, due to fore ration of the n-type semiconductor layer 108 , voltage drop of the base currents in the base can be reduced.
[0039] When compared with the semiconductor device 10 shown in FIG. 1 , since an additional MOS device is provided in the semiconductor device 100 shown in FIG. 9 , the semiconductor device 100 shown in FIG. 9 may have improved electrical performance such as increased driving currents and on-state resistance than the semiconductor device 10 shown in FIG. 1 . Therefore, the electrical performances such as driving current and on-state resistance of the elements in the semiconductor device 100 can he maintained or improved currently with the trend of size reduction of the semiconductor device 100 and the region of the IGBT in the semiconductor device 100 . Moreover, since the semiconductor device 100 shown in FIG. 9 is formed over a SOI substrate and a deep trench isolation 118 is formed in a portion of the semiconductor layer 108 of the SOI substrate, noises affecting the semiconductor device 100 can be reduced and a latch-up effect in the semiconductor device 100 is thus prevented.
[0040] The scope of the invention is not limited to the semiconductor device 100 shown in FIG. 9 , and a plurality of IGBT can be provided and properly arranged in the semiconductor device. For the purpose of simplicity, fabrications and arrangements thereof are not described here.
[0041] While the invention has been described by way of example and in terms of the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.
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A semiconductor device includes: a semiconductor layer; a first doped well region disposed in a portion of the semiconductor layer; a first doped region disposed in the first doped well region; a second doped well region of an asymmetrical cross-sectional profile disposed in another portion of the semiconductor layer; second, third, and fourth doped regions formed in the second doped well region; a first gate structure disposed over a portion of the semiconductor layer, practically covering the second doped well region; and a second gate structure embedded in a portion of the semiconductor layer, penetrating a portion of the second doped well region.
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FIELD OF THE INVENTION
The present invention relates to ceramic cores for use in investment casting of metallic industrial gas turbine engine blades and vanes having internal passageways and large airfoil pitch.
BACKGROUND OF THE INVENTION
In casting gas turbine engine blades and vanes using conventional equiaxed and directional solidification techniques, ceramic cores are positioned in an investment shell mold to form internal cooling passageways. During service in the gas turbine engine, cooling air is directed through the passageways to maintain blade temperature within an acceptable range. In manufacture of large gas turbine engine blades and vanes for industrial gas turbine engines, correspondingly larger ceramic cores are used to form the internal passages. The ceramic cores used in investment casting can be prone to distortion and loss of the required dimensional tolerance during core manufacture, especially of the airfoil core pitch. The problem of airfoil pitch distortion is greater for larger ceramic cores used in the manufacture of industrial gas turbine engines.
An object of the present invention is to provide a method of making a ceramic core and the core so made in a manner that reduces airfoil pitch shrinkage and loss of dimensional tolerance.
SUMMARY OF THE INVENTION
An embodiment of the present invention provides a method of making a ceramic core having an airfoil section for use in making a gas turbine engine airfoil casting by forming a precursor core (hereinafter referred to as a chill) of smaller dimensions than the final desired ceramic core, firing the chill, applying a thin ceramic skin to the fired chill to form a coated core, and then firing the coated core. Firing shrinkage of the thin ceramic skin during the second firing operation is minimal compared to that of the chill in the first firing. Shrinkage, distortion and loss of dimensional tolerance of the airfoil pitch of the final core is thereby reduced.
The invention provides a ceramic core for use in making large industrial gas turbine engine airfoil castings having an airfoil pitch of one inch and greater and having an airfoil pitch shrinkage of the core of about 0.5% or less.
The above objects and advantages of the present invention will become more readily apparent from the following detailed description taken with the following drawings.
DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are schematic views of a method of making a ceramic core pursuant to an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The invention provides a ceramic core especially useful in casting large industrial gas turbine engine (IGT) blades and vanes (airfoils). The core 20 , FIG. 1B, has an airfoil section 21 with a pitch P of one (1) inch and greater where the pitch P is the maximum cross-sectional thickness of airfoil section taken on a plane perpendicular to a longitudinal axis (known as stack axis) of the airfoil section. The invention is especially useful in making ceramic cores that exhibit core airfoil pitch shrinkage of about 0.5% or less when made pursuant to the invention.
Referring to FIGS. 1A and 1B, an illustrative chill (precursor core) 10 of smaller dimensions than the final desired ceramic core 20 is shown and first formed by preparing a mixture of one or more suitable ceramic powders and a binder. The chill 10 includes airfoil shaped section 10 a . The binder can be either an organometallic liquid, such as prehydrolized ethyl silicate, a thermoplastic wax-based binder, or a thermosetting resin mixed with ceramic powders in appropriate proportions to form a ceramic/binder mixture for molding to shape. The ceramic powders can be blended using a conventional V-cone blender, pneumatic blender, or other such blending equipment. The binder can be added using conventional high-shear mixing equipment at room temperature or elevated temperature. The ceramic powders may comprise alumina, silica, zirconia and other powders suitable for casting a particular metal or alloy. For example, the ceramic powders may have the following proportional ranges as a dry blend of powders:
Dry Blend
Wt % Range
Continental Minerals −325 mesh Zircon
15%-35%
Minco −200 mesh Fused Silica (MlnSil−40)
15%-20%
CE Minerals Inc. 10 micron Fused Silica
12%-20%
CE Minerals −140/+325 mesh Fused Silica
0%-30%
CE Minerals −70/+100 mesh Fused Silica
10%-50%
The zircon powder was available from Continental Minerals Processing Corporation, P.O. Box 62005, Cincinnati, Ohio, while the silica powders were available from Minco Inc., 510 Midway Circle, Midway, Tenn. and CE Minerals Inc., P.O.Box 1540, Snappferry Road, Greenville, Tenn.
A desired chill airfoil shape is formed by transferring the fluid ceramic/binder mixture into an aluminum or steel die either by injection or by pouring. The die defines a molding cavity having the chill configuration desired. The chill can be molded with integral conical protrusions 16 on the chill, FIG. 1A, and/or with an integral extension 18 a of the chill core print 18 that allows the chill to be held in position in a final core die discussed below. The Injection pressures in the range of 500 psi to 2000 psi are used to pressurize the fluid ceramic/binder mixture in the molding cavity of the die. The dies may be cooled, held at room temperature, or slightly heated depending upon the complexity of the desired chill configuration. After the ceramic/binder mixture solidifies in the die, the die is opened, and the green, unfired chill is removed. The green, unfired chill then is subjected to a heat treatment with the chill positioned on a ceramic setter contoured to the shape of the chill. The ceramic setter, which includes a top half and a bottom half between which the chill is positioned, acts as a support for the chill and enables it to retain its shape during thermal processing. Sintering of the chill is achieved by means of this heat treatment to an elevated temperature based on the requirements of the filler powders.
The fired chill is positioned into the final core die such that the protrusions or “bumpers” 16 hold it off or away from the inner surface of the die, forming a small cavity between the chill and the final core die surface. The chill can be held away from the die surface using the protrusions 16 molded integrally on the chill, FIG. 1A, or using the extension 18 a of the chill core print 18 that is adapted to be held in position in the die outside the molding cavity, or using positioning pins extending from the main core die. The ceramic skin 12 typically comprises the same or similar material used to form the chill. The ceramic skin is applied by either pouring or injecting a slurry of the ceramic material into the cavity formed between the die and the chill to have a constant thickness in the range of about 0.050 inch to 0.200 inch on all surfaces of the fired chill. The slurry can then be pressurized in the final core die to complete forming of the final core 14 having airfoil section 21 . The final core 14 then is fired at elevated temperature based on requirements of the core materials. In some embodiments of the invention, the skin can be ignited to burn alcohols present in the binder and fired to an elevated temperature based on the requirements of the ceramic materials. As a result of the small thickness of the ceramic skin, there is little or essentially no firing shrinkage of the skin on the fired chill. This reduces or eliminates distortion due to proportional linear shrink of the widely varying cross-sections in core geometries used in casting. In particular, the coated cores (chill with ceramic skin), FIG. 1B, exhibit an airfoil pitch shrinkage of about 0.5% or less upon firing of the coated chill pursuant to the invention. In addition, the rigid fired chill provides body and stiffness to the core skin during firing to help minimize warping from firing.
The following Examples are offered to further illustrate, but not limit, the invention. In the Examples below, Wt % of ceramic powders is weight percent and −140/+325 mesh means greater than 140 mesh and less than 325 mesh powder and so on where mesh is U.S. standard sieve.
EXAMPLES
Example 1
One embodiment may be produced with a wax-injected ceramic chill, which is fired and used to produce the final core by pouring a liquid ceramic slurry around the fired chill. The binder for the chill can be made up of a thermoplastic wax-based material having a low melting temperature and composition of the type described in U.S. Pat. No. 4,837,187 incorporated herein by reference. The thermoplastic wax-based binder typically includes a thermoplastic wax, an anti-segregation agent, and a dispersing agent in proportions set forth in U.S. Pat. No. 4,837,187. A suitable thermoplastic wax for the binder is available as Durachem wax from Dura Commodities Corp., Harrison, N.Y., This wax exhibits a melting point of 165 degrees F. A strengthening wax can be added to the thermoplastic wax to provide the as-molded core with higher green strength. A suitable strengthening wax is available as Strahl & Pitsch 462-C from Strahl & Pitsch, Inc. West Babylon, N.Y. A suitable anti-segregation agent is an ethylene vinyl acetate copolymer such as DuPont Elvax 310 available from E.I. DuPont de Nemours Co., Wilimington, Del. A suitable dispersing agent is oleic acid. The ceramic powders can be blended using a conventional V-blender, pneumatic blender or other such blending equipment. The binder is added using high-shear mixing equipment at room temperature or elevated temperature as required by the melt temperature of the binder. The ceramic powders comprise silica and zircon in a 4:1 volumetric ratio. A desired chill shape is formed by injecting the ceramic/binder system into a steel die at elevated temperature and pressure. Injection pressures in the range of 500 psi to 2000 psi may be used to pressurize the fluid ceramic/binder mixture in the molding cavity. The die is typically held at temperatures ranging from 150 to 200 farenheight. After the ceramic/binder mixture solidifies in the molding cavity, the die is opened, and the green, unfired chill is removed. The green, unfired chill is placed in a ceramic setter contoured to the shape of the chill. A fine powdered material with a high surface area such as clay or graphite is placed on top of the chill while it is subjected to a prebake treatment designed to melt the wax binder. During this prebake treatment, the liquid binder is extracted from the chill into the powder through capillary action. A suitable prebake treatment may be conducted for approximately 5 hours at 550 to 600 degrees F. for a maximum turbine blade airfoil core thickness of approximately 2.2 inches. The chill in the ceramic setter is then covered with a top setter contoured to the shape of the top contour of the chill. The green chill with setter top and bottom is then fired or sintered to a temperature suitable to remove some of the porosity and impart a strength to the chill adequate for further processing. A suitable firing treatment may be conducted for approximately five hours at 2050 degrees F. The fired chill is then placed in the final core die designed to produce the outer contour of the finished core. The “bumpers” designed into the chill rest against the surface of the core die and hold it a constant distance from the die on all surfaces. The final core is then formed by pouring a ceramic slurry into the die with the chill inside. The ceramic slurry encapsulates the chill and hardens onto it forming a skin. The ceramic powders used for the skin are comprised of the following:
Dry Blend
Wt %
Continental Minerals −325 mesh Zircon
30.28%
Minco −200 mesh Fused Silica (MinSil−40)
16.13%
CE Minerals Inc. 10 micron Fused Silica
14.23%
CE Minerals −140/+325 mesh Fused Silica
26.43%
CE Minerals −70/+100 mesh Fused Silica
12.93%
These ceramic powders are mixed with prehydrolized ethyl silicate (Remet R-25) in a ratio appropriate to form a low viscosity slurry. The solid/liquid ratio typically used is 4:1 resulting in a viscosity ranging from 700 to 1200 centipoise. Prior to pouring the ceramic slurry into the mold, it is combined with a basic catalyst such as ammonium hydroxide or morpholine which crosslinks the ethylsilicate producing a ceramic gel structure and effectively hardens the ceramic slurry in the shape of the core die cavity. The concentration of the catalyst is adjusted with water to allow for a working time of 3 to 5 minutes prior to hardening. The slurry/catalyst ratio typically used is 20:1 to 22:1 by volume. The slurry skin is ignited immediately upon opening the die (rapid heating to elevated temperature) to further harden the skin binder. After a 20 to 30 second burn, the flames are extinguished by a blast of air, and the green core is removed from the die. Once the core has been removed from the die, it is placed on a controlled surface and re-ignited and allowed to completely burn out. This combustion process allows the alcohols in the binder to be removed and further hardens the core surface. The coated core 14 then is fired at elevated temperature to complete the removal of any organics. A suitable firing cycle for the final core is conducted for approximately 1 to 2 hours at 1700 to 1800 degrees F. The core is then impregnated with silica by soaking it in a 30% by weight aqueous colloidal silica sol. This colloidal silica sol is commercially marketed under the Dupont Ludox trade name. The cores are then placed in a dryer held at 180 to 200 degrees F. until the water is sufficiently removed. These cores may be dipped and dried once or numerous times in order to fill the pour structure of the core with amorphous silica. After the final dry cycle the cores are loaded back into the firing setter and subjected to a final sintering cycle for 1 to 2 hours at 1700 to 1800 degrees Fahrenheit.
Example 2
Another embodiment is comprised of a ceramic chill and skin both produced by pouring a liquid ceramic slurry into molds and subjected to sequential heat treatments. In this case, the binder for the chill is the same as that described above for the skin. The ceramic powders are comprised of the following formulation.
Dry Blend
Wt %
Continental Minerals −325 mesh Zircon
30.28%
Minco −200 mesh Fused Silica (MinSil−40)
16.13%
CE Minerals Inc. 10 micron Fused Silica
14.23%
CE Minerals −140/+325 mesh Fused Silica
26.43%
CE Minerals −70/+100 mesh Fused Silica
12.93%
The binder is mixed with the powders in a 4:1 weight ratio of powders to binder. A desired chill shape is formed by mixing the ceramic slurry with a catalyst in the manner described in example one, pouring or injecting the ceramic/binder system into an aluminum die at room temperature and applying pressure by means of a hydraulic cylinder. Pressures in the range of 100 psi to 1000 psi may be used to pressurize the fluid ceramic/binder mixture in the molding cavity. After the ceramic/binder mixture solidifies in the molding cavity, the die is opened, and the chill is ignited as described in example one for the skin. After 20 to 30 seconds, the flames are extinguished, the chill removed from the die, placed on a contoured burn fixture, re-ignited, and allowed to burn out. The chill is then placed in a firing setter and fired to 1700 to 1800 degrees F. for 1 to 2 hours to remove the organics. It is then dipped in colloidal silica in order to harden it for subsequent use in the final core die. The fired chill is then placed in the final core die designed to produce the outer contour of the finished core. The final core is then formed exactly as described in example 1 above.
Ten core test bars having a cross section thickness of 0.450″ produced using example 2 exhibited an average pitch shrinkage of 0.43%. A core having a cross section thickness of 1.7″ produced using example 2 exhibited a pitch shrinkage of 0.5%. The same core produced using no chill and the same material as in example 2 exhibited a pitch shrinkage of 1.6%.
Example 3
Another embodiment is comprised of a ceramic chill and skin both produced by pouring a liquid ceramic slurry into molds and subjected to sequential heat treatments. In this case, the binder for the chill is the same as that described above for the skin. The ceramic powders are comprised of the following formulation.
Dry Blend
Wt %
−325 mesh zircon
18.80%
−200 mesh Fused Silica (MinSil−40)
17.28%
10 micron Fused Silica
15.24%
−70/+100 mesh Fused Silica
48.67%
The binder is mixed with the powders in a 4:1 weight ratio of powders to binder. A desired chill shape is formed by mixing the ceramic slurry with a catalyst in the manner described in example one, pouring or injecting the ceramic/binder system into an aluminum die at room temperature and applying pressure by means of a hydraulic cylinder. Pressures in the range of 100 psi to 1000 psi may be used to pressurize the fluid ceramic/binder mixture in the molding cavity. After the ceramic/binder mixture solidifies in the molding cavity, the die is opened, and the chill is ignited as described in example one for the skin. After 20 to 30 seconds, the flames are extinguished, the chill removed from the die, placed on a contoured burn fixture, re-ignited, and allowed to burn out. The chill is then dipped in colloidal silica as described for the core in example 1, placed in a firing setter and fired to 1700 to 1800 degrees F. for 1 to 2 hours to remove the organics. The fired chill is then placed in the final core die designed to produce the outer contour of the finished core. The final core is then formed exactly as described in example 1 above.
Ten core test bars having a cross section thickness of 0.450″ produced using example 2 exhibited an average pitch shrinkage of 0.3%. A core having a cross section thickness of 1.7″ produced using example 2 exhibited a pitch shrinkage of 0.5%. The same core produced using no chill and the same material as in example 2 exhibited a pitch shrinkage of 1.6%.
Example 4
Another embodiment is comprised of a ceramic chill and skin both produced by pouring a liquid ceramic slurry into a mold, and upon removal from the mold, subjecting it to sequential heat treatments. In this case, the binder for the chill is the same as that described above for the skin. The ceramic powders are comprised of the following formulation.
Dry Blend
Wt %
−325 mesh zircon
18.80%
−200 mesh Fused Silica (MinSil−40)
17.28%
10 micron Fused Silica
15.24%
−70/+100 mesh Fused Silica
48.67%
The binder is mixed with the powders in a 4:1 weight ratio of powders to binder. A desired chill shape is formed by mixing the ceramic slurry with a catalyst in the manner described in example one, pouring or injecting the ceramic/binder system into an aluminum die at room temperature and applying pressure by means of a hydraulic cylinder. Pressures in the range of 100 psi to 1000 psi may be used to pressurize the fluid ceramic/binder mixture in the molding cavity. After the ceramic/binder mixture solidifies in the molding cavity, the die is opened, and the chill is ignited as described in example one for the skin. After 20 to 30 seconds, the flames are extinguished, the chill removed from the die, placed on a contoured burn fixture, re-ignited, and allowed to burn out. The chill is then dipped in colloidal silica as described for the core in example 1, placed in a firing setter and fired to 1700 to 1800 degrees F. for 1 to 2 hours to remove the organics. The fired chill is then placed in the final core die designed to produce the outer contour of the finished core. The “bumpers” designed into the chill rest against the surface of the core die and hold it a constant distance from the die on all surfaces. The fired chill is then placed in the final core die designed to produce the outer contour of the finished core. The final core is then formed by pouring a ceramic slurry into the die with the chill inside. The ceramic slurry encapsulates the chill and hardens onto it forming a skin. The ceramic powders used for the skin are comprised of the following:
Dry Blend
Wt %
−325 mesh zircon
18.80%
−200 mesh Fused Silica (MinSil−40)
17.28%
10 micron Fused Silica
15.24%
−70/+100 mesh Fused Silica
48.67%
These ceramic powders are mixed with a liquid organometallic binder such as prehydrolised ethyl silicate in a ratio appropriate to form a low viscosity slurry. The solid/liquid ratio typically used is 4:1 resulting in a viscosity ranging from 700 to 1200 centipoise. Prior to pouring the ceramic slurry into the mold, it is combined with a basic catalyst such as ammonium hydroxide or morpholine which crosslinks the ethylsilicate producing a ceramic gel structure and effectively hardens the ceramic slurry in the shape of the core die cavity. The concentration of the catalyst is adjusted with water to allow for a working time of 3 to 5 minutes prior to hardening. The slurry/catalyst ratio typically used is 20:1 to 22:1 by volume. The slurry skin is ignited immediately upon opening the die (rapid heating to elevated temperature) to further harden the skin binder. After a 20 to 30 second burn, the flames are extinguished by a blast of air, and the green core is removed from the die. Once the core has been removed from the die, it is placed on a controlled surface and re-ignited and allowed to completely burn out. This combustion process allows the alcohols in the binder to be removed and further hardens the core surface. The core is then impregnated with silica by soaking it in a 30% by weight aqueous colloidal silica sol. This colloidal silica sol is commercially marketed under the Dupont Ludox trade name. The cores are then placed in a dryer held at 180 to 200 degrees F. until the water is sufficiently removed. These cores may be dipped and dried once or numerous times in order to fill the pour structure of the core and amorphous silica. After the final dry cycle the cores are loaded back into the firing setter and subjected to a final sintering cycle for 1 to 2 hours at 1700 to 1800 degrees Fahrenheit.
Ten core test bars having a cross section thickness of 0.450″ produced using example 4 exhibited an average pitch shrinkage of 0.19%. A core having a cross section thickness of 1.7″ produced using example 4 exhibited a pitch shrinkage of 0.4%. The same core produced using no chill and the same material as in example 2 exhibited a pitch shrinkage of 1.6%.
Although the invention has been described with respect to certain embodiments thereof, those skilled in the art will appreciate that the invention is not limited to these embodiments and changes, modifications, and the like can be made therein within the scope of the invention as set forth in the appended claims.
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Method of making a ceramic core for casting an industrial gas turbine engine airfoil having a large airfoil pitch by forming a precursor core (chill) of smaller dimensions than the final desired ceramic core, firing the chill, applying a thin ceramic skin to the fired chill to form a coated core of final dimensions, and then firing the coated core. Firing of the thin ceramic skin reduces airfoil pitch shrinkage resulting from the latter firing operation to reduce overall core dimensional tolerance variations.
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RELATED APPLICATION
The present application is an improvement upon the invention of an earlier copending application, Ser. No. 032,960, filed Apr. 24, 1979, now U.S. Pat. No. 4,287,844, entitled "Bulky Composite Fabric and Method of Making Same".
FIELD OF THE INVENTION
The present invention relates to structures comprising composite knitted fabrics, and has particular application to grounding structures which require a heat-resistant conductive material which is sufficiently flexible to adapt to various structural configurations, and yet which is relatively inexpensive and sufficiently durable to maintain its integrity under severe conditions of use.
BACKGROUND OF THE INVENTION
Grounding straps for various uses comprise flat strips of conductive metal or twisted or braided strands of conductive wire, depending upon the use which the grounding strap is applied. The flat band has a wide surface exposure and may be used where the flexibility of the strap is not a significant design factor. However, where flexibility is desired, it has been common practice to use solid, twisted, or braided strands of conductive wire.
SUMMARY OF THE PRESENT INVENTION
With the foregoing in mind the present invention provides improved composite knitted fabrics which may be knitted with conductive strands such as wire to produce a grounding element.
More specifically the present invention provides novel structures which effectively utilize the characteristics of knitted fabrics to produce an improved grounding element in an effective and economical fashion.
DESCRIPTION OF DRAWINGS
All of the objectives of the present invention are more fully set forth hereinafter with reference to the accompanying drawings wherein:
FIG. 1 is a schematic cross-section through a bag filter embodying a grounding wire composed of a composite fabric in accordance with the present invention;
FIG. 2 is an enlarged sectional view as seen from the line 2--2 in FIG. 1;
FIG. 3 is an irregular sectional view taken on the line 3--3 of FIG. 2; and
FIG. 4 is a schematic illustration of the stitch pattern embodied in the tubular fabric components of the composite fabric shown in FIGS. 1-3, the tubular fabric being split and opened out to facilitate the illustration of the stitch pattern.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A preferred application of the invention is illustrated in FIGS. 1 through 3 inclusive. In these figures, a bag filter is shown which incorporates a grounding strap made in accordance with the present invention. As shown in FIG. 1, a conventional bag filter comprises a casing 102 having a horizontal partition 103 adjacent the top wall to divide the interior of the casing 102 into a lower pressure chamber 104 and an upper suction chamber 105. A dirty-air inlet 106 introduces dust-laden air into the pressure chamber 104 and an exhaust conduit 107 exhausts clean air from the suction chamber 105. The partition 103 has a plurality of openings therein, conventionally circular in outline, and within each such opening a bag-type filter element is positioned. The filter element comprises a mounting ring adapted to mount the bag within the partition opening and a depending cylindrical tube which is closed at its lower end. Frames may be mounted within the cylindrical tube to maintain it in its annular tubular form so as to provide passageway for air to flow upwardly throughout the entire length of the bag, air entering the bag throughout its length radially inward, and depositing dust or other foreign material on the exterior of the bag. Periodically or intermittently the bag filter operates to dislodge the accumulated dust or other foreign material from the exterior surface of the bag so that it falls into the bottom of the pressure chamber 104 where it may discharged by a suitable dust-discharging device. The dislodgement from the dust from the filter bags may be accomplished pneumatically by causing reverse air flow through the cylindrical bags from inside to out, or may be accomplished mechanically by jogging the bags. After a period of operation the fabric component of the bags tends to become dirt-clogged thereby impairing the efficiency of the filter apparatus and to this end the bags are designed to be readily removed and replaced. In this event, the lid of the dryer casing 102 is opened to permit upward displacement of individual bag elements out of their position in the filter partition 103, as indicated in broken lines at 109' in FIG. 1.
In accordance with the invention of a co-pending application of Thomas A. Weil, the construction of the bag may be simplified to facilitate mounting and dismounting of the bag element 109 from the partition 103. To this end as shown in FIG. 3, the bag member 109 comprises a generally cylindrical bag element 112 composed of a suitable filtration material, in the present instance a woven fabric. The tubular fabric 112 is closed at its lower end and is open at its upper end so as to communicate the interior of the tubular member 109 with the suction chamber 105 at the top of the filter housing above the partition 103.
At the upper end, the bag element 109 is designed to releasably engage with an opening 113 in the partition element 103. As stated above the opening 113 is preferably of circular outline so that the cylindrical tubular bag element 109 fits neatly within the opening 113. At the upper end, the fabric of the bag 109 is turned back on itself and sewn as indicated at 114, embracing a ring member 116 which serves to mount the bag element 109 within the opening 113. The ring member 116 includes an annular wall, in the present instance a spring steel strap 117 formed into a circlet which is slightly smaller in outer diameter than the periphery of the circular opening 113 in the partition 103 so that a limited clearance is provided between the annular wall 117 of the strap and the periphery of the opening 113. A composite fabric 118 is mounted on the outer surface of the annular wall 117 within the clearance space between the wall 117 and the periphery of the opening 113.
The composite fabric 118 comprises a pair of bulky knit tubular components 123 and 124 which are mounted in spaced parallel relationship upon a third component comprising a base fabric 125. In the present instance the base fabric 125 is a woven structure having an elastomeric coating 126 on one surface. The bulky knit tubular components 123 and 124 are secured to the uncoated surface of the fabric 125 by straight lines of stitching (not shown). The elastomeric coating 126, in the present instance serves as a bonding agent to permanently mount the base fabric 125 on the outer surface of the annular wall 117. The mounting device 116 thereby comprises the strap 117 with the composite fabric 118 securely bonded thereto. The mounting device 116 is retained within the hem of the cylindrical tube formed by the turned back portion of the fabric which is sewn to itself at 114. The bulky knit tubular components 123 and 124 are readily compressible and are sufficiently bulky to spring back and engage on opposite sides of the periphery of the opening 113 and the partition 103. The spacing between the components 123 and 124 is selected to correspond to the thickness of the marginal portion of the opening 113 so as to releasably anchor the filter bag 109 in place within the opening 113 of the partition 103.
The filter fabric making up the tube 112 and the components of the composite fabric 118 must be of heat-resistant material in order to avoid deterioration when subjected to the hot gases which pass through the filter casing. Bag filters of this type are frequently used to treat the drying medium in dryers and in such installations the temperature of the gaseous medium to be filtered may be substantially greater than the degradation temperature of normal textile material. Of course, where the gaseous medium being filtered is not subject to high temperature limitations, the textile components of the bag elements may be comprised of standard textile materials. In any event the use of a composite fabric with a plain annular metallic wall of spring steel such as shown in FIG. 3 permits the fabrication of the filter elements in a simple and highly economical fashion and permits the selection of the textile materials which resist the adverse effects of the particular gaseous medium and the entrained foreign matter which is being filtered.
In bag filters of this character, there is frequently a problem which arises due to the generation of static electricity charges on the bag which if not dissipated may create danger of explosion or fire.
To dissipate the electrostatic charge which might otherwise build up on the filter components, grounding means is incorporated into the filter bags which is effective to dissipate any electrostatic charge which might otherwise build up. While standard grounding wires may prove effective, in order to assure the dissipation of the complete charge the grounding wire should present a large surface exposure to the gaseous flow. A single strand of conductive material may tend to become coated with particulate material which is filtered out of the gaseous flow and may lose its efficiency as a grounding means. Likewise if the surface of the grounding element is sufficiently wide, it tends to create a problem due to the stiffness or rigidity of the grounding component which must have sufficient durability to withstand the impacts to which it is subjected during the periodic or intermittent operation of the filter mechanismn to dislodge the accumulated foreign matter from the filter bags. Thus, the present invention provides a grounding element which is possessed of a large area of exposed surface but which also is sufficient flexible and durable to withstand the stresses which are imparted to it when the filter bags are cleaned of their accumulated foreign matter. Furthermore since it is desirable to permanently mount the grounding element within the filter fabric, the grounding element should have a flexibility comparable to the flexibility of the filter fabric in which it is incorporated, and should be of sufficiently open construction to permit attachment of the element to the filter bag, for example by standard sewing techniques.
A suitable grounding element comprises a double thickness of a tubular knit metallic strand which may be fabricated into knit tubes on the same knitter-braider manufactured by the Lamb Knitting Machine Corporation of Chicopee, Massachusetts which is used to form the bulky knit tubes in accordance with the invention of U.S. application Ser. No. 032,960.
With reference to FIG. 4, the Lamb knitter braider is capable of knitting small diameter wire into the stitch pattern shown. The wire is bare of insulation so that the entire surface of the wire is capable of conducting and dissipating electrostatic charges which may otherwise build up in the filter tube, and the continuity of the knitted stitches assures conduction of the charge to a grounding point from any point along the entire length of the grounding element. To this end as shown in FIGS. 2 and 3, the grounding element is shown at 131 and is attached to the fabric 112 of the filter bag 109 and extends throughout the length and is wrapped around the cuff provided by the turned back portion at the top of the cylindrical tube.
In the present instance the grounding element 113 comprises a tube of knitted wire which is knitted in circumscribing relationship to a second tube of knitted wire, both tubes having been formed on the knitter-braider described above and having the stitch pattern shown in FIG. 4. In this case each tube is formed as shown in FIG. 4 with four wales of knitted loops 41,42,43 and 44 formed from four strands of wire 45, 46, 47 and 48. In each wale, the loops alternate between two strands of wire, each strand of wire in turn alternating between adjacent wales of needle loops. In the fabrication of the grounding elements, a first knitted tube of wire is formed on the knitter-braider and is collected in a suitable collection can or it may be loosely wound on a package. The strand thus formed is then fed through the hollow cylinder of a subsequent knitter-braider and a second knitted tube is knitted around the previously-knit tube and the two tubes are drawn off together telescopically-related one within the other, and are flattened to form the grounding element shown at 131 in FIGS. 2 and 3. The flattening of the two telescopically-related knitted structures insures surface-to-surface contact between the several strands which compose the grounding element, and the multiple-loop structure afforded by the knitted fabrics insures multiple conductive paths between the strands comprising the grounding component.
The grounding element is not limited to use in a filter system as shown in FIG. 1, but has a wide applicability in other structures which require a grounding element having good electrical conductivity, wide surface exposure, good flexibility and durability under stress, such as required for dissipating electrostatic charges.
While a particular embodiment of the present invention has been herein illustrated and described it is not intended to limit the invention to such disclosure. For example, the grounding component may be knitted as a single component and flattened to provide multiple conductive paths between the loops formed by the strands in diagonally-opposite walls. Other changes and modifications may be made therein and thereto within the scope of the following claims.
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A grounding component for dissipating electrostatic charges in bag filters, which is adapted to be attached to the filter bags to extend along the length thereof. The component comprises a pair of telescopically-related knitted tubes formed from stands of electrically-conductive material. Each tube has a number of wales equal to the number of strands and is knitted with a non-run stretch pattern.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 12/247,012, filed Oct. 7, 2008, which is a Divisional Application of U.S. patent application Ser. No. 10/746,210, filed Dec. 23, 2003, now U.S. Pat. No. 7,449,024 the disclosure of which is incorporated herein by this reference.
BACKGROUND
[0002] 1. Background and Relevant Art
[0003] The present invention relates generally to apparatus and methods for the suturing of body lumens. More particularly, the present invention relates to techniques for percutaneous closure of arterial and venous puncture sites, which are usually accessed through a tissue tract.
[0004] A number of diagnostic and interventional vascular procedures are now performed translumenally. A catheter is introduced to the vascular system at a convenient access location and guided through the vascular system to a target location using established techniques. Such procedures require vascular access, which is usually established during the well-known Seldinger technique, as described, for example, in William Grossman's “Cardiac Catheterization and Angioplasty,” 3.sup.rd Ed., Lea and Febiger, Philadelphia, 1986, incorporated herein by reference. Vascular access is generally provided through an introducer sheath, which is positioned to extend from outside the patient body into the vascular lumen.
[0005] When vascular access is no longer required, the introducer sheath is removed and bleeding at the puncture site stopped. One common approach for providing hemostasis (the cessation of bleeding) is to apply external force near and upstream from the puncture site, typically by manual or “digital” compression. This approach suffers from a number of disadvantages. It is time consuming, frequently requiring one-half hour or more of compression before hemostasis is assured. Additionally, such compression techniques rely on clot formation, which can be delayed until anticoagulants used in vascular therapy procedures (such as for heart attacks, stent deployment, non-optical PTCA results, and the like) wear off. This can take two to four hours, thereby increasing the time required before completion of the compression technique. The compression procedure is further uncomfortable for the patient and frequently requires analgesics to be tolerable. Moreover, the application excessive pressure can at times totally occlude the underlying blood vessel, resulting in ischemia and/or thrombosis. Following manual compression, the patient typically remains recumbent from four to as much as twelve hours or more under close observation so as to assure continued hemostasis. During this time renewed bleeding may occur, resulting in blood loss through the tract, hematoma and/or pseudoaneurysm formation, as well as arteriovenous fistula formation. These complications may require blood transfusion and/or surgical intervention.
[0006] The incidence of complications from compression-induced hemostasis increases when the size of the introducer sheath grows larger, and/or when the patient is anticoagulated. It is clear that the compression technique for arterial closure can be risky, and is expensive and onerous to the patient. Although the risk of complications can be reduced by using highly trained individuals, dedicating such personnel to this task is both expensive and inefficient. Nonetheless, as the number and efficacy of translumenally performed diagnostic and interventional vascular procedures increases, the number of patients requiring effective hemostasis for a vascular puncture continues to increase.
[0007] To overcome the problems associated with manual compression, the use of bioabsorbable fasteners or sealing bodies to stop bleeding has previously been proposed. Generally, these approaches rely on the placement of a thrombogenic and bioabsorbable material, such as collagen, at the superficial arterial wall over the puncture site. While potentially effective, this approach suffers from a number of problems. It can be difficult to properly locate the interface of the overlying tissue and the adventitial surface of the blood vessel. Locating the fastener too far from that interface can result in failure to provide hemostasis, and subsequent hematoma and/or pseudo-aneurysm formation. Conversely, if the sealing body intrudes into the arterial lumen, intravascular clots and/or collagen pieces with thrombus attached can form and embolize downstream, causing vascular occlusion. Also, thrombus formation on the surface of a sealing body protruding into the lumen can cause a stenosis, which can obstruct normal blood flow. Other possible complications include infection, as well as adverse reaction to the collagen or other implant.
[0008] A more effective approach for vascular closure has been proposed in U.S. Pat. Nos. 5,417,699, 5,613,974; and PCT published Patent Application No. PCT/US96/10271 filed on Jun. 12, 1996, the full disclosures of which are incorporated herein by reference. A suture-applying device is introduced through the tissue tract with a distal end of the device extending through the vascular puncture. One or more needles in the device are then used to draw suture through the blood vessel wall on opposite sides of the puncture, and the suture is secured directly over the adventitial surface of the blood vessel wall to provide highly reliable closure.
[0009] While a significant improvement over the use of manual pressure, clamps, and collagen plugs, certain design criteria have been found to be important to successful suturing to achieve vascular closure. For example, it is highly beneficial to properly direct the needles through the blood vessel wall at a significant distance from the puncture so that the suture is well anchored in the tissue and can provide tight closure. It is also highly beneficial to insure that the needle deployment takes place when the device is properly positioned relative to the vessel wall. The ease of deployment and efficacy of the procedure can further be enhanced by reducing the cross-section of that portion of the device, which is inserted into the tissue tract and/or the vessel itself, which may also allow closure of the vessel in a relatively short amount of time without imposing excessive injury to the tissue tract or vessel.
[0010] For the above reasons, it would be desirable to provide improved devices, systems, and methods for suturing vascular punctures. The new device should have the capability of delivering a pre-tied knot to an incision site. It would be particularly beneficial if these improved devices provided some or all of the benefits while overcoming one or more of the disadvantages discussed above.
[0011] 2. Description of the Background Art
[0012] U.S. Pat. Nos. 5,700,273, 5,836,956, and 5,846,253 describe a wound closure apparatus and method in which needles are threaded with suture inside a blood vessel. U.S. Pat. No. 5,496,332 describes a wound closure apparatus and method for its use, while U.S. Pat. No. 5,364,408 describes an endoscopic suture system.
[0013] U.S. Pat. No. 5,374,275 describes a surgical suturing device and method of use, while U.S. Pat. No. 5,417,699 describes a device and method for the percutaneous suturing of a vascular puncture site. An instrument for closing trocar puncture wounds is described in U.S. Pat. No. 5,470,338, and a related device is described in U.S. Pat. No. 5,527,321. U.S. Pat. No. 5,507,757 also describes a method of closing puncture wounds.
[0014] U.S. Pat. No. 6,245,079, describes another suturing system, the complete disclosure of which is incorporated herein by reference in its entirety for all purposes.
BRIEF SUMMARY
[0015] The present invention provides a device for suturing an opening in a tissue. In various embodiments, the device includes an elongated shaft with a pair of deployable arms. When deployed, these arms are non-perpendicular to the longitudinal axis of the shaft. In one embodiment, the arms are independently deployable. In one embodiment, a first arm is an anterior arm which is deployed by being rotated less than 90 degrees to the longitudinal axis of the shaft, and the second arm is a posterior arm which is deployed by being rotated more than 90 degrees to the longitudinal axis of the shaft. A pivot stop may be provided on the elongated shaft to limit rotation of the arms when they reach their fully deployed position. Each of the first and second arms may include a needle receiving portion thereon. Needles may be advanced longitudinally along the shaft toward the needle receiving portions on the arms. The needles may exit through a side wall of the shaft at a location proximal to the arms.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a cross-sectional view of a suturing system with its distal end inserted through an arterial wall. ( FIG. 1 corresponds to FIG. 41 of U.S. Pat. No. 6,245,079).
[0017] FIG. 2 is a cross-sectional view of the device of FIG. 41 in a partially deployed state. ( FIG. 2 corresponds to FIG. 42 of U.S. Pat. No. 6,245,079).
[0018] FIG. 3 is cross-sectional view of the device of FIG. 1 with the suture clasp member fully deployed. ( FIG. 3 corresponds to FIG. 47 of U.S. Pat. No. 6,245,079).
[0019] FIG. 4A is a front plan view of the present invention in its compact position (i.e. prior to deployment).
[0020] FIG. 4B is a left side elevation view of the present invention prior to deployment.
[0021] FIG. 5A is a front plan view of the present invention after deployment.
[0022] FIG. 5B is a right side elevation view of the present invention after deployment.
[0023] FIG. 6 is an illustration of the system of FIG. 5B deployed at a non perpendicular angle relative to the axis of a blood vessel while the first and second arms 610 and 620 are positioned longitudinally along the inside of the wall of blood vessel.
[0024] FIG. 7 is an embodiment of the present split arm invention, incorporating a pre-tied knot.
DETAILED DESCRIPTION
[0025] FIGS. 1 , 2 and 3 show a suturing device corresponding to the suturing device described in U.S. Pat. No. 6,245,079, the complete disclosure of which is incorporated herein by reference in its entirety for all purposes. Specifically, FIGS. 1 , 2 , and 3 correspond to FIGS. 41, 42 and 47 of U.S. Pat. No. 6,245,079.
[0026] Referring to FIG. 1 , distal portion of the suturing device 520 is positioned in femoral artery 16 . Suturing device 520 comprises a suture introducer head 522 attached to the distal end of a hollow elongated body 514 . Suture clasp member 500 and the needles 546 reside in the same longitudinal space. In other words, the needles 546 share the same housing as the suture clasp member 500 (while they are all in their retracted state), but are higher up (proximally) in the suturing device 520 than the suture clasp member 500 . Flexible needles 546 bend outward, away from the axis of the device 520 , when in the extended position (as shown in FIG. 3 ).
[0027] As shown in FIGS. 2 and 3 , the suture introducer head 522 has two needle ports or apertures 510 formed therein (one per needle 546 ) proximal to the suture clasp arms 524 . Each needle port includes a needle guiding portion 512 (“needle guide”), in the form of an outwardly curved groove or channel, which guides the corresponding needle 546 along a particular path. The needle guides 512 may be formed within the suture introducer head 522 (as shown in FIG. 1 ) as part of a mold, or may be separate pieces (not shown) that are inserted into the suture introducer head 522 during manufacture.
[0028] Bleed back is accomplished by the hole 540 at the distal end 504 of the suture introducer head 522 , the suture clasp arm apertures 508 and any other openings in the suture introducer head 522 . The direction of blood flow for bleed back is shown by the dashed arrows in FIG. 1 .
[0029] Suture 40 closes the artery vessel opening 26 transverse to the flow of blood. Proper insertion of the needles 546 reduces the risk of damage to the vessel walls 22 , 506 .
[0030] Suturing device 520 includes a single, resilient suture clasp member 500 attached to the actuating rod 50 . The suture clasp member 500 comprises a center or hinge portion 542 and two suture clasp arms 524 (one for each needle 546 ). Each suture clasp arm 524 has a suture clasp 544 at the end thereof.
[0031] The hinge portion 542 of the suture clasp member 500 acts as a “living hinge” because it has a memory which causes the member 500 to return to a partially open, unretracted position ( FIG. 2 ) when a force (applied via rod 50 ) is released. This can be seen in FIGS. 1 and 2 . In FIG. 2 , the suture clasp member 500 is deployed in the artery 16 in its predisposed (relaxed or natural) position. In FIG. 1 , the suture clasp member 500 is retracted into the suture introducer head 522 in its compressed (stressed or tensed) position. The arms 524 are moved to the retracted position by applying a distal force to the actuator rod 50 , which causes the arms to contact deflection surfaces 518 ( FIG. 2 ).
[0032] This suture clasp member 500 is preferably composed of a resilient shape memory material such as NITENOL, but may alternatively be composed of another material with spring-like characteristics, such as plastic, spring steel, stainless steel or any variations thereof. Further, the suture clasp member 500 could be composed of two arms that are hingedly connected to the actuating rod 50 without the use of a resilient hinge.
[0033] Needles 546 are flexible and preferably made from a material with shape memory, such as SUPERFLEX NITENOL. Alternatively, the needles 546 may be composed of spring steel, surgical stainless steel or any variation thereof.
[0034] When the needles 546 are advanced distally and come in contact with the needle insertion guides 512 , the needle insertion guides cause the needles 546 to bend radially outward. The needles 546 also preferably further bend slightly (radially outward) when they come in contact with the angled surfaces 545 of the suture clasp arms 524 , as shown in FIG. 3 . When the needles 546 are retracted into the needle lumens 516 , they resume a straight configuration as a result of their resiliency.
[0035] The proximal portion of the suturing device 520 preferably includes a handle which allows the physician to externally operate the suture clasp arms 524 and the needles 546 inside the blood vessel 16 . This handle preferably has three actions: a first action in which the actuating rod 50 applies a proximal force to the hinge portion 542 to deploy and maintain arms 524 in a fully outward position ( FIG. 3 ); a second action to advance the needles 546 distally ( FIG. 3 ) and pull the needles 546 back proximally using one or more springs; and a third action in which the actuating rod 50 applies a distal force to the hinge portion 542 to retract the arms 524 ( FIG. 1 ).
[0036] The locked position of the suture clasp arms 524 provides a stable base or foundation for holding the looped ends of the suture 40 while the needles 546 come in contact with the suture clasp arms 524 and capture the suture 40 . The suture clasp arms 524 are locked in the locked position by the proximal force of the actuating rod 50 , the stationary inside edges 536 of the apertures 508 and the protrusions 528 at the ‘elbow’ end of each arm 524 ( FIG. 3 ). Specifically, when the suture clasp arms 524 become substantially parallel with each other (i.e., each arm 524 is at an angle of approximately 90 degrees from the actuating rod 50 ), the protrusions 528 at the ‘elbow’ end of each arm 524 come into contact with each other and prevent the arms 524 from bending any further than the configuration shown in FIG. 3 . The suture clasp member 500 cannot open any farther, even when the needles 546 are inserted distally and come in contact with the suture clasp arms 524 . The protrusions 528 prevent the suture clasp member 500 from moving unintentionally (opening any farther) when the needles 546 come in contact with the suture clasp arms 524 . This reduces the risk of the looped ends of the suture 40 being accidentally displaced from the suture clasps 544 when the needles 546 engage the suture clasps 544 . Thus, the combination of forces asserted by the actuating rod 50 , the proximal inside edges 536 of the aperture 508 and the two protrusions 528 sustain the suture clasp arms 524 in a rigid, locked position to facilitate the proper removal of the suture looped ends from the suture clasps 544 .
[0037] The slits of the suture clasps 544 are angled in a proximal, radially inward direction. Thus, the face of the looped ends of the suture 40 face in a proximal, radially inward direction. In this configuration, there is less chance of the looped ends of the suture 40 falling off the suture clasps 544 improperly or prematurely. When the needles 546 engage the suture clasp arms 524 , the only direction the looped ends may move is in a proximal, radially inward direction, which is in the opposite direction of the inserted needles 546 . When the needles 546 retract proximally (as shown in FIG. 3 ), the looped ends reliably fall into the suture catches 38 of the needles 546 . It is the proximal movement of the needles 546 which causes the suture catches 38 on the needles 546 to catch the looped ends of the suture 40 . This configuration does not rely on a radially outward tension in the looped ends to fasten the looped ends onto the suture catches 38 when the needles 546 are inserted distally.
[0038] The description of each of introducer sheath 6 , suture catches 38 , needle incisions 248 , pivot pin 502 and lumen 530 is provided by reference to identically numbered elements in U.S. Pat. No. 6,245,079.
[0039] A first important disadvantage of the suturing system illustrated in FIGS. 1 , 2 and 3 is that both of the arms 524 deploy to a position that is exactly 90 degrees from the axis of suturing device. This is because protrusions 528 abut one another when suture clasp 500 is fully opened (as shown in FIG. 3 ). As described above, and in U.S. Pat. No. 6,245,079, it is an advantage of the system of FIGS. 1 to 3 that arms 542 of suture clasp 500 do not open more than 90 degrees to reduce the risk of the looped ends of the suture 40 being accidentally displaced from the suture clasps 544 when the needles 546 engage the suture clasps 544 .
[0040] Unfortunately, this is particularly problematic when suturing inside a blood vessel, since it may be preferred to enter the blood vessel at a non-perpendicular (e.g.: oblique) angle. In the system of FIGS. 1 to 3 , the distal end of the suturing device must therefore be extended to some distance into the blood vessel during operation.
[0041] A first feature of the embodiments of the present split arm suturing device is that each of its arms may be extended to different angles from the body of the device. In various embodiments, such angles are non-perpendicular to the longitudinal axis of the suturing device. More particularly, one arm may be extended to a position less than 90 degrees to the body of the device, whereas the other arm may be extended to a position more than 90 degrees to the body of the device.
[0042] A second feature of various embodiments of the present split arm suturing device is that each of its arms may be extended one at a time.
[0043] Separately, or taken together, these two features of the present invention provide a system which may be conveniently positioned to enter the blood vessel at a non-perpendicular angle, thus minimizing the potential for damage to the blood vessel, while ensuring proper placement of the suture. Thus, an operator can gain better access to smaller arteries and maintain a smaller elbow height, as compared to the suturing device of FIGS. 1 to 3 . Thus, the present independently operable split arm suturing device offers significantly increased flexibility to the operator, as compared to the suturing device of FIGS. 1 to 3 .
[0044] Referring first to FIGS. 4A and 4B , split arm suturing device 600 is shown prior to deployment (i.e. in its compact position). Suturing device 600 has moveable arms 610 and 620 which can be pivoted relative to the longitudinal axis L of suturing device 600 . Arms 610 and 620 may be independently moveable. As will be shown herein, when deployed, arm 610 will preferably be deployed in an anterior direction, and arm 620 will preferably be deployed in a posterior direction.
[0045] Anterior arm 610 and posterior arm 620 may be made independently moveably by any of a variety of mechanisms, all keeping within the scope of the present invention. In the illustrated embodiments, arms 610 and 620 are independently actionable (i.e. moveable between compact and deployed positions) by flexible linkages in tension or compression. It is to be understood, however, that any push pull wire, gear or cam system, or any other suitable actuation system may be used, all keeping within the scope of the present invention. As illustrated in FIG. 5B , arm 610 may be deployed by moving linkage 612 , and arm 620 may be deployed by moving linkage 622 . Specifically, by pulling linkage 612 proximally, anterior arm 610 rotates around pivot 614 until finger 611 contacts pivot stop 625 . Similarly, by pulling linkage 622 proximally, posterior arm 620 rotates (in an opposite direction) around pivot 624 until stop surface 621 contacts pivot stop 625 . Specifically, anterior arm 610 moves through angle A 1 when moved from its compact position to its deployed position. Referring to FIG. 6 , posterior arm 620 moves through angle A 2 when moved from its compact position to its deployed position. As can be appreciated, by instead distally pushing linkages 612 and 622 , arms 610 and 620 can be moved back to their compact (i.e.: non-deployed) position.
[0046] After deploying arms 610 and 620 (by retracting linkages 612 and 622 ) a first needle 616 , and a second needle 626 can then be advanced toward the distal ends of arms 610 and 620 , respectively to retrieve opposite ends of a suture 40 . In various embodiments, needles 616 and 626 are longitudinally advanceable along the shaft 601 of suturing device 600 , and exit through side wall openings 630 and 640 at locations proximal to the arms 610 and 620 , respectively.
[0047] FIG. 6 shows an embodiment of the present invention deployed at a non perpendicular angle relative to the axis of a blood vessel BV while the anterior arm 610 and posterior arm 620 are positioned longitudinally along the inside of the wall of blood vessel BV. Specifically, the distal end of suturing device 600 is positioned though a puncture P in blood vessel BV.
[0048] Needles 616 and 626 are advanced longitudinally along through shaft, and exit through side wall openings 630 and 640 , and then puncture through respective needle punctures NP 1 and NP 2 in the wall of blood vessel BV. Thereafter, needles 616 and 626 can be retracted pulling the opposite ends of suture 40 upwardly through punctures NP 1 and NP 2 in the wall of blood vessel BV.
[0049] In various embodiments, cuffs 618 and 628 can be provided at opposite ends of suture 40 to ensure that the distal ends of needles 616 and 626 connect securely onto the opposite ends of suture 40 . Various embodiments of cuffs, links, barbs, fasteners, or combinations thereof are also contemplated to ensure that the distal ends of needles 616 and 626 connect securely onto the opposite ends of suture 40 . Thus, cuffs 618 and 628 may be any of a variety of different designs.
[0050] Referring again to FIGS. 5A and 5B , by moving linkages 612 and 622 independently, and to different distances, arms 610 and 620 may be independently deployed to different angles relative to the longitudinal axis L of the body of suturing device 600 . For example, as shown in FIGS. 5A and 5B , arm 610 may be rotated less than 90 degrees from the axis of the elongated body of suturing device 600 , whereas 620 may be rotated more than 90 degrees from the axis of the elongated body of suturing device 600 .
[0051] As shown in FIG. 6 , this advantageously allows the elongated body of suturing device 600 to be positioned through tissue Tract T (entering through skin S) at a non-perpendicular angle relative to the axis of a blood vessel BV while the first and second arms 610 and 620 are positioned longitudinally along the inside of the wall of blood vessel BV for placement of the suture axially along the blood vessel and across the puncture. Specifically, suturing device 600 can be used to position the ends of suture 40 at locations such that they can be retrieved by needles 616 and 626 , and pulled upwardly through needle punctures NP 1 and NP 2 , respectively.
[0052] In various embodiments, the elongated body of suturing device 600 is sufficiently rigid to maintain alignment of needles 616 and 626 with arms 610 and 620 , respectively. As can be seen, in various embodiments, needles 616 and 626 may be of different lengths.
[0053] As shown in FIG. 7 , a pre-tied knot feature may also be incorporated into suturing device 600 . The pre-tied knot may initially be positioned wrapped around an exterior surface of the suturing device. Specifically, a length of suture 40 having opposite ends and a bight 680 of suture therebetween may be provided with bight 680 being disposed around an exterior surface of device 600 . Bight 680 may alternately be pre-arranged around one of the needles and within the elongated body.
[0054] Bight 680 includes one or more loops of suture that form a pre-tied knot 690 when one or more ends of suture 40 are advanced through bight 680 . Bight 680 of suture may be prearranged in any of several configurations on the device. For example, bight 680 may be pre-arranged so as to define a square knot, a clinch knot or a variety of known or new surgical knots.
[0055] In various embodiments, suture 40 is arranged to provide the pre-tied knot 680 that automatically travels down from the shaft of the device 600 where it is stored prior to delivery to the tissue wall. In various embodiments, to distinguish the ends of suture 40 , during deployment, the ends of the suture may be distinguished from each other by changing the color of one end (e.g. with dye), providing an attachment on one end (e.g. shrink wrap tubing, a bead, etc.) or with the suture itself (e.g. tying a knot in one end).
[0056] In accordance with the present invention, suture bight 680 is disposed on the outside surface of device 600 , as shown. In this embodiment, suture 40 does not pass through the interior of the device. It should be understood, however, that other embodiments of the invention may include suture 40 and bight 680 stored inside the shaft or housing of the device rather than on the outside. Yet other configurations may include detachable tips and connecting filaments to enable a pre-tied knot.
[0057] After needles 616 and 626 retrieve opposite ends of suture 40 , and pull these ends of the suture back up through the center of bight 680 to define the pre-tied knot 690 , and arms 610 and 620 are rotated back to a non-deployed position, device 600 may be removed from the patient. Pre-tied knot 690 will slide down the shaft, resulting in a suture pattern in which the opposite ends of suture 40 pass upwardly through the center of bight 680 .
[0058] While embodiments and applications of this invention have been shown and described, it will be apparent to those skilled in the art that various modifications are possible without departing from the scope of the invention. It is, therefore, to be understood that within the scope of the appended claims, this invention may be practiced otherwise than as specifically described.
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A device for suturing an opening in a tissue, having an elongated shaft, at least two arms movable to a deployed positioning which the arms are non-perpendicular to the shaft, the arms having needle receiving portions; and needles advanceable longitudinally along the shaft toward the needle receiving portions, the needles exiting through side walls of the shaft at a location proximal to the arms.
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PRIORITY
[0001] This application claims priority to U.S. Provisional Application No. 62/302,543, filed Mar. 2, 2016, and entitled KART KANOPY, which is incorporated herein by reference.
FIELD OF THE DISCLOSURE
[0002] The present disclosure relates generally to a protective canopy and associated housing. In particular, but without limitation, the present disclosure relates to a collapsible and retractable canopy that may protect a user from sun, rain, or other objects and may be attached to other objects, such as golf carts.
BACKGROUND OF THE DISCLOSURE
[0003] In recent years, wheeled push carts for carrying golf bags have become popular with golfers who walk golf courses. These golf push carts typically have three or four wheels that form a stable base and hold a golf bag at an angle of approximately 45 degrees. They also typically have a handle extending from an area near the top of the golf bag that can be used to push the cart and to attach accessories. For the purposes of the present disclosure, the term “golf carts” may be used to refer to these types of carts, rather than to motorized driving golf carts in which a driver and one or more passengers can sit.
[0004] Some golf carts have an umbrella holder as an accessory attached to the handle, in recognition of the need golfers have for rain and sun protection. Sun protection is especially crucial since the sunniest days encourage golfers to stay out for many hours. As golfers become more aware of the risks of excessive sun exposure, such as skin cancer, more golfers require adequate sun protection while golfing. While an umbrella can provide some protection, there are some limitations to its effectiveness in an umbrella holder. One main limitation is that the area of shade provided by the umbrella changes size, shape, and location based on the position of the sun. When a golfer is stationary and not moving the golf cart, the golfer may position him or herself in the shade, but when the golfer is pushing the cart, he or she must necessarily stand and walk near the handle. This location may be underneath the umbrella, but the shade cast by the umbrella may be in a different location, and the golfer may still be exposed to direct sunlight. Another limitation to umbrellas in umbrella holders is that they are prone to being blown away even in light winds. It is also impractical for a golfer to hold an umbrella in hand while pushing a golf cart. Therefore, a need exists for convenient, lightweight protective covers that remedy these problems. A need exists for apparatuses that can be conveniently attached to objects, including golf carts, to provide adequate shade and other protection for users.
SUMMARY
[0005] One aspect of the present disclosure provides a collapsible protective canopy comprising a plurality of inflatable frame members, the frame members forming a rectangular top frame having a first end and a second end, and a rectangular back frame having a first end and a second end, the first end of the rectangular top frame being attached to the first end of the rectangular back frame. The protective canopy may further comprise at least one diagonal frame member attached to the second end of the rectangular top frame and the second end of the rectangular back frame. The canopy may further comprise one or more flexible shade panels, wherein at least one of the flexible shade panels is disposed between the plurality of frame members forming the rectangular top frame.
[0006] Another aspect of the disclosure provides a collapsible canopy system, which may comprise an inflatable canopy cover. The inflatable canopy cover may itself comprise a plurality of inflatable frame members, the frame members forming a top frame having a first end and a second end, and a back frame having a first end and a second end. The first end of the top frame may be attached to the first end of the back frame. The inflatable canopy may comprise one or more flexible shade panels, wherein at least one of the flexible shade panels is disposed between the plurality of frame members forming the top frame. The system may also comprise a canopy housing, which itself may comprise an air pump configured to pump air into at least a portion of the inflatable canopy cover, a mechanism for attaching the canopy housing to another object, and a storage compartment configured to retain the inflatable canopy cover when it is in a deflated state.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 shows a canopy system of the present disclosure comprising a canopy cover in an inflated configuration attached to a canopy housing.
[0008] FIG. 2 shows a back perspective view of a canopy cover in accordance with an embodiment of the present disclosure.
[0009] FIG. 3 shows a front perspective view of the canopy cover of FIG. 2
[0010] FIG. 4 shows a back side elevation view of the canopy cover of FIG. 2
[0011] FIG. 5 shows a left side elevation view of the canopy cover of FIG. 2
[0012] FIG. 6 shows a right side elevation view of the canopy cover of FIG. 2
[0013] FIG. 7 shows a top plan view of the canopy cover of FIG. 2
[0014] FIG. 8 shows a front elevation view of the canopy cover of FIG. 2
[0015] FIG. 9 shows an exemplary canopy housing apparatus in accordance with the present disclosure retaining a canopy cover in a deflated position.
[0016] FIG. 10 shows an exemplary canopy housing apparatus in accordance with the present disclosure with some interior components exposed.
DETAILED DESCRIPTION
[0017] All illustrations of the drawings are for the purpose of describing embodiments of the present disclosure, and are not intended to limit its scope. The following description may be best understood with reference to the accompanying numbered figures.
[0018] FIG. 1 shows an embodiment of a collapsible canopy system 100 in accordance with the present disclosure. The collapsible canopy system 100 (which may also be referred to solely as a “canopy system”) shown comprises a canopy housing 110 , which will be described in further detail later in the disclosure, and a canopy cover 120 disposed thereon. The canopy cover 120 may be inflatable, flexible, and collapsible into a storage configuration. The mechanism for inflating, collapsing, and storing of the canopy cover 120 will be described in detail later in the disclosure. The collapsible canopy system 100 may be particularly suitable for attachment to a handle of a golf cart, and its overall design may provide many advantages when used in conjunction with a golf cart; however, the collapsible canopy system 100 of the present disclosure should not be construed to be limited to such uses. The canopy system 100 may be attached to other objects or surfaces, such as a stroller or a stationary rail, for example. The canopy cover 120 is shown in its fully inflated configuration and attached to the canopy housing 110 in FIG. 1 .
[0019] FIG. 2 shows a perspective view of the canopy cover 200 (similar to canopy cover 120 of FIG. 1 ) by itself. As shown, it comprises a frame 225 , which itself may comprise a plurality of “structural frame members” ( 231 - 237 ) and two “diagonal frame members,” ( 261 , 262 ) as they may be referred to throughout the disclosure. Each of the frame members may comprise substantially hollow, flexible, collapsible tubes. These hollow tubes may be configured as a plurality of individual segments joined together, and be made of fabric, plastics, polymers, or other suitable flexible material. The seams (e.g., seams 227 , 229 ) show where individual segments may be joined together by stitching, welding, gluing, or any other form of attachment. In other embodiments, the hollow tubes may be formed by a unitary construction, or segments may be joined together at different locations.
[0020] In the configuration shown, the frame 225 of the canopy cover 220 may comprise top frame members (structural frame members) 231 , 232 , 233 , and 234 , which form a “top frame” 230 . In the embodiment shown, the top frame 230 is rectangular, but it is contemplated that in other embodiments, the top frame may form a different geometrical shape (e.g., rounded or curved in parts). The frame 225 may further comprise back frame members 235 , 236 , and 237 , which together with top frame member 234 form a back frame 240 . In the embodiment shown, the back frame 240 is rectangular, but it may be shaped differently in other embodiments. The back frame 240 may be attached to two mounting frame members 251 and 252 . The mounting frame members 251 and 252 may be attached to back frame member 137 as well as to back frame members 235 and 236 for structural support. In some embodiments, the attachment points may allow air to flow from the mounting frame members 251 and 252 and into back frame members 235 , 236 , and 237 to inflate them.
[0021] The top frame 230 and back frame 240 may be supported at a substantially right angle in relation to one another by diagonal frame members 261 and 262 . In other embodiments, the angle between the top frame and back frame may be more obtuse or acute. The space between the diagonal members 261 and 262 may form a front opening, within which a user may stand in the shade provided by the canopy cover 200 . The diagonal members 261 and 262 are shown attached at approximately 45 degree angles from the top frame 230 and back frame 240 , but in other embodiments, they may be arranged at different angles.
[0022] It is contemplated that in some embodiments, each of the individual frame members may be hollow and inflatable. However, in other embodiments, some of the frame members may be of solid (i.e., non-hollow) construction while others may be of hollow construction. Additionally, some frame members may be thicker than others to provide the desired structural support for a particular embodiment. There may be additional supporting frame members other than the ones shown in FIG. 2 (e.g., crossing or parallel buttressing members), or the frame members may be arranged in different configurations The variations in configuration may allow for different embodiments to be lighter or heavier, more flexible or less flexible, and more quickly or more slowly inflatable.
[0023] Turning now to FIG. 3 , the canopy cover 200 of FIG. 2 is shown from a different perspective as canopy cover 300 . The canopy cover 300 comprises several flexible panels between the tubes of the frame 325 . A top shade panel 330 may comprise substantially or completely opaque material and provide shade for a user below. Referring briefly to FIG. 4 , which shows the canopy cover 400 from a back elevation view, a back shade panel 410 may also comprise substantially or completely opaque material to provide shade from the direction it faces. The back shade panel 410 may also comprise a window 430 within the opaque material that is made of a translucent or transparent material. This window 430 may allow the golfer to stay in the shade and protection provided by the opaque material while walking with the cart while still being able to see where the golfer is walking. The back shade panel 450 may also comprise a cut-out opening 450 . This cut-out opening 450 may be large enough for a golfer to reach his or her hand through and pull a golf club out of his or her bag. The opening 450 may provide the most convenient way to access the golf clubs while the canopy cover is in its inflated position. Because of the way the canopy system may be mounted on a particular golf cart, the canopy cover may sometimes be in the pathway through which golf clubs are usually taken out of the golf bag.
[0024] Turning back to FIG. 3 , the canopy cover may further comprise side panels 340 and 350 . These side panels 340 and 350 may be transparent or translucent, depending on the embodiment. They may also be interchangeable in some embodiments. Some embodiments may utilize translucent side panels that are somewhat dark and provide some shade while simultaneously allowing a golfer standing inside to see through them. The shade panels 330 and 410 (of FIG. 4 ), as well as side panels 340 and 350 , may all be formed out of a flexible material that allows the entire canopy cover to collapse and be rolled up and stored when the frame is deflated. Any suitable flexible material may be used, such as fabric, plastic, or polymers. In some embodiments, thin PVC sheeting may be used.
[0025] FIGS. 5 through 8 show the canopy cover of FIG. 2 from different perspectives for clarity. FIG. 5 shows a left side elevation view, FIG. 6 shows a mirror image right side elevation view, FIG. 7 shows a top plan view, and FIG. 8 shows a front elevation view. The canopy cover may be made in any suitable size, and may have a variety of shapes without departing from the disclosure. For example, some embodiments may have longer top panels or longer back panels; some may be rounded or curved; some may have only one diagonal frame member; and some may have detachable panels.
[0026] Another aspect of the present disclosure is an apparatus for inflation, deflation, and storage for the canopy cover. The apparatus may be referred to throughout this disclosure as a “canopy housing,” and may include mechanisms by which to attach the canopy cover to a handle of a golf cart (or any other object, such as a railing, pole, stand, other cart handle, etc.). FIG. 9 shows an embodiment of a canopy housing 900 in accordance with the present disclosure. In the embodiment shown, the canopy housing 900 comprises a substantially cylindrical body 910 . The cylindrical body 910 may be attached to a top side of golf cart handle on its underside. The cylindrical body 910 may be attached using any suitable mechanism, such as hook-and-loop fabric straps, clamps, clips, buttons, or the like. Such attachment mechanisms may be suited to allow a user to install a canopy housing onto a variety of existing golf cart handles themselves, or may be specifically designed to fit a particular make and/or model of golf cart. The canopy housing and canopy cover together are designed to be lightweight, such that even when the canopy cover is fully extended and the golf cart is empty, the weight of the cart canopy would not cause the golf cart to tip or be imbalanced. In some embodiments, the mechanism for attachment to another object may include a mechanism for raising and lowering the height of the entire canopy system. Such mechanisms may include, for example, telescoping poles, springs, folding stands, pistons, or hydraulic lifts. In some embodiments, the mechanism for attachment to another object may include a rotating mechanism, such as a wheel with locking pins, to allow the entire canopy system to articulate forward and backward along an axis parallel to a longitudinal axis of the cylindrical body 910 .
[0027] Still referring to FIG. 9 , the canopy housing 900 comprises a top cover 920 that is configured to slide over the canopy cover when it is in a deflated and/or collapsed position and retained within the cylindrical body 910 . In the embodiment shown, the top cover 920 may roll to the front, away from the mounting frame members 940 and 950 . Referring briefly to FIG. 10 , a rolled-up version of the canopy cover 1050 is shown with a top cover hidden from view. In some embodiments, the collapsed canopy cover may be manually rolled up and tucked into the cylindrical body. In other embodiments, the collapsed canopy cover may be automatically retracted into the cylindrical body 910 . Such a retraction may be accomplished by, for example, a motorized roller, or a mechanical spring-loaded roller, which is not shown. The retraction could alternatively be accomplished by the automatic folding of the canopy cover structure as it gets deflated. Regardless of the mechanism by which the canopy cover is retracted, when the canopy cover is tucked within the cylindrical body 910 , it may be retained by the top cover 920 sliding back over it. Because the canopy cover can be collapsed, retracted, and stored, the canopy housing 900 provides the benefit of being able to keep the canopy cover out of the way and protected from damage when it is not needed.
[0028] FIG. 9 shows how the mounting frame members 940 and 950 may attach to the canopy housing at respective base attachment ends 945 and 955 . These base attachment ends 945 and 955 may attach to a mounting bracket 970 of the canopy housing 900 . The mounting members 940 and 950 may protrude from the cylindrical body 910 through cut-outs 915 and 917 .
[0029] Turning to FIG. 10 , the canopy housing 1000 is shown with the top cover and a cover for an inflation mechanism housing 1040 removed. The mounting members 940 and 950 shown in FIG. 9 are not shown in FIG. 10 . The canopy housing 1000 may also comprise an inflation mechanism 1030 , such as a motorized (or, alternatively, manual) air pump. The inflation mechanism 1030 may push air into the canopy cover through one or more holes in one or more tubes of the canopy cover. In the embodiment shown, a hole 1070 through the cylindrical body 1010 allows the inflation mechanism 1030 to inflate the canopy cover 1050 . It is contemplated that in various embodiments, the inflation hole or holes may be located in different places based on several factors, such as how quickly the canopy cover needs to be inflated or the particular configuration of the inflatable tubes of the canopy cover.
[0030] The inflation mechanism 1030 , if motorized, may be battery-powered. FIG. 10 shows a battery pack 1035 that may comprise disposable or rechargeable batteries. If rechargeable batteries are used, the canopy housing may further comprise a charging port 1037 . In some embodiments, one or more solar panels may be disposed on the canopy cover or canopy housing to provide power to charge the batteries. In some embodiments, the inflation mechanism may also be a deflation mechanism, such as a motorized air pump that runs in reverse and sucks the air out of the canopy cover. One or more buttons 1055 may be disposed on an outer surface of the canopy housing to initiate inflation and/or deflation, which allow for easy set up and take-down of the canopy cover 1050 . In other embodiments, the canopy cover may be deflated simply by opening or uncovering one or more valves through which air can escape. In such embodiments, excess air may be forced out of the valve or valves when the canopy cover 1050 is manually or automatically rolled or retracted. The valves may be located in any place on the structure of the canopy to allow the air to escape efficiently.
[0031] The canopy housing 1000 may be composed of a substantially rigid, durable material that is suitable for protecting its components from weather or other damage. Suitable materials may include, but are not limited to plastics, metals, and polymers. Various materials may be chosen based on their desirable features, including, for example, their durability, lightness, and their properties when exposed to sunlight for prolonged periods of time. It is contemplated that a suitable material would not be very reflective, such as to avoid causing a glare, and would not retain excessive heat, such as to avoid being too hot to the touch. Further, a suitable material would be fairly resistant to damage from sun exposure, and would likely be waterproof.
[0032] The canopy housing 1000 may comprise various attachment points to the canopy housing 1000 for the structure of the canopy cover when it is fully extended or inflated. The attachment points may be in addition to any attachment points specifically for the inflation of the structure or the attachment points of the mounting members 940 and 950 shown in FIG. 9 . The attachment points may be coupled to mechanisms for adjusting the position of the canopy cover separately from the canopy housing 1000 when fully extended. For example, the distal ends 1060 and 1080 of the canopy housing may comprise telescoping poles or other raising mechanisms for raising the entire canopy cover vertically, in order to adjust its height for taller users. The distal ends 1060 and 1080 may also comprise a rotating mechanism to allow the entire canopy cover to rotate downward.
[0033] The collapsible canopy and canopy system described in the present disclosure may advantageously allow a golfer to stand underneath the canopy protected from sun, wind, and other hazards. The canopy system itself may be lightweight, easy to install, easy to use, and quick to inflate, deflate, and store.
[0034] 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.
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A collapsible canopy system comprises an inflatable canopy cover, which may itself comprise a plurality of inflatable frame members, the frame members forming a top frame having a first end and a second end, and a back frame having a first end and a second end, the first end of the top frame being attached to the first end of the back frame and one or more flexible shade panels, wherein at least one of the flexible shade panels is disposed between the plurality of frame members forming the top frame. The system may comprise a canopy housing itself comprising an air pump configured to pump air into at least a portion of the inflatable canopy cover, a mechanism for attaching the canopy housing to another object, and a storage compartment configured to retain the inflatable canopy cover when it is in a deflated state.
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RELATED APPLICATION DATA
[0001] This application claims the priority of U.S. Provisional Application No. 61/032,244, filed on Feb. 28, 2008, which is hereby incorporated in its entirety by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to determining the position of body parts which are connected to a joint of an anatomical body, for example of a human or animal. The joint can for example be a knee joint, a shoulder joint, a hip joint, etc. These joints each have the property that there is a left joint and a right joint which exhibit symmetrical kinematics, i.e. in the ideal case of a healthy body, the possible movement trajectories are symmetrical, in particular with respect to a symmetry plane and/or symmetry axis. The invention uses the kinematic symmetry of the joints to deduce—from the position of body parts which are connected to a joint on one side of the body—a possible or desired position of body parts which are connected to the joint which is symmetrical to it on the other side of the body part. With respect to the kinematics of the joints, reference may be made to the standard work by I. A. Kapandji “The Physiology of the Joints”, in which the human biomechanics, including the kinematics, of the joints is described.
[0003] The present invention also relates not only to using anatomical symmetry to the extent that it relates to the kinematics of the movement, but also or alternatively relates to using anatomical symmetry to the extent that it relates to the static position of the body parts. In particular, the static symmetry is used to determine the position of body parts or the relative position of body parts. In the ideal case, the anatomical body is symmetrical with respect to a symmetry plane, the median sagittal plane. On the basis of this ideal assumption, it is possible to calculate the position of a body part which it would occupy, given an ideal symmetry. It is also possible to calculate what the relative position of the body parts would look like, given an ideal anatomical (static) symmetry.
BACKGROUND OF THE INVENTION
[0004] A method for determining the femoral anchorage point of a cruciate knee ligament is described in European patent specification DE 693 19 212 T2. Measuring an antetorsion angle of a femur is known from US 2007/0161929 A1 and EP 1 788 581 A1. Reference is also made to these documents, which are hereby incorporated into the disclosure, with respect to determining axes and orientations of a body part and assigning reference frames to a body part.
SUMMARY OF THE INVENTION
[0005] It is an object of the invention to determine the position or relative position of body parts, taking into account the anatomical symmetry of an anatomical body which is given in the ideal case.
[0006] It is in particular an object of the invention to determine the position which a body part occupies or would occupy if the joint connected to it had kinematics which are symmetrical with respect to the corresponding joint arranged on the other side of the body.
[0007] The above object is solved by the subjects of the independent claims. Advantageous developments follow from the sub-claims.
[0008] The invention is in particular intended to assist in identifying and quantifying misplacements of body parts which follow from anatomical symmetry observations. It is then of course left to the physician to assess whether there is a misplacement and which of the two sides of the body has a misplacement and which side represents a healthy placement. The invention can also help in assessing relative placements of body parts. It is for example possible to compare the extent of a varus or valgus on one side of an anatomical body with the extent of a varus or valgus on the other side. It is also for example possible by means of the invention to compare the maximum abduction of the femur on one side with the maximum abduction of the femur on the other side. It is in particular possible to determine where a body part would be situated after a movement about a joint, if it behaved symmetrically with respect to the body part which anatomically corresponds to it.
[0009] The invention relates to calculating the position or relative position of body parts, using symmetry rules. The symmetry rules are based in particular on providing data (symmetry plane data) which determines or implies the position of a symmetry plane of the body—also referred to here as a body symmetry plane—in particular relative to the body parts and/or in a common reference frame. The position of a symmetry plane is in particular implied if it is presupposed that two anatomically corresponding body parts (for example, a left and right upper leg), the position of which is described by body part data (see below), are arranged symmetrically with respect to the symmetry plane, wherein a first-side body part is a body part which lies on one of the two sides of the anatomical body which are separated by the body symmetry plane. The second-side body part lies on the other side. First-side body part data describes the position of the at least one first-side body part. The invention can thus be applied to one, two, three or more body parts on each side. The second-side body part data correspondingly describes the position of the at least one second-side body part. The position of a body part or of two or more body parts is preferably mirrored on the body symmetry plane. Preferably, the mirrored position of a second-side body part is compared with the position of the first-side body part which anatomically corresponds to the second-side body part. In particular, a deviation between the mirrored position of the second-side body part and the position of the anatomically corresponding first-side body part is determined and/or displayed. It is in particular displayed overlapping, such that both the mirrored position of the second-side body part and the non-mirrored position of the first-side body part are visible to the observer. They can be displayed simultaneously, or the observer can switch back and forth between the two images, or they are for example arranged next to each other.
[0010] In addition to or as an alternative to comparing a non-mirrored position with a mirrored position, the positions of at least two second-side body parts are compared with each other; to this end, a relative position of the at least two second-side body parts is in particular determined or provided. The determination of the mirrored relative position is based on the second-side body part data and the symmetry plane data.
[0011] The aforesaid determination of the mirrored relative position can be made in various ways. For example, the position of a first second-side body part can be mirrored and the position of a second second-side body part can likewise be mirrored. The relative position between the mirrored position of the first second-side body part and the mirrored position of the second second-side body part is then calculated. This is then the mirrored relative position. As an alternative to this, a relative variable can be determined which describes the relative position of the first second-side body part relative to the second second-side body part (on the second side of the body symmetry plane). This relative variable can for example be a vector or can also be two vectors. In the case of two vectors, one vector for example links the starting points of a distance which describes the position of the second-side body parts, and the second vector links the end points of a distance which describes the position of the second-side body parts. This vector or these vectors are then mirrored on the symmetry plane. The mirrored vector or vectors then represent the mirrored relative position.
[0012] The relative position can describe not only the relative position between two different body parts, but also the relative position which one and the same body part occupies when it has two different placements (positions). One position can for example represent the position of the lower leg when the leg is extended, and the other position can represent the position of the lower leg during flexion (for example, 90° flexion). The body part (lower leg) thus occupies two different placements. The relative position between these two different placements is also referred to here as the “placement relative position”. Preferably, a mirrored placement relative position is calculated in accordance with an embodiment. This can for example be performed such that the position of the body part in a first placement is mirrored, and the position of the body part in a second placement is likewise mirrored. The two different mirrored positions, which represent the body part in two different mirrored placements, have a position relative to each other which represents the mirrored placement relative position. In accordance with another approach, the relative position between two placements of the body part can be described by a relative variable, which is for example one or more vectors such as have already been illustrated above. This relative variable (vector or vectors) is then mirrored on the symmetry plane. The mirrored relative variable then describes the mirrored placement relative position. In accordance with an embodiment, the placement relative position mirrored onto one side can then for example be compared with the placement relative position which is given on this side, so as to determine deviations from an ideal anatomical symmetry. In accordance with a particular embodiment, it is in particular possible to determine, on the basis of the mirrored placement relative position, how the anatomically corresponding body part (for example, the left upper leg) would behave when transitioning from a first placement to a second placement, if it underwent the movement—mirrored on the body symmetry plane—of the anatomically corresponding body part on the other side of the body. To this end, one or two vectors are for example positioned on the (first-side) body part which describe the mirrored placement relative position. One vector is for example positioned at the start of a distance which represents the position of the body part, while the other vector is positioned at the end of this distance. If the tips of the vectors are then connected, this results in a distance which represents the placement of the body part if it behaved exactly like the anatomically corresponding body part when moving. Due to the particular importance of this aim, an independent claim is additionally directed to it. The corresponding embodiment is illustrated further below.
[0013] The placement of the body part which is determined in this way can then in turn be compared with the actual placement of the body part. It is thus in particular possible to identify differences in the movement trajectories or in the placement relative positions between one side of the body and the other.
[0014] In one of the embodiments, calculating the mirrored position or positions and/or the mirrored relative positions includes the step of projecting the position or relative position into a plane. This plane is referred to here as the projection plane. If, for example, the varus or valgus of a leg is of interest, then this can be described by a relative variable. The relative variable is in particular an angle which is formed between the lower leg and the upper leg when the leg is extended. This angle can then for example be determined from the positions projected into the projection plane. The so-called frontal plane or coronal plane, which is perpendicular to the sagittal plane, is preferred in this case as the projection plane. The projected position can then be mirrored on the body symmetry plane. It is for example also possible to take a different approach, such as mirroring the non-projected positions first and then projecting the mirrored positions into the projection plane. A relative variable—such as for example the angle between the two body parts in the projection plane—is then in particular determined.
[0015] The position of a body part is for example represented by a distance, as already mentioned. The end points of the distance can for example be determined using landmarks. The position of a body part can also be described by characteristic axes, such as for example a tibial axis, or by planes, for example a plane which virtually lies on the acetabulum. Finally, a generic model of the body part or three-dimensional body part data, which is acquired by means of magnetic resonance or a three-dimensional x-ray recording (CT), can also be used to describe the position of the body part.
[0016] The invention is in particular intended to be used in planning incisions into a body part, in particular bones, for example in planning incision locations such as the location of an anchorage point or the location of a drilling in the body part. It is in particular intended to help in planning incisions which have an effect on the subsequent kinematics of the joint connected to the body part, such as for example a cruciate ligament operation or implanting artificial joints. In the latter case, the body parts connected to the joint are at least partially artificial and not natural.
[0017] One advantage of the invention is that by examining the kinematics of a healthy joint, in particular on the basis of relative placements which body parts of a healthy joint occupy, it is possible to deduce desired kinematics—in particular, desired relative placements (nominal relative placements or nominal neutral placements)—of body parts which are connected to a diseased joint and therefore do not (inherently) occupy or do not stably occupy one or more desired relative placements. Advantageously, the non-ideal kinematics of a diseased joint can be identified and/or prevented from resulting in the operation being incorrectly planned, in particular in the incision location being incorrectly determined. It is also possible to identify when the body parts occupy a relative placement (for example, the so-called “anterior drawer” in the case of a cruciate ligament rupture) which does not correspond to that of a healthy joint.
[0018] Using the present invention, it is advantageously possible—after an operation—to check whether the kinematics achieved by the operation for the joint operated on correspond to the desired kinematics, wherein the kinematics can advantageously be described and measured by at least two, preferably three or more relative placements.
[0019] The method in accordance with the invention serves to calculate the position of body parts which are connected to kinematically symmetrical joints. The flexion-extension movement of the left knee joint is for example symmetrical with respect to the flexion-extension movement of the right knee joint. Raising the left upper arm outwards and to the left is for example symmetrical with respect to raising the right upper arm outwards and to the right. The median sagittal plane of the anatomical body can in particular be adduced as a symmetry plane (body symmetry plane), in order to deduce—from the relative position of two body parts connected to a joint—the position, symmetrical to it, of the body parts which are connected to the joint on the other side of the body. Kinematically symmetrical joints of a body are thus given if the body parts connected to the two joints (one joint on each side of the body, respectively) exhibit a symmetrical movement trajectory when the two joints are actuated in order to achieve an identical movement (for example, flexion, extension; adduction, abduction; internal rotation, external rotation; inclination, reclination, etc.).
[0020] In the following, one side of the body, i.e. for example the side on the left of a symmetry line or plane, for example the median sagittal plane, is referred to as the first side, and the other side of the body, i.e. for example the side on the right of the symmetry line or plane, for example the median sagittal plane, is referred to as the second side. The first side can thus relate to the left or right, and the second side to the other side in each case. The kinematics of the joint on the first side are symmetrical with respect to the kinematics of the corresponding joint on the second side, in the case of an ideally healthy body.
[0021] Using the method in accordance with the invention, it is advantageously possible to calculate the position of a body part on a first side, i.e. a first-side body part (for example, the left lower leg), in particular by calculating the position or relative position of the body parts on the other side of the body, i.e. the second-side body parts (for example, the right upper and lower leg), which are connected to the second-side joint, for example the right knee joint.
[0022] Examples of a first and second first-side body part are the left upper and lower leg. Examples of a first and second second-side body part are the right upper and lower leg. The first-side body parts are connected by a first-side joint, i.e. for example the left knee joint. There is a symmetrical second-side joint with respect to this first-side joint, i.e. for example the right knee joint. In particular, there is an anatomical correspondence (symmetrical anatomical function) between the first first-side body part and the first second-side body part (for example, both are an upper leg). In particular, there is also an anatomical correspondence between the second first-side body part and the second second-side body part (for example, they are both lower legs).
[0023] For rotational movements, for example an external rotation and internal rotation of the arm or leg, a symmetry axis which passes along, for example through, the leg is preferably determined, in order to then derive the corresponding symmetrical movement from this, wherein it is in particular the case that an external rotation on one side corresponds to an external rotation on the other side. The same applies to the internal rotation.
[0024] In accordance with the invention, second-side relative position data is advantageously provided which describes the position of the first second-side body part, for example the right upper leg, relative to the second second-side body part, for example the right lower leg. The relative position data preferably describes this relative position for at least two relative placements of the second-side body part, which are therefore also called second-side relative placements. One example of this is the full extension, i.e. 0° flexion, of the right leg as the first second-side relative placement and a 90° flexion of the right leg as the second second-side relative placement. A third second-side relative placement would for example be a 30° flexion. The relative position data can be described in a reference frame which lies in a first body part, wherein the position of the second body part is described in this reference frame. The relative position data can also be described in another reference frame which for example lies in the operating theatre or in the reference frame of a marker detection device such as is used in a surgical navigation system (IGS, image-guided surgery). The relative position data can describe not only the relative position of the body parts but also the (absolute) position of at least some of the body parts in the reference frame. They can in particular include: the first-side and second-side relative position data, the positions of the first and second first-side and second-side body parts for the first and second second-side relative placement and for the first first-side relative placement and the position of the first first-side body part in the second first-side relative placement, as well as the position of a body symmetry plane.
[0025] The relative position data is preferably determined using markers which have a predetermined, in particular known fixed position with respect to each of the first body part and the second body part. The markers can be active or passive markers which for example passively reflect electromagnetic waves, in particular light, in particular infrared light or ultrasound waves, or emit such waves, wherein a marker device consisting for example of three or more markers (for example, a reference star) is for example connected to one body part and another marker device is connected to the other body part. The connection can be non-invasive, i.e. a flexible marker strap with markers attached to it can for example be wound around a body part, for example the upper leg or lower leg. Alternatively or additionally, individual markers can also be adhered onto the upper leg. This is in particular preferable if said body parts are healthy body parts which are not to be operated on. For the body parts which are to be operated on, a marker device which is fixedly connected to the respective bone and for example screwed into the bone is preferably, but not compulsorily, provided. Preferably, landmarks on the body part are additionally measured, for example by means of pointers or a navigated instrument, which preferably likewise comprise markers and likewise represent an example of a marker device. Two or more markers are for example attached to a pointer, wherein their position relative to the pointer tip is known.
[0026] When determining the deviation between a position or relative position and an ideally symmetrical situation, non-invasive markers such as marker straps or individual markers which can in particular be adhered on the skin are preferably used, so as to burden the patient as little as possible.
[0027] Preferably, first-side relative position data is also provided which describes the position of a first first-side body part, i.e. for example the left upper leg, in a first first-side relative placement, i.e. for example in full extension (0° flexion), relative to a second first-side body part, for example the left lower leg. This relative position data is preferably likewise detected by detecting a reference star or individual markers (for example two, three or more) attached to the first and/or second first-side body part, and/or by detecting landmarks by means of pointers or a navigated instrument. The relative position data is preferably determined by marker detection (reference star and/or pointers) if there is a good probability that the position of the body parts in the first first-side relative placement is not impaired by the disease of the joint, i.e. the position of the first second-side body part relative to the second second-side body part, i.e. for example the right upper leg relative to the right lower leg, is not impaired by the disease. The extension of the leg is cited here as an example in the case of a cruciate ligament rupture. The cruciate ligament rupture impairs the relative position during flexion, but has no effect on the relative position of the left upper leg and left lower leg in full extension. In particular when such a reliable relative placement is not given, the relative position of the first-side body parts in the first first-side relative placement can be deduced from the relative position of the two second-side body parts in a first second-side relative placement by referring to the second-side relative position data and taking into account the symmetry, without measuring the relative position of the first-side body parts in the first first-side relative placement, for example by marker detection. The position of the first first-side body part relative to the second first-side body part, which is described by the first-side relative position data, can be described in any reference frame, for example in a reference frame which lies in the operating theatre or in the reference frame of the aforesaid navigation system. The relative position of the two first-side body parts can in particular also be described in a reference frame which lies in one of the two body parts. In the following, it is assumed that the first-side relative position data determined by marker detection relates to the first first-side relative position. Its is therefore also called the first first-side relative position data. It is also assumed that second and subsequent first-side relative position data relates to the second and subsequent relative placements and is calculated on the basis of the second-side relative position data (without marker detection).
[0028] Thus, the first first-side relative position data can, as stated above, be determined by detecting marker devices, for example a reference star and/or pointers. In accordance with an alternative embodiment, however, the first first-side relative position data is also calculated from the first second-side relative position data which relates to the first second-side relative placement, using symmetry considerations. The position of the first and second second-side body part (for example, in the reference frame of the navigation system) is for example mirrored, for example on the median sagittal plane, so as to calculate the position of the first and second first-side body part in the first relative placement. The relative position of the two first-side body parts in the first first-side relative placement can then also be calculated from this calculated position (see below). The result of the calculation can then for example also be compared with the detected position of the first and/or second first-side body part, whereby deviations between the arrangement of body parts and the ideally symmetrical arrangement can be identified. This can also be performed in accordance with the invention for a single relative placement, such that in this variant of the invention, the calculations relating to the second relative placement are not necessary. Relative placements calculated in accordance with the invention, more specifically the calculated relative position of the first-side body parts in the second first-side relative placement (calculated for example in the way described above), can also be compared with detected positions of the first-side body parts in the second first-side relative placements, whereby deviations between the first-side relative placements and the second-side relative placements, which may in particular be attributed to a deviation between the kinematics of the first-side joint and the kinematics of the second-side joint, can be identified. This can in particular be used to identify diseased joints and/or check the result of an operation.
[0029] Preferably, the first first-side relative placement is symmetrical with respect to the first second-side relative placement, and the second first-side relative placement is symmetrical with respect to the second second-side relative placement. Positions of the body parts are linked to the respective relative placements. These positions are preferably determined for the first first-side relative placement, the first second-side relative placement and the second second-side relative placement by means of a detection device, i.e. they are based on detection signal data.
[0030] In accordance with the invention, the position of the first first-side body part relative to the second first-side body part in the second first-side relative placement is preferably calculated from the first-side and second-side relative position data, i.e. for example, the relative position of the left upper leg and lower leg at 90° flexion is calculated from the relative position of the left upper leg and lower leg at 0° flexion (full extension) and from the relative position of the right upper leg and lower leg at 0° flexion and 90° flexion.
[0031] A pivot angle (for example, 90°), by which the second second-side body part (for example, the right lower leg) pivots relative to the first second-side body part (for example, the right upper leg) when transitioning from the first second-side relative placement (0° flexion) to the second second-side relative placement (90° flexion), is for example determined from the second-side relative position data. Preferably, the second first-side body part (for example, the left lower leg) is then pivoted relative to the first first-side body part (for example, the left upper leg) by the same pivot angle (for example, 90°), starting from the first relative placement (for example, 0° flexion), so as to calculate the position of the second first-side body part (for example, the left lower leg) in the second first-side relative placement (90° flexion).
[0032] When determining the second first-side relative placement, symmetry rules are preferably taken into account which describe the kinematic symmetry of the joint movement. To this end, at least one second-side relative vector is for example mirrored on a body symmetry plane, in particular on the median sagittal plane. At least one second-side relative vector, which describes the transition from the first second-side relative placement to the second second-side relative placement, is for example broken down into components, for each of which a symmetry rule is applied. The vector can for example exhibit a component in a plane which is parallel to the median sagittal plane, which is referred to as the parallel component, and a component which is perpendicular to the median sagittal plane, which is referred to as the perpendicular component. It is possible to apply, to the parallel component, the symmetry rule that it is adopted non-mirrored for a first-side relative vector. For the perpendicular component, it is possible to apply the symmetry rule that it is mirrored on the median sagittal plane. Adding the parallel component and the mirrored perpendicular component produces the first-side relative vector which describes the transition from the first first-side relative placement to the second first-side relative placement. Preferably, two second-side relative vectors are determined for the first second-side body part which are for example positioned at defined points, for example at two points on the body part which are defined by landmarks. First-side relative vectors are then determined from these which are symmetrical to them and positioned at the corresponding points on the first first-side body part and describe the transition.
[0033] The first-side and second-side relative position data has preferably also been acquired in a position or determined for a position in which the first first-side body part and the first second-side body part are arranged symmetrically with respect to each other relative to the median sagittal plane. The first-side and second-side relative vectors are then preferably determined and/or applied on the basis of this presupposition or assumption.
[0034] It is not compulsory to determine or provide the position of the median sagittal plane. Thus, even without determining the median sagittal plane, the calculations can also be based on the assumption that the movement is only performed in one plane which is parallel to the median sagittal plane, i.e. a perpendicular component does therefore not exist.
[0035] If the position of the median sagittal plane is not known (not provided), the median sagittal plane can then for example be determined by means of pointers, by tapping landmarks on the body which are typically symmetrical with respect to the median sagittal plane. If these landmarks are connected by a straight line, and a plane which is perpendicular to the line is placed halfway along it, then the plane thus obtained can be defined as the median sagittal plane. If, for example, the first first-side body part and the first second-side body part are situated in a defined placement (for example, 0° flexion) parallel to each other, the position data for the first first-side body part and the first second-side body part can also be used, so as to determine the median sagittal plane by using a virtual connection between the body parts and determining a plane which is perpendicular to the connection.
[0036] It is in particular possible to determine regions which fulfill a particular property with regard to their relative position, depending on the placement of the first first-side body part relative to the second first-side body part. It is in particular possible to determine the position relative to the second second-side region which applies to a first second-side region when the second-side joint for example performs a particular movement. In this way, it is possible to define a nominal function for the relative position of the regions. This nominal function can then be compared with the function which is given on the first side, so as for example to determine whether the second-side joint is healthy.
[0037] Examples of regions are points or regions on the surface of the body part or recesses or drillings in the body part. A relative variable provides an indication of the relative position between the first region and the second region. The calculation of the relative variable depends on the position of the first region relative to the second region. In particular, it describes a geometric relationship between the regions. Examples of relative variables are an angular relationship between straight lines or axes which pass through the regions and/or body parts, or the relative distance between the regions, or a vector which connects the two regions. In particular, one of the regions is situated on a first first-side body part, and the other region is situated on a second first-side body part.
[0038] The position of the regions can be specified in a general reference frame, for example the reference frame of the navigation system or the reference frame of the operating theatre. They can however also for example be specified in the reference frame of the body part in which the region lies. The relative variables are in particular calculated by incorporating the data concerning the relative position between the two body parts. This calculation is preferably made for the different relative placements, so as to be able to determine how the relative variable changes depending on the relative placement.
[0039] The region data which describes the relative position of the regions in the first and/or second relative placement can for example be acquired by means of pointers which are brought into contact with the respective region in the first and/or second relative placement. The pointers typically comprise at least two markers. By detecting the markers, and due to the known relative position between the markers and the pointer tip, it is then possible to determine the position of the region which is in contact with the pointer tip, for example in the reference frame of the body part in which the region is situated or in the reference frame of the navigation system. On the basis of this, the relative position between the regions is then calculated, so as to determine the region data.
[0040] In one embodiment of the invention, it is not necessary for the body parts to occupy the first and/or second first-side relative placement in order to capture the region data. It can also be captured in another relative placement which does not match the first and/or second relative placement. However, the position of the first and second first-side body part relative to their position in the first and/or second relative placement is preferably likewise known for this other relative placement. On the basis of this, the method in accordance with the invention can then calculate where the region would be situated in the first and/or second relative placement. In this way, the region data for the first and/or second relative placement is then likewise produced.
[0041] The region data can also be processed in current time, i.e. with no time lag, and it is possible to check whether it fulfills a predetermined function, i.e. it is for example possible to calculate, on the basis of the current region data which for example follows from the current position of a pointer, whether the relative variable changes during a transition from the first to the second relative placement, or whether it remains the same. It is sufficient for this purpose to detect the position of one of the two regions on one of the two first-side body parts, for example using a pointer, in any first-side relative placement. The region on the other of the two body parts is then detected, for example by means of a pointer, and a calculation is made in current time as to whether a predetermined condition is fulfilled or not. The condition can for example be that the relative variable does not change during a transition from the first to the second relative placement. The pointer can then be moved, so as to change one of the two regions. Preferably, a determination as to whether the condition is fulfilled is made in current time for each placement of the pointer. This is in particular displayed. It is for example displayed that the predetermined condition is fulfilled in the current placement of the pointer. The surgeon then knows that he has found a matching region. This is possible in accordance with the invention, without moving the body parts relative to each other. In particular, the body parts do not have to be moved in order to occupy the first and second first-side relative placements, but can occupy any other first-side relative placement, at which for example the surgeon can most easily introduce the pointer. The body parts are then moved into the first and second first-side relative placements, and the regions are detected in these placements, by calculation, i.e. virtually.
[0042] In accordance with one embodiment, the different relative placements are used to determine a movement trajectory, for example on the second side. This movement trajectory can then be converted into a nominal movement trajectory for the first side, using the method in accordance with the invention and in particular by taking into consideration symmetry rules. In particular, a movement trajectory (actual movement trajectory) for the first side can likewise be determined by measuring a plurality of relative placements of the first side, and this actual movement trajectory can be compared with the nominal movement trajectory determined by the second-side relative placements. In particular, it is possible to display if there is a deviation between the nominal movement trajectory and the actual movement trajectory.
[0043] For determining the second-side relative position data, marker devices are advantageously used which in particular are not fastened to a bone but rather preferably do not or do not substantially penetrate the skin of the body part. Preferably, a marker device is for example used which can be bound around the body part in a force fit and/or positive fit, i.e. for example a marker strap (for example, a so-called headband). Thus, the marker devices preferably do not penetrate the body part, but rather preferably maintain a fixed relative position relative to the body part by contact with the surface.
[0044] The invention is also directed to a program which performs the predetermined method, in particular using a data processing device, for example a computer. It is also directed to a storage medium, such as for example a ROM or CD, which stores the program, and to a signal wave which for example transfers the information constituting the program, for example in an internet downloading process.
[0045] The invention also relates to a navigation system which comprises a detection device for detecting markers of marker devices, for example reference stars or pointers, so as to detect the position of the body parts and/or the position of regions of the body parts. The detection device generates detection signals which are implemented by the data processing facility in order to determine the relative position data and/or region data which then forms the basis for the subsequent calculation in accordance with the methods in accordance with the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0046] FIG. 1 shows a femur and a tibia, together with a cruciate ligament substitute.
[0047] FIG. 2 schematically shows a left and right leg from above, and a navigation system which detects reference stars attached to the legs.
[0048] FIG. 3 shows relative vectors being determined for two relative placements.
[0049] FIG. 4 shows the determined relative vectors being used to calculate the relative position of the left lower leg.
[0050] FIG. 5 shows the invention being applied to the left and right arm.
[0051] FIG. 6 shows a scenario in which an ideal symmetry is not given.
[0052] FIG. 7 shows the situation from FIG. 6 , with a mirrored femur and a mirrored tibia.
DETAILED DESCRIPTION
[0053] FIG. 1 shows the joint-side end of the femur 10 and the tibia 20 . A patella tendon or an implant ligament 100 which is fastened at its ends to each of the femur and the tibia via screws 110 and 120 , is for example used as the cruciate ligament substitute. The ligament 100 passes through a drilling channel in the femur 10 and in the tibia 20 . These drilling channels have joint-side exit openings 111 (on the femur) and 122 (on the tibia). In order to be able to substitute the function of the cruciate ligament well, it is desirable for the relative distance between the exit openings 111 and 122 to remain as constant as possible, irrespective of the degree of flexion. These exit openings 111 and 122 represent examples of the aforesaid regions for which the relative variable (the distance) is intended to be as invariable as possible, irrespective of the relative placements.
[0054] FIG. 2 schematically shows the left and right leg of a recumbent person, as viewed from above. The left femur is indicated by 10 l , and the left tibia by 20 l . The right femur is indicated by 10 r , and the right tibia by 20 r . The median sagittal plane 200 is indicated by a broken line. The right and left leg are arranged symmetrically with respect to this plane. Marker devices 22 l , 12 l , 22 r and 12 r , each comprising markers 1 , 2 and 3 which are detected by the detection device 300 , are situated on each leg. It is assumed that the left knee joint is diseased, i.e. for example, that it has a cruciate ligament rupture and is therefore operated on. In this case, the marker devices (reference stars 22 l and 12 l ) are preferably fixedly connected to the femur and the tibia. On the healthy right leg, the marker devices (for example, the “ENT headband” 12 r and 22 r ) are preferably not attached invasively, but are rather for example wound around each of the femur and the tibia by means of a flexible strap. Alternatively or additionally, individual markers can also be adhered onto the femur or the tibia, wherein so-called headbands which are known from head operations can be used.
[0055] Preferably, reference frames are assigned to the femur 10 l and 10 r and the tibia 20 l and 20 r . To this end, a joint-side landmark—preferably, the tibial plateau—is detected by a navigation system at said landmark, i.e. the tibial plateau, preferably by means of a pointer 30 , wherein the navigation system detects the markers on the pointer and thus detects the position of the pointer tip. During detection, the anterior-posterior direction is preferably selected as the direction of the pointer 30 , such that this direction is also detected by the navigation system. Subsequently, the pointer 30 is then preferably placed halfway up the tibia at the most anterior point, in order to detect this landmark. This landmark is then shifted by the data processing device of the navigation system in the anterior-posterior direction already detected, until a line is intersected which starts from the tibial plateau landmark already detected and is perpendicular to the anterior-posterior direction. This intersection point, together with the tibial plateau landmark, then defines the direction of the tibial axis. This tibial axis can then form one of the axes of the coordinate system associated with the tibia. The other two axes are for example perpendicular to this, wherein one can for example point in the anterior-posterior direction. The lines 20 l and 20 r shown in FIG. 2 may be interpreted as portions of the tibial axis which for example start from the tibial plateau point, which for example matches the end point 20 ar , and extend over a predetermined length, for example from a point 20 ar to a point 20 er , wherein the point 20 ar designates the end facing the joint. Correspondingly, there are end points 20 al and 20 el on the left tibial axis 20 l . The position of the end points in the respective tibial reference frame is therefore also known.
[0056] Using the registration process described above, the position of the tibial reference frame relative to the reference stars 22 r and 22 l and thus relative to their markers is respectively known, and the respective reference frames are thus registered in the reference frame of the navigation system.
[0057] As the next step, the reference frames of the femur then also have to be respectively determined. To this end, the following approach is for example taken. The reference frame associated with the tibia is copied and shifted along the tibial axis, in particular by a predetermined length (for example by referring to the point 20 ar or 20 al ), in the direction of the femur, such that the origin of the copied reference frame lies in the femur. The copied reference frame thus obtained then becomes the reference frame of the femur. The portions 10 r and 10 l shown in FIG. 2 can in particular be part of a coordinate axis of the femoral reference frame which, when the leg is extended, is part of an extended tibial axis. Alternatively, a femoral reference frame can also be defined by detecting landmarks on the femur.
[0058] The respective axial portions 20 l , 20 r , 10 r and 10 l are then registered in the reference frame of the navigation system in the way cited above. In particular, the position of the axial portions relative to each other is known, and end points 10 ar , 10 er and 20 ar and 20 er of the femoral portion can in particular also be determined, wherein it is for example defined that in the state of extension, a predetermined distance exists between 20 ar and 10 ar and/or between 20 er and 10 er . It is also possible to determine that a predetermined distance exists between 10 ar and 10 er and between 20 ar and 20 er . The relative position of the axial portions and also the relative position of the end points can thus be determined by detecting the marker devices 22 l , 12 l , 22 r and 12 r . The relative position data for the right side and the left side can thus be derived from said detection signal data.
[0059] FIG. 3 shows the transition from 0° flexion to 90° flexion on the right side. The axial portions for 0° flexion (extension) are indicated by 10 r and 20 r . The axial portions for 90° flexion are indicated by 10 r and 20 ′ r . The relative position between 10 r and 20 ′ r is detected by means of marker devices, and the detection signals are for example fed to a data processing device 400 (see FIG. 2 ). As described above, the relative position between 10 r and 20 r is already known. Correspondingly, it is also possible to determine the position of the end points 20 ′ a r and 20 ′ e r. Thus, as a whole, relative vectors va and ve can be determined from the available data. The relative vector va points from the end point 20 ar to the end point 20 ′ a r. The relative vector ve points from the end point 20 er to the end point 20 ′ e r. This merely represents one example. Another approach would for example be to determine relative vectors from the end points 10 ar to the end point 20 ′ a r and from the end point 10 er to the end point 20 ′ e r. The change in the position could also be described using angles, for example the 90° angle, and by the plane in which the distance portions 20 r , 20 ′ r and 10 r lie. The invention is described in the following, by way of example, with the aid of the aforesaid vectors va and ve.
[0060] As shown in FIG. 4 , the leg is in extension in the known initial placement, i.e. the position of the leg is described by the distance portions 10 l and 20 l . The aforesaid vectors va and ve, which have already been calculated, are used to then calculate what the relative position of the left leg would look like at 90° flexion, without actually moving the left leg into 90° flexion. The vector va is positioned at the end point 20 al , in order to point to the end point 20 ′ a l. The vector ve is positioned at the end point 20 el , in order to point to the end point 20 ′ e l. This means that it is assumed that the left tibia performs the same movement relative to the left femur as the right tibia performs relative to the right femur. In the aforesaid example, it has been assumed that the movement is performed in a plane which is parallel to the median sagittal plane. The movement can of course also contain components which deviate from this exact parallelism. This case can be dealt with in accordance with the invention by taking into account symmetry rules. This is illustrated in the following on the basis of an example as shown in FIG. 5 .
[0061] FIG. 5 is for example intended to be a view from above onto an upright patient who is raising his right and left arm. 50 l designates the left upper arm which is dorsally stretched out perpendicular to the median sagittal plane, and 50 r designates the right upper arm which is dorsally stretched out perpendicular to the median sagittal plane 200 . The left lower arm 60 l is situated in an extension of the left upper arm 50 l , and the right lower arm 60 r is situated in an extension of the right upper arm 50 r . The placements of 50 l relative to 60 l and of 50 r relative to 60 r are in turn each detected using marker devices, and the axial portions 50 l to 60 l and 50 r to 60 r are in turn each detected using a pointer, such that in analogy with the method described in FIG. 2 , they are known in a reference frame, in particular in the reference frame of the navigation system. It is also assumed that the right side is the healthy side, i.e. the right elbow joint is healthy, while the left elbow joint is diseased. While 50 r and 60 r together form the first second-side relative placement, 50 r and 60 ′ r form the second second-side relative placement, for which the relative position between 50 r and 60 ′ r is likewise again determined by means of marker detection. It is in particular also possible to determine the relative positions between end points of the distance portions 50 r and 60 ′ r . By comparing the position of these end points, relative vectors we and wa can be determined in an analogous way to FIG. 3 . These relative vectors can then be broken down into components parallel to and perpendicular to the median sagittal plane. The parallel component of we is indicated by wep, and the perpendicular component is indicated by wes. The perpendicular components are parallel to the frontal plane. As described above, it is assumed that the first second-side relative position comprising the axial portions 50 r and 60 r is symmetrical with respect to the first first-side relative position, which is described by 50 l and 60 l , relative to the median sagittal plane 200 . Given this presupposition, the relative vector w′e for the left side, which is calculated from wep-wes, is determined from the vector we and in particular from the components wes and wep. It thus follows that the resultant vector w′e is symmetrical with respect to the vector we, relative to the median sagittal plane. Correspondingly, a vector w′a is also calculated which is symmetrical with respect to the vector wa. The symmetrical vector w′e is then positioned at the end of the axial portion 60 l which faces away from the elbow joint, and the relative vector w′a is positioned at the end of the axial portion 60 l which faces the elbow joint. The tips of the two vectors then point to the respective ends of the axial portion 60 ′ l which is pivoted (by 90°), such that the position of the axial portion 60 ′ l results, wherein the symmetry rules have been considered. The position of the axial portion 60 ′ l thus designates the position of the left lower arm, assuming that the latter is moved symmetrically with respect to the right lower arm and is thus likewise bent or pivoted by 90°. It is thus possible to determine how the left lower arm would lie at 90° flexion, if the left elbow joint exhibited kinematic symmetry with respect to the right elbow joint and likewise behaved like a healthy joint.
[0062] In addition to the aforementioned examples of 90° flexion, other degrees of flexion are of course also possible, such as in particular 30°, 20° or 60°. The change in the relative position can also be mathematically described in ways other than by means of vectors as described above, such as for example by using angles and planes in which the movement is to be performed.
[0063] The calculation is based on the aforementioned relative position data, assuming in particular that it was acquired in the neutral position of the respective body parts. For the leg, it is for example the case that in extension, the tibia is twisted relative to the femur in a way which allows a small clearance in a relative rotation of the tibia relative to the femur. In other relative positions, for example 30° flexion or 90° flexion, this way of twisting is not given. This applies in particular to the diseased leg (cruciate ligament rupture), for which reason virtually flexing the diseased leg in accordance with the invention is regarded as advantageous. For the healthy leg, the tibia is rotated relative to the femur in order to define the second or subsequent relative placements, i.e. in order to define the respective neutral placement, and the average value of the two extreme rotational angles (maximum internal rotation and maximum external rotation) is selected as the neutral placement. As already stated, this is not possible with the diseased leg, in particular the cruciate ligament rupture, because in this case, the cruciate ligament no longer limits the rotational angles for the internal and external rotation.
[0064] In order to find regions which fulfill a particular condition, i.e. for which a relative variable is for example constant, it is possible to proceed as described in the following. A particular region 20 ′B is for example designated using a pointer (see FIG. 4 ), said region for example being suitable as a joint-side end of a drilling through the tibia, in order to guide a strap 100 (see FIG. 1 ) through it. A region 10 B (see FIG. 4 ) is for example also determined by means of a pointer, said region likewise for example being situated in the vicinity of the joint-side end of the femur. In the example shown in FIG. 4 , the regions 20 ′B and 10 B lie on the respective axial portions. This is purely by way of example. In practice, they can perfectly well lie outside the axial portion. One example of the region 20 ′B is the region 122 shown in FIG. 1 . This has been correspondingly marked in FIG. 4 . One example of the region 10 B is the region 111 in FIG. 1 .
[0065] Using the pointer, the relative position of the regions 20 ′B and 10 B relative to the coordinate system of the tibia and the femur is known. In particular, positions relative to the end points 20 ′ a l and 20 ′ e l as well as 10 al and 10 el are for example also known.
[0066] In accordance with the invention, the leg can then be moved purely virtually. The tibia is for example moved from the position indicated by 20 ′ l to the position 20 l (see FIG. 4 ). Other intermediate positions can also be occupied. As a whole, this therefore results in at least two relative placements for which the relative position between the region 20 ′B and the region 10 B can be calculated. It is in particular possible to check whether the distance for the different relative placements is the same or changes. If the distance changes, then this can be displayed and a surgeon can then for example move the pointer in order to find a new region on the femur which is for example likewise in the vicinity of the joint and which fulfils the desired condition.
[0067] As mentioned above, the position of the left diseased leg at 90° flexion is not reliable. However, it can be advantageous in this placement to tap regions between the joint using the pointer, since it is easier at 90° flexion to get the pointer between the femur and the tibia. In order to still have a defined placement at 90° flexion for the tibia, it is possible to check—by means of the marker device attached to the tibia—whether this 90° flexion placement matches the calculated 90° flexion placement (the neutral placement at 90° flexion). If there is a match, this can then be displayed and the surgeon can then tap the regions using the pointer in this 90° flexion placement which has been identified as a neutral placement. Alternatively or additionally, it is possible—by detecting the marker device attached to the tibia—to calculate where the region tapped using the pointer would lie if the tibia occupied a calculated relative placement and/or the first first-side relative placement. In this way, it is possible to calculate—for each position of the pointer—whether the distance between 20 ′B and 10 B is equal to the distance between 20 B and 10 B, without moving the leg. This can of course also be calculated for a plurality of relative placements. The pointer is for example moved to different points 10 B, and the display 500 of the navigation system 300 , 400 and 500 displays if the distance is the same or for example deviates by less than a predetermined percentage for the different calculated relative placements.
[0068] The present invention is also suitable for checking the movement and relative placements of a diseased joint by comparing them with movements and relative placements of the healthy joint. It is in particular possible to detect and store a plurality of relative placements for the healthy joint and to calculate a movement trajectory from these. Using the method in accordance with the invention, corresponding (kinematically symmetrical) relative placements and movement trajectories can then be calculated for the side of the body comprising the diseased joint. It is then possible to check, on the basis of the marker devices attached (invasively or non-invasively) to the diseased side, whether the movement trajectory is kinematically symmetrical with respect to the healthy joint or whether a kinematically symmetrical placement has been occupied. It is thus in particular also possible to identify whether the movement trajectory corresponds to a healthy trajectory. Cruciate ligament ruptures can thus for example also be identified.
[0069] In addition to the median sagittal plane 200 described above, other symmetry planes or symmetry axes can also be adduced when determining the second first-side relative placement. If, for example, the external rotation and internal rotation of a joint is considered, the axis about which the rotation is performed can likewise be regarded as a symmetry axis. If this is determined for both sides, then an external rotation of the second second-side joint, for example the right tibia, by a particular angle in a particular direction of rotation can for example be converted into a corresponding external rotation of the second first-side body part, i.e. for example the left tibia, by the same angle in the opposite direction of rotation, by applying the symmetry considerations. The tibial axis which has already been determined can for example be adduced as the symmetry axis of rotation for the respective side.
[0070] The navigation system in accordance with the invention is likewise schematically shown in FIG. 2 . The detection device 300 detects signals from the marker devices 22 r , 12 r , 10 l and 22 l and relays the detection signals to the data processing device 400 , which performs the method in accordance with the invention and displays display signals on the monitor 500 .
[0071] FIG. 5 can also be adduced as an example of another embodiment of the invention, in which the positions of the right and left upper arm and lower arm are given, and one wishes to determine whether the transition from full extension to 90° flexion is symmetrical for both sides. To this end, it is possible to simply mirror the relative vectors of one side, which represent a relative variable which describes the relative position, at the median sagittal plane 200 , i.e. the vectors we and wa, which are situated on the right side, describe the placement relative position of the right lower arm between the position in the placement before extension and the position in the placement at 90° flexion. The vectors we and wa can then be mirrored on the median sagittal plane. The mirrored vectors are the vectors w′a and w′e, which describe what the placement relative position on the left side would look like if the body is ideally symmetrical, i.e. they describe the placement relative position as mirrored from right to left.
[0072] It is assumed in the example shown in FIG. 5 that first-side body part data is predetermined which describes the position 60 l for the left lower arm in full extension and the position 60 ′ l at 90° flexion. In this case, the mirrored relative vector w′e is identical to a relative vector which is situated on the left side and connects the end of the axial portion 60 l to the end of the axial portion 60 ′ l . The mirrored vector w′a is identical to the vector which connects the start of the axial portion 60 l to the start of the axial portion 60 ′ l . The arrangement shown in FIG. 5 would accordingly be ideally symmetrical, from full extension to 90° flexion, with respect to the placement relative position of the lower arm. In reality, deviations may of course occur, which can be visualized by displaying the mirrored relative vectors and the actual relative vectors on the left side. It is in particular possible to calculate variables which represent a value for the existing symmetry in the transition from full extension to 90° flexion, from the difference between the mirrored vectors and the relative vectors existing on the left side.
[0073] FIG. 6 shows a scenario in which such ideal symmetry is not given. The right and left leg are intended to be in extension. The patient has a varus of different magnitudes of extent. The varus on the right side is more pronounced than on the left side. In order to be able to determine the deviation between the right-side varus and the left-side varus, the femur 10 r and the tibia 20 r are mirrored on the median sagittal plane 200 in accordance with the invention, such that the situation shown in FIG. 7 results. The mirrored right tibia is indicated by 20 ′ r , and the mirrored right femur is indicated by 10 ′ r . The left femur is indicated by 10 l , and the left tibia is indicated by 20 l . In one embodiment in accordance with the invention, distance portions 20 ′ r , 10 ′ r , 10 l and 20 l are displayed on a monitor, in order to provide an indication of deviations from an ideally symmetrical arrangement of the body parts. It can in particular be seen that the non-mirrored left body parts deviate in their position from the mirrored right body parts. This deviation can also be described by relative variables. An angle α between the mirrored distance portions 20 ′ r and 10 ′ r can for example be determined. A corresponding angle can be determined between the distance portions 20 l and 10 l . The angular difference then represents a relative variable which provides an indication of how pronounced a deviation from the ideally symmetrical arrangement of the body parts which is given is. Alternatively, a distance Δ can also be determined which for example connects the end points of the distance 10 r and 10 ′ r which are respectively closest to the distance 20 l and 20 ′ r . The greater the distance Δ, the greater the deviation from the ideally symmetrical arrangement.
[0074] Computer program elements of the invention may be embodied in hardware and/or software (including firmware, resident software, micro-code, etc.). The computer program elements of the invention may take the form of a computer program product which may be embodied by a computer-usable or computer-readable storage medium comprising computer-usable or computer-readable program instructions, “code” or a “computer program” embodied in said medium for use by or in connection with the instruction executing system. Within the context of this application, a computer-usable or computer-readable medium may be any medium which can contain, store, communicate, propagate or transport the program for use by or in connection with the instruction executing system, apparatus or device. The computer-usable or computer-readable medium may for example be, but is not limited to, an electronic, magnetic, optical, electromagnetic, infrared or semiconductor system, apparatus, device or medium of propagation such as for example the Internet. The computer-usable or computer-readable medium could even for example be paper or another suitable medium on which the program is printed, since the program could be electronically captured, for example by optically scanning the paper or other suitable medium, and then compiled, interpreted or otherwise processed in a suitable manner. The computer program product and any software and/or hardware described here form the various means for performing the functions of the invention in the example embodiments.
[0075] Although the invention has been shown and described with respect to one or more particular preferred embodiments, it is clear that equivalent amendments or modifications will occur to the person skilled in the art when reading and interpreting the text and enclosed drawings of this specification. In particular with regard to the various functions performed by the elements (components, assemblies, devices, compositions, etc.) described above, the terms used to describe such elements (including any reference to a “means”) are intended, unless expressly indicated otherwise, to correspond to any element which performs the specified function of the element described, i.e. which is functionally equivalent to it, even if it is not structurally equivalent to the disclosed structure which performs the function in the example embodiment or embodiments illustrated here. Moreover, while a particular feature of the invention may have been described above with respect to only one or some of the embodiments illustrated, such a feature may also be combined with one or more other features of the other embodiments, in any way such as may be desirable or advantageous for any given application of the invention.
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The present application relates to a method for determining the position or relative position of body parts, taking into account the anatomical symmetry, wherein at least one first-side body part is provided on the first side of an anatomical body, and at least one second-side body part is provided on the second side of the anatomical body, wherein the first side is separated from the second side by a body symmetry plane, said method comprising the steps of: providing first-side body part data which describes or implies the position of the at least one first-side body part; providing second-side body part data which describes the position of the at least one second-side body part; providing symmetry plane data which describes the position of the body symmetry plane; calculating the mirrored position or mirrored positions of the at least one second-side body part which results after the position of the at least one second-side body part has been mirrored on the body symmetry plane, on the basis of the second-side body part data and the symmetry plane data, and determining and/or displaying a deviation between the mirrored position or positions of the at least one second-side body part and the position or positions of the at least one first-side body part; and/or determining a mirrored relative position of the second-side body parts, on the basis of the second-side body part data and the symmetry plane data.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to video games. More specifically, the present invention relates to a game program for realizing a role playing game (hereinafter referred to as RPG) which changes a development of a story forming the game on a screen according to an operational input by a player.
2. Description of the Related Art
A video game using cards, such as playing cards is known. In addition, RPGs, using cards have been put in practical use. An RPG using cards makes cards for generating predetermined effects in a game such as magic cards and power-up cards to appear. A character in the game uses each of these cards as one of items that the character can use.
However, in the above-mentioned card game, an ordinary card game using cards is simply played on a screen, thus, although it is convenient in progressing the game, amusement more than that inherent in the card game cannot be offered to a player. In addition, in the RPG using cards, card items simply appear as either weapon items or protection items that have been used frequently in the RPG. Thus, originality and amusement arising from using cards cannot be offered to a player.
SUMMARY OF THE INVENTION
The present invention has been devised in view of these problems, and it is an object of the present invention to provide a game program for enabling a player to play an RPG using cards having originality and amusement, a recording medium having the game program stored therein, a method of processing story developments in an RPG and a game apparatus.
In order to solve the above-mentioned problems, according to an aspect of the present invention, a game program for causing a computer to execute a role playing game which changes a development of a story forming the game on a screen according to an operational input of a player is provided. The game program causes the computer to execute a displaying procedure for displaying a group of cards on the screen; a selecting procedure for selecting one of the displayed cards according to an operational input of the player; and a determining procedure for determining a development of the story according to a selected card.
Therefore, the computer executes processing in accordance with the game program to display the group of cards on the screen and one of the cards is selected by an operational input of the player, whereby the story in the RPG is developed in various ways. Thus, originality and amusement of the RPG using cards can be offered to the player.
In addition, according to another aspect of the present invention, the game program causes the computer to display the cards in a scene for selecting a course of a character appearing in the game, and, determine the course of the character in the game according to the selected card. Therefore, when a card is selected by the operational input of the player, a course of the character is determined in various ways according to the selected card. Thus, a story is developed in various ways for each player.
In addition, according to another aspect of the present invention, the game program causes the computer to display the cards in a scene for selecting an action of a character appearing in the game, and, determine an action of the character in the game according to the selected card. Therefore, when a card is selected by the operational input of the player, an action of the character is determined in various ways according to the selected card. Thus, a story is developed in various ways.
In addition, according to another aspect of the present invention, a scenario of the story is determined according to the selected card. Therefore, when a card is selected by an operational input of a player, a scenario of the story changes according the selected card. Thus, the story is surely developed in various ways.
In addition, according to another aspect of the present invention, the game program causes the computer to execute a procedure for having the character virtually obtain a group of cards corresponding to different scenarios, respectively. Moreover, in the determining procedure, a scenario corresponding to any of the selected cards is determined as a scenario of the story. Therefore, after the character virtually obtains a group of cards corresponding to different scenarios, respectively, a scenario of the story is determined at the point when any of the cards is selected. The story thereafter is developed in accordance with the determined scenario.
In addition, according to another aspect of the present invention, the game program causes the computer to execute the obtaining procedure in the first scene of the role playing game. Therefore, a development of the story varies for each player from the start of the role playing game, and thus, amusement of the RPG is increased.
In addition, according to other aspects of the present invention, the game program causes the computer to read a program recorded in a recording medium, whereby effects similar to those described above can be realized. In addition, according to other aspects of the present invention, the game program causes the computer to execute processing in steps to be written, whereby effects similar to those described above can be realized. Therefore, processing steps to be written are executed using hardware such as a general-purpose computer or a general-purpose game apparatus. Consequently, a story development technology in the role playing game of the present invention can be easily implemented using the hardware.
Other objects and advantages besides those discussed above shall be apparent to those skilled in the art from the description of preferred embodiments of the invention which follows. In the description, reference is made to accompanying drawings, which form a part hereof, and which illustrate an example of the invention. Such an example, however, is not exhaustive of the various embodiments of the invention, and therefore reference is made to the claims which follow the description for determining the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing an overall configuration of a game apparatus to which an embodiment of the present invention is applied;
FIG. 2 is a main flow chart showing processing procedures of a CPU;
FIG. 3 illustrates an example of display of a player character in the form of a card;
FIG. 4 illustrates examples of display of a scenario card;
FIG. 5 is a flow chart showing details of exemplary processing for game developments based on a scenario;
FIG. 6 illustrates examples of display of a geographical feature (obstacle geographical feature) card;
FIGS. 7A and 7B illustrate examples of display of a PC card and a wild card;
FIG. 8 illustrates examples of display of an item card;
FIG. 9 is a flow chart showing details of exemplary processing of a battle screen;
FIG. 10 illustrates examples of display of an enemy card;
FIG. 11 illustrates examples of a trick card;
FIG. 12 illustrates examples of a magic card; and
FIG. 13 illustrates an example of a screen of an entire game screen.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the present invention will be hereinafter described with reference to the accompanying drawings. Further, in the following descriptions, the case in which the present invention is applied to a game machine for home use will be explained as an example.
FIG. 1 is a block diagram showing a configuration of a game apparatus in accordance with this embodiment of the present invention. As shown in the figure, this game apparatus 1 includes, for example, a game machine main body 2 , a keypad 3 , a memory card 4 , a TV set 5 and a CD-ROM 6 .
The game machine main body 2 is composed of, for example, a CPU 8 (Central Processing Unit), an ROM (Read Only Memory) 18 , an RAM (Random Access Memory) 9 , an HDD (Hard Disk) 10 , an interface unit 11 , a sound processing unit 12 , a graphics processing unit 13 , a CD-ROM (Compact Disc Read Only Memory) drive 14 , a detachable CD-ROM 6 and a communications interface 15 , which are connected to each other via a bus 7 .
The CPU 8 sequentially executes a program stored in the RAM 9 to perform processing for progressing a game based on a basic program such as a boot program and an OS (Operating System) stored in the ROM 18 . In addition, the CPU 8 controls operations of each of components 9 to 15 in the game machine main body 2 .
The RAM 9 is used as a main memory of the game machine main body 2 and stores a program and data required for progress of a game, which are transferred from the CD-ROM 6 . In addition, the RAM 9 is also used as a work area in executing a program. That is, a program storage area 91 , a data storage area 92 , a work area 93 and the like are allocated to the RAM 9 . A program and data to be stored in the program storage area 91 and the data storage area 92 are read from the CD-ROM 6 by a CD-ROM drive 14 in accordance with control of the CPU 8 and transferred to the RAM 9 . Various kinds of data required during progress of a game are temporarily stored in the work area 93 .
A game program and data received from an external network 17 via the communications interface 15 and a communications line 16 are stored in the HDD 10 . The detachable keypad 3 and the memory card 4 are connected to the interface unit 11 . The interface unit 11 controls exchanges of data between the keypad 3 and the memory card 4 that are in the outside of the game machine main body 2 and the CPU 8 and the RAM 9 . Further, the keypad 3 is provided with direction keys and various buttons. A player operates these keys and buttons to execute inputs required for progress of a game, such as an instruction to move and an instruction to operate to the player's own character. In addition, the memory card 4 saves data indicating a state of progress of a game.
The sound processing unit 12 performs processing for reproducing sound data such as BGM (Background Music) and sound effects corresponding to a state of progress of a game in accordance with an instruction from the CPU 8 and outputs the sound data to the TV set 5 as a voice signal.
The graphics processing unit 13 performs three-dimensional graphic processing in accordance with an instruction from the CPU 8 and generates image data corresponding to a state of progress of a game. The graphics processing unit 13 adds a predetermined synchronization signal to the generated image data to output the data to the TV set 5 as a video signal.
The CD-ROM drive 14 drives the CD-ROM 6 set in the game machine main body 2 in accordance with an instruction from the CPU 8 and transfers a program and data stored in the CD-ROM 6 to the RAM 9 via the bus 7 .
The communications interface 15 is connected to the external network 17 via the communications line 16 and performs processing for exchanging a program and data with the external network 17 in accordance with an instruction from the CPU 8 .
The CD-ROM 6 stores a program and data (game program 6 a ) required for progress of a game. The CD-ROM 6 is driven by the CD-ROM drive 14 , whereby the stored program and data are read. The program and data read from the CD-ROM 6 are transferred to the RAM 9 from the CD-ROM drive 14 via the bus 7 .
The TV set 5 is provided with a display screen 51 consisting of a CRT (Cathode Ray Tube) or the like for displaying an image corresponding to a video signal from the graphics processing unit 13 and a speaker 52 for outputting voices corresponding to a voice signal from the sound processing unit 12 . Usually, a television receiver is used as the TV set 5 .
In this embodiment in accordance with the above-mentioned configuration, when a game is started, the CPU 8 secures an area for storing information in the RAM 9 , whereby the program storage area 91 , the data storage area 92 , the work area 93 and the like are secured in the RAM 9 . Then, upon receiving a game starting request, the CPU 8 reads information required for a game to be started from the CD-ROM 6 into the RAM 9 , whereby a game program is stored in the program storage area 91 and various kinds of data are stored in the data storage area 92 . The CPU 8 executes processing indicated in a flow chart of FIG. 2 in the first place based on the game program stored in the program storage area 91 .
That is, the CPU 8 executes character determination processing first (step S 1 ). This character determination processing is processing for determining a character of the player among a group of characters and causes the display 51 to display a group of (e.g., seven) questions consisting of a group of choices, respectively. When selection of any choice is completed in response to all the questions, a specific character is determined as a character of the player (player character PC), and the player character PC is displayed on the display 51 as a card as shown in FIG. 3 . That is, in this embodiment, unlike an ordinary RPG, the player character PC appears in the form of a card instead of appearing as a personified character.
Further, this processing of step S 1 is only executed when an RPG in accordance with this embodiment is played for the first time. When the game is subsequently started, processing is started regarding the selected character as a player character PC (card) based on saved data stored in the memory card 4 . In addition, on the display 51 , display is divided into an upper and lower part. In the lower part of the screen, a player character PC in the form of a card is mainly displayed, and an enemy character and other characters in the form of a card, which appear in the following description, are mainly displayed in the upper part of the screen.
Subsequently, after setting “0” in a counter C for counting the number of cleared scenarios (step S 2 ), scenario obtaining processing is executed (step S 3 ). A player character PC meets a character operated by a computer in a predetermined place (e.g., a town) and obtains information concerning a certain scenario by the character, whereby a scenario card for the scenario can be obtained. Therefore, the number of available scenario cards varies according to the number of characters that the player character PC meets. In addition, in this scene, the player may propose that a character the player character PC meets be a comrade of the player character PC. In this way, it becomes possible to increase the number of allies. Here, scenario cards are associated with scenarios forming a different development and a story, respectively.
Next, scenario selection processing is executed (step S 4 ). In this scenario selection processing, the scenario card obtained in step S 3 is used. As shown in an example of FIG. 4, scenario cards 511 , 512 and 513 obtained by the player character PC are displayed on the display 51 . Any one of the three scenario cards 511 , 512 and 513 is selected according to operation of the keypad 3 by the player.
When any one of the scenario cards is selected, game development processing based on the scenario to be described later is executed (step S 5 ), and then if the scenario is cleared by this game development processing, a value of the counter C is incremented (step S 6 ). Further, whether the scenario is cleared or not is determined by whether a mission is accomplished or not as described later. A mission provided for each scenario in this context includes tasks such as defeating a boss monster of an opponent or finding a predetermined item.
When game processing based on the scenario ends in accordance with operation of the keypad 3 by the player and progress of a game, in the two remaining scenario cards among the above-mentioned three scenario cards 511 , 512 and 513 , game development processing based on a scenario corresponding to any one of the cards is started (step S 7 ). Then, if the scenario is cleared by this game development processing, a value of the counter C is incremented (step S 8 ).
In addition, when a game based on the scenario ends, game development processing based on a scenario of the remaining one scenario card among the above-mentioned three scenario cards 511 , 512 and 513 is executed (step S 9 ). If the scenario is cleared in this game development processing, a value of the counter C is incremented (step 10 ).
Subsequently, it is determined whether or not the number of scenarios required for clearing the stage is cleared based on the value of the counter C (step S 11 ). If the number of scenarios required for clearing the stage is not cleared, the processing of step S 3 and subsequent steps is repeated. Further, scenario cards of the number required for clearing a stage or more (e.g., five) are obtained before starting the stage and an arbitrary three scenario cards among them are cleared, whereby the stage may be cleared.
Then, if the number of scenarios required for clearing the stage is cleared (step S 11 ; YES), it is determined whether or not the stage cleared this time is a final stage among all the stages set in this RPG (step S 12 ). If it is not the final stage and stages that should be cleared still remain, the processing moves to the next stage (step S 13 ) and processing of step S 2 and subsequent steps is repeated. In addition, here, the processing may return to step S 1 instead of step S 2 . In this way, it becomes possible for a player to play using a different player character for each stage.
That is, the same processing as in the above-mentioned step S 2 to step S 12 is performed in each stage, and games are developed by stories based on three types of scenarios corresponding to three scenario cards. Then, when all the games based on the three types of scenarios corresponding to the three scenario cards are cleared, the processing moves to the next stage. Finally, when all the stages set in this RPG are cleared, the determination in step S 12 is YES, and the game is completely performed.
FIG. 5 is a flow chart showing details of exemplary game development processing based on scenarios to be executed in the above-mentioned steps S 5 , S 7 and S 9 . First, course selection processing (selection processing of a transit card) is executed (step S 31 ). In this course selection processing (selection processing of a transit card), a group of transit cards are displayed on the display 51 . On the surface of each of the transit cards, a figure indicating “climb a ladder”, “go up the stairs”, “open a door” or the like is displayed. The player selects a transit card corresponding to an action that the player wishes a character to take among the displayed transit cards by operation of the keypad 3 . Thus, game processing is executed according to the selected transit card and the RPG progresses.
Subsequently, a geographic feature card relating to the selected transit card is displayed on the display 51 . Examples of the geographic feature card are shown in 514 , 515 and 516 of FIG. 6 . Figures indicating “passage where a skeleton is lying”, “cave”, “lake” or the like are displayed on displaying surface of these geographic feature cards.
The player instructs the player character PC to take any action with respect to a geographic feature card displayed on the screen. In addition, in the case of a certain geographic feature card, an enemy character appears simultaneously with it. In this case, a battle is started. Battle processing will be described in detail later.
In a scene in which the player character PC does not encounter an enemy (scene other than a battle), the player executes selection processing for selecting any one of PC (player character) cards and wild cards with respect to the displayed geographic feature card (step S 37 ). These cards are PC (player character) cards and wild cards that the player character PC owns virtually, with which a player character PC determines an operation on a game.
Here, as specific examples of the wild card, there are cards indicating “advance”, “look out over”, “try at any rate” and the like. On the other hand, as specific examples of the PC (player character) card, there are cards indicating “run away”, “check well”, “medical herb”, “jump”, “release a trap”, “open a lock”, “thrust”, “cut”, “release an arrow”, “magic of fire”, “magic of water” and the like.
One of a group of cards consisting of PC cards and a group of cards consisting of wild cards is displayed on a lower part 537 of the screen as shown in FIG. 13 according to an operation of the player. Then, the player operates the keypad 3 to select one of the cards, whereby an action of the player character PC is determined.
For example, in a geographic feature card indicating a certain place (a cave, a hole opened in a large tree, or the like), a “look out over” card being a wild card is used. Then, a geographic card indicating a treasure box is displayed. Here, a “check well” card being a PC (player character) card is used. Then, it is displayed on the screen that releasing of a trap and opening a lock are required to open this treasure box. Thus, “release a trap” and “open a lock” cards being PC (player character) cards are used, whereby the treasure box is opened and items inside the treasure box are displayed on the screen. Subsequently, a “try at any rate” card being a wild card is used, whereby the items in the box can be obtained.
Here, as available items, there are money and a key 521 , a knife 522 , a protector 523 , a pot 524 and the like shown in FIG. 8 . Any player character PC is selected by an operation of the keypad 3 to have the player character PC to hold the obtained items, whereby the obtained item can be used.
In addition, if it is not particularly necessary to take a specific action such as “check well” with respect to the displayed geographical feature, an “advance” card being a wild card is used, whereby the processing advances to the next geographical feature card (transit card).
That is, when selection of a transit card is executed in step S 31 , a geographical card relating to the selected transit card is displayed on the display 51 (step S 32 ). Subsequently, it is determined whether or not an enemy character has appeared simultaneously with the appearance of this geographical feature card (step S 33 ) and, if an enemy character has appeared, processing of a battle screen to be described later is executed (step S 34 ). Thereafter, in this processing of battle screen, it is determined whether or not the player character PC has attained a mission set on the scenario (step S 35 ) and, if the mission has not been attained, the processing of step S 31 and subsequent steps is repeated. Then, if the player character PC has attained the mission set on the scenario, it is determined that the scenario is cleared (step S 36 ).
In addition, if it is determined that an enemy character has appeared as a result of the determination in step S 33 , processing for selecting a wild card or a PC card is executed (step S 37 ). In the processing for selecting a wild card or a PC card, as shown in FIGS. 7A and 7B, the computer causes the display 51 to display PC cards 520 or wild cards 517 to 519 . Here, the wild cards 517 , 518 and 519 showing examples indicate “advance”, “look out over” and “try at any rate”, respectively, and the PC card 520 is a card indicating “open a lock”. That is, in an ordinary RPG, a player character PC takes an action on a screen according to an operation of the keypad 3 , whereas, in the RPG in accordance with this embodiment, a player character PC is not made to take an action on the screen. Instead, the PC cards and wild cards 517 to 520 are selected, whereby it is assumed that the player character PC has taken an action corresponding to the selected card. Thus, the game processing is executed according the selected PC cards or the wild cards 517 to 520 and the RPG progresses. Then, in step S 38 , it is determined whether or not selection of the next wild cards or PC cards is necessary. If it is necessary, the processing of step S 37 and subsequent steps is repeated. If it is unnecessary, the processing advances to the above-mentioned step S 35 .
FIG. 9 is a flow chart showing details of the above-mentioned processing of a battle scene (step S 34 ). In this processing of a battle scene, processing of encounter with an enemy is executed first (step S 341 ). That is, when any geographical feature card is selected in the above-mentioned processing of step S 32 , any of enemy cards 525 to 528 shown in FIG. 10 as examples may be displayed on the display 51 , whereby it is assumed that the player character PC has encountered an enemy character.
Next, processing of mutual attacks is executed (step S 342 ). In this processing of mutual attacks, the computer causes the display 51 to display trick cards 529 to 532 shown in FIG. 11 or magic cards 533 to 536 shown in FIG. 12 . Then, for example, with the trick cards 529 to 532 displayed, any of them is selected by operation of the keypad 3 . When a trick card is selected, numerals in a range set in the trick card in advance are sequentially displayed at a high speed on the card. Then, when buttons are operated on the keypad 3 at the timing when any of the numerals is displayed, the numeral is determined as a value of attacking power of the player character PC. The determined value of attacking power of the player character PC is compared with a value of an enemy character card that is an object of attack of the player character PC at that point, whereby a result of the battle is determined. Moreover, if a result of the battle is determined in this way, subtraction processing is performed with respect to a life point set in the player character PC (card) in advance and a life point set in the enemy character (card) in advance.
Next, it is determined whether or not the life point set in the player character PC (card) in advance or the life point set in the enemy character (card) has become “0” (step S 343 ). If any of the life points has become “0”, it is determined whether or not it is the life point of the player character PC (card) (step S 344 ) and, if it is the life point of the player character PC (card), the card is turned over to be displayed (step S 345 ). In addition, if it is not the life point of the player character PC (card) but the life point of the enemy character (card), the enemy character (card) is eliminated (step S 346 ). After turning over the player character card (step S 345 ) and after eliminating the enemy character (step 346 ), processing returns to that in FIG. 5, step 35 .
Further, although the case in which the present invention is realized with a game machine for home use as a platform is described in this embodiment, the present invention may be realized with a general-purpose computer such as a personal computer or an arcade game machine as a platform.
Moreover, a program and data for realizing the present invention are stored in a CD-ROM, which is used as a recording medium in this embodiment. However, a recording medium is not limited to a CD-ROM and may be a DVD (Digital Versatile Disc), other computer readable magnetic and optical recording media or a semiconductor memory. Furthermore, a program and data for realizing the present invention may be provided in the form of being preinstalled in a storage device of a game machine or a computer in advance.
In addition, a program and data for realizing the present invention may be in the form of being downloaded from another apparatus on the network 17 connected by the communications interface 15 shown in FIG. 1 via the communications line 16 to the HDD 10 and used. In addition, the program and the data may be in the form of being recorded in a memory on another apparatus side on the communications line 16 and sequentially stored in the RAM 9 if necessary via the communications line 16 and used.
In addition, a form of providing a program and data for realizing the present invention may be such that the program and the data is provided as a computer data signal superimposed on a carrier wave from another apparatus on the network 17 . In this case, the other apparatus on the network 17 is requested from the communications interface 15 via the communications line 16 to transmit the computer data, and the transmitted computer data signal is received and stored in the RAM 9 . It is also possible to realize the present invention in the game apparatus 1 using the program and the data stored in the RAM 9 in this way.
As described above, according to the present invention, any of a group of cards displayed on a screen is selected according to an operational input by a player, whereby a story in an RPG can be developed in various ways according to the selected card. Thus, it becomes possible to offer the player originality and amusement of an RPG using cards.
The present invention is not limited to the above embodiments and various changes and modifications can be made within the spirit and scope of the present invention. Therefore, to apprise the public of the scope of the present invention the following claims are made.
The present disclosure relates to subject matter contained in priority Japanese Application No. 2001-087448, filed on Mar. 26, 2001, the contents of which is herein expressly incorporated by reference in its entirety.
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A game program realizes a role playing game using cards with originality and amusement. In processing for selecting a scenario, a character is solicited to obtain three scenario cards in advance. Any of the scenario cards is selected from the three scenario cards according to operation of a player. When any of the scenario cards is selected, game development processing based on a scenario of the selected scenario card is executed. Subsequently, it is determined if conditions for clearing a scenario, for which the game development processing is executed, defined in the scenario in advance are met. The game development processing based on the scenario continues to be executed until the conditions for clearing the scenario are met. When the conditions for clearing the scenario are met, games based on scenarios of the remaining two scenario cards are developed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
THE NAMES OF THE PARTIES TO A JOINT RESEARCH AGREEMENT
[0003] Not Applicable
INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC OR AS A TEXT FILE VIE THE OFFICE ELECTRONIC FILING SYSTEM.
[0004] Not Applicable
STATEMENT REGARDING PRIOR DISCLOSURES BY THE INVENTOR OR JOINT INVENTOR
[0005] Not Applicable
BACKGROUND OF THE INVENTION
(1) Field of the Invention
(2) Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98
[0006] The disclosure and prior art relates to bracket devices and more particularly pertains to a new bracket device for automating extension and retraction of a paver platform extension to correspond to and be driven by extension and retraction of a pre-existing laterally extendable paver mechanism.
BRIEF SUMMARY OF THE INVENTION
[0007] An embodiment of the disclosure meets the needs presented above by generally comprising a bracket configured for coupling to a laterally extending paver mechanism of a paver. A post is coupled to and extends from the bracket such that said post is configured for coupling to a paver platform extension such that the paver platform extension is extended and retracted respectively by extension and retraction of the paver mechanism.
[0008] There has thus been outlined, rather broadly, the more important features of the disclosure in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are additional features of the disclosure that will be described hereinafter and which will form the subject matter of the claims appended hereto.
[0009] The objects of the disclosure, along with the various features of novelty which characterize the disclosure, are pointed out with particularity in the claims annexed to and forming a part of this disclosure.
BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWING(S)
[0010] The disclosure will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
[0011] FIG. 1 is a top front perspective view of a paver extension bracket device according to an embodiment of the disclosure.
[0012] FIG. 2 is a bottom view of an embodiment of the disclosure.
[0013] FIG. 3 is a bottom view of an embodiment of the disclosure in a fully retracted position.
[0014] FIG. 4 is a bottom view of an embodiment of the disclosure in a fully extended position.
DETAILED DESCRIPTION OF THE INVENTION
[0015] With reference now to the drawings, and in particular to FIGS. 1 through 4 thereof, a new bracket device embodying the principles and concepts of an embodiment of the disclosure and generally designated by the reference numeral 10 will be described.
[0016] As best illustrated in FIGS. 1 through 4 , the paver extension bracket device 10 generally provides for a platform extension 12 of a paver 14 to be automatically extended laterally relative to the paver 14 when a laterally extendable paver mechanism 16 of the paver 14 is extended. The paver mechanism 16 is of conventional design and a pre-existing element of the paver 14 . A bracket 18 has a first end 20 configured for being coupled to a laterally extendable paver mechanism 16 of the paver 14 . The laterally extendable paver mechanism 16 is of a conventional design and part of a conventional pre-existing paver 14 . The bracket 18 has a base 24 , a lower arm 26 extending from the base 24 , and an upper arm 28 extending from the base 24 . The lower arm 26 is perpendicular to the base 24 . A distal end 30 of the upper arm 28 relative to the base 24 is coupled to a distal end 34 of the lower arm 26 relative to the base 24 . The upper arm 26 is straight such that the bracket is right triangle shaped and planar. The planar design of the bracket 24 allows the bracket to be coupled to the laterally extendable paver mechanism 16 extending rearwardly parallel to a line of travel of the paver 14 . Thus, the bracket 18 is positioned close to an outer lateral edge of the paver 14 and does not substantially increase the overall width of the paver 14 when attached. The bracket 18 may include a medial support 36 coupled to and extending between the lower arm 26 and the upper arm 28 . The base 24 has a pair of spaced mounting holes 38 extending therethrough wherein the base 24 is configured for being secured to the laterally extendable paver mechanism 16 in a conventional manner using bolts or the like.
[0017] A post 40 has a first end 42 coupled to the bracket 18 proximate a junction 42 of the upper arm 28 and the lower arm 26 . A collar 44 is coupled to the platform extension 12 . The platform extension 12 has a substantially planar top surface 46 and a pair of longitudinal flanges 48 extending downwardly from a peripheral edge 70 of the top surface 46 . The collar 44 is centrally positioned along a short side 50 of the platform extension 12 . If an end brace 72 is extending between the longitudinal flanges 48 then a break 74 is aligned with collar 44 . The post 40 extends through the collar 44 such that the post 40 is slidable within the collar 44 . The collar 44 may be elongated to facilitate alignment of the post 40 relative to the platform extension 12 . A plate 54 is coupled to a second end 56 of the post 40 . The plate 54 engages the platform extension 12 as the post 40 is moved generally with the bracket 18 such that the platform extension 12 is configured for being extended and retracted relative to a fixed platform 58 coupled to the paver 14 by extension and retraction of the laterally extendable paver mechanism 16 .
[0018] Typically, the extendable length of the platform extension 12 is less than the length of extension of the laterally extendable paver mechanism 16 . A medial brace 60 is coupled to and extends between longitudinal sides 62 of the platform extension 12 . The medial brace 60 may be fixed to the longitudinal flanges 48 and/or an underside of the planar top 46 . The medial brace 60 has a gap 64 therein aligned with the collar 44 . The post 40 extends through the gap 64 . The plate 54 is positioned between the medial brace 60 and an outer brace 66 of the platform extension 12 . A distance between the medial brace 60 and the outer brace 66 is equivalent to the difference in extension lengths of the platform extension 12 and the laterally extendable paver mechanism 16 . Thus, the platform extension 12 is extended from the fixed platform 58 of the paver 14 when the plate 54 abuts the medial brace 60 to urge the platform extension 12 outwardly from the fixed platform 58 . The plate 54 abuts the outer brace 66 of the platform extension 12 to urge the platform extension 12 inwardly to the fixed platform 58 .
[0019] In use, the bracket 18 and post 40 may be installed on a pre-existing paver 14 or provided as part of the original manufacture of the paver 14 . When added to an existing paver, as the platform extension 12 is typically a pre-existing component of the paver 14 , the medial brace 60 is added to the platform extension 12 at the desired position to create lag in the movement of the platform extension 12 relative to the laterally extendable paver mechanism 16 . The device 10 thus automates extension and retraction of the platform extension 12 corresponding to extension and retraction of the laterally extendable paver mechanism 16 . Guides such as rails and stops, or the like, conventionally used and provided with a pre-existing platform extension are not shown.
[0020] With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of an embodiment enabled by the disclosure, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by an embodiment of the disclosure.
[0021] Therefore, the foregoing is considered as illustrative only of the principles of the disclosure. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the disclosure to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the disclosure. In this patent document, the word “comprising” is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be only one of the elements.
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A paver extension bracket device automates extension and retraction of a paver platform extension to correspond to and be driven by extension and retraction of a pre-existing laterally extendable paver mechanism. The device includes a bracket configured for coupling to a laterally extending paver mechanism of a paver. A post is coupled to and extends from the bracket such that said post is configured for coupling to a paver platform extension such that the paver platform extension is extended and retracted respectively by extension and retraction of the paver mechanism.
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BACKGROUND OF THE INVENTION
The gums of this invention are all known to be useful in stabilizing mild products which contain milk solids, fat, sugar, and water in various amounts. They are also used in various combinations. For example, see U.S. Pat. No. 3,996,389, Dec. 7, 1976, which teaches combinations of (1) carageenan with guar and locust bean gum, (2) xanthan gum, locust bean gum and guar gum, and (3) guar gum and xanthan gum in the ratio 99-90:1-10.
SUMMARY OF THE INVENTION
A novel blend of gums has now been found. This blend contains guar gum, xanthan gum, carrageenan, and, optionally, locust bean gum in the following ratios:
______________________________________ Range______________________________________Guar 53-68%Xanthan 20-35Carrageenan 9-13Locust Bean 0-5______________________________________
At a usage level of 0.14-0.25%, this blend of gums is particularly useful for stabilizing mild compositions containing milk solids, fat, sugar, and water such as milk shakes, soft serve frozen desserts, and like frozen confections.
DETAILED DESCRIPTION OF THE INVENTION
All of the gums of this invention are commercially available. Guar gum, classified as a galactomannan, is a nonionic polysaccharide derived from the seed of the guar plant, Cyamopsis tetragonolobus, family Leguminosae.
Xanthan gum is an extracellular polysaccharide derived from an organism of the genus Xanthomonas, preferably from X. campestris.
Carrageenan is a mixture of several polysaccharides derived from algae of the class Rhodophyceae (red seaweed), the specific composition depending on the source of the seaweed. Although all of the carrageenans are within the scope of this invention it is preferred that kappa, iota or blends of these be used.
Locust beam gum is also a galactomannan derived from the seed of the locust bean or carob, Ceratonia siliqua, family Leguminosae.
These gums are all available in food grade quality with variations depending on source of supply and processing techniques. All of the commercially available products are useable in the invention. It has been found, however, that coarse mesh gums (i.e., those passing through a 20 mesh screen but retained on a 200 mesh screen) are easier to disperse in an aqueous mixture although harder to dissolve whereas finer mesh gums are harder to disperse but easier to dissolve. Where a mix utilizes another ingredient such as sugar which acts to aid dispersion, the finer mesh gums are useable. Where the mix is low in sugar, coarse mesh gums are preferred.
The gum blend of this invention is used to stabilize milk products, specifically those containing fat (either animal or vegetable), sugar and milk, either as whole milk, cream or milk solids to which water is later added. These products can be used to prepare milk shakes, soft serve frozen desserts, and like frozen confections.
In the past, the gums of this invention have been used in various ratios to stabilize milk products. However, it has been found that guar and xanthan gum alone in the ratio 70/30 when used at the useage levels of this invention do not prevent whey-off in, for example, a milk shake mix for prolonged periods of time. Such a mix should be stable for about 10 days in order to ensure useability at retail distribution sites. This allows time for preparation at the factory, distribution to said sites, and storage at the retail site prior to sale to the public. The inclusion of carrageenan, and optionally locust bean gum to the 70/30 guar/xanthan blend imparts such prolonged stability to a milk shake mix, the length of stability depending on the amount of carrageenan added.
The gums of this invention are useable in the following ratios:
______________________________________ Range Preferred______________________________________Guar 53-68% 62.63%Xanthan 20-35% 25.95%Carrageenan 9-13% 10.52%Locust Bean 0-5% 0.90%______________________________________
In varying these ratios, it is preferred to keep the guar/xanthan/carrageenan in approximately the ratio 2.41:1:0.40. Where such a blend is used in a milk shake mix at a level of 0.14-0.25% (preferably 0.17 to 0.20), the milk shake mix is stabilized for 10 days, which is necessary and sufficient for the commercial distribution of such a mix. Where lesser amounts of carrageenan are used in such a blend, the length of stabilization is decreased.
The invention is further described in the following examples, which are intended to be illustrative and not limiting. The levels of the various ingredients in the formulation can be achieved by various means. For example, milk solids can be supplied by using commercially available dry milk solids or by using condensed milk or whole milk. When condensed milk or whole milk is used, there is a corresponding decrease in water added.
EXAMPLE 1
Milk Shake Formulation (Laboratory Scale)
Gum blend, milk solids not fat (MSNF), and sugar are added to cream and water in a vat at room temperature and mixed for 10 minutes. The mix is pasteurized via HTST (high temperature, short time) at 79.4° C. for 25 seconds, homogenized at 1800/500 psi and then cooled to 4.4° C. This mix is observed for whey-off and viscosity. The mix is frozen in a Taylor freezer, spindled on a multimixer for 45-60 seconds, and evaluated for firmness, overrun, iciness, and body. During spindling, chocolate or other flavor can optionally be added.
______________________________________ % by Weight______________________________________Milk solids not fat 9-14Fat 2-4Sucrose 7-10Water 72-82 Visc.* Whey-offStabilizer Level (cP) (7 days)______________________________________Guar/xanthan (70/30) 0.2% 135 very slightgumGuar/xanthan (70/30) 0.2 210 nonecarrageenan 0.015______________________________________ Viscosity is measured in centipoise (cP) in a Brookfield LVT viscometer a 60 rpm, spindle 2, 11° C.
EXAMPLE 2
Milk Shake Formulation (Commercial Dairy Scale)
1090 gallons of mix are prepared with the following composition
______________________________________ Weight %______________________________________MSNF 9-12Fat 2.5-4Sucrose 8-10Water 74-80.5Gum Blend 0.21______________________________________
The gum blend contains 62.63% guar, 25.95% xanthan gum, 10.52% carrageenan, and 0.90% locust bean gum.
The MSNF is supplied as a milk powder which is combined with the gum blend and then incorporated into the other ingredients under moderate agitation in a holding tank. The mix is then HTST pasteurized, homogenized, and packaged under normal dairy conditions. The mix exhibits acceptable viscosity. After 10 days, the mix is inspected and its surface is uniform, thus indicating a lack of whey-off.
EXAMPLE 3
Milk Shake Formulation Using Coconut Oil Instead of Milk Fat
The following milk shake formulation is prepared:
______________________________________ %______________________________________Coconut oil 3.5MSNF 13.0Sugar 8.0Salt 0.02Water 75.25Guar/xanthan 70/30 0.17Carrageenan 0.01______________________________________
One aliquot is vat pasteurized at 71.1° C. for 30 minutes, the other via HTST and the following data are obtained:
______________________________________ Visc. (cP) Initial 24 hours______________________________________Vat Sample 215 200HTST Sample 205 230______________________________________
Part of the two mixes is frozen in a Taylor freezer and chocolate added after removal from the freezer. The milk shakes both exhibit good primary and secondary overrun, good body, and a slight amount of iciness.
The mixes are tested for whey-off as follows. Part of the two mixes is poured into beakers and part into milk cans. After 10 days, the following separation and sedimentation observations are made:
______________________________________ Beaker Can______________________________________Vat Sample No sep., Very slight sep. no sed.HTST Sample Faint sep., Slight sep. no sed______________________________________
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A blend of gums is disclosed which is useful as a milk shake stabilizer. The blend comprises guar, xanthan gum, carrageenan, and, optionally, locust bean gum.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a manufacturing method of a semiconductor device for selectively removing the etching residue on a silicon substrate, and a silicon substrate cassette for selective etching for use in such manufacturing method.
2. Description of Related Art
A conventional MOS type semiconductor device is generally composed as follows. As shown in FIG. 19, reference numeral 101 is a p type Si substrate, 102 is an element separation oxide film, 103 is a gate oxide film, 104 is a gate electrode, 105a, 105b are n + impurity diffusion layers, 106 is an interlayer insulating film, 107 is an opening formed by opening the interlayer insulating film 106 to expose part of the impurity diffusion layer 105a, 108 is a low resistance polycrystalline silicon film, 109 is a resist pattern, 110 is a capacitor lower electrode, 111 is a residue of the low resistance polycrystalline silicon film 108, 112 is a capacitor dielectric film, 113 is a capacitor upper electrode, 114 is an interlayer insulating film, 115 is an opening formed by opening the interlayer insulating films 106 and 114 to expose part of the impurity diffusion layer 105b, and 116 is a bit line electrode.
In the semiconductor device, first as shown in FIG. 14 and FIG. 20, a separation oxide film (a thick silicon oxide film) 102 for element separation is formed by LOCOS method in a specified region on a principal surface of the p type single crystal substrate 101, and a gate oxide film layer (not shown) is formed on the entire surface by thermal oxidation method, then a low resistance polycrystalline silicon layer (not shown) is formed on the gate oxide film layer by CVD method. Then, by patterning by lithographic technique and dry etching technique, the gate oxide film 103 and gate electrode 104 are formed. Using the gate electrode 104 as mask, by implanting As ions in the condition of 50 keV, 4×10 15 cm -2 , a pair of n + impurity diffusion layers (source/drain regions) 105a, 105b are formed by self-aligning. Afterwards, by heat treatment, the n + impurity diffusion layers 105a, 106b are electrically activated.
Consequently, as shown in FIG. 15 and FIG. 21, the interlayer insulating film 106 is formed on the entire surface by CVD method, and the opening 107 is formed in the region positioned on the impurity diffusion layer 105a of the interlayer insulating film 106 by lithographic technique and dry etching technique. As a result, part of the n + impurity diffusion layer 105a is exposed.
Furthermore, as shown in FIG. 16 and FIG. 22, the low resistance polycrystalline silicon layer 108 doped with phosphorus (P) is formed so as to connect electrically with the n + impurity diffusion layer 105a exposed by CVD technique and extend on the interlayer insulating film 106, and a resist pattern 109 is formed on the low resistance polycrystalline silicon layer 108 by lithographic technique. As shown in FIG. 17 and FIG. 23, the resist pattern 109 is transferred by anisotropic dry etching technique represented by reactive ion etching (RIE), and the capacitor lower electrode 110 is formed. By this anisotropic dry etching, the low resistance polycrystalline silicon residue 111 is formed as side wall in the step portion.
Next, as shown in FIG. 18 and FIG. 24, the capacitor dielectric film 112 is formed on the capacitor lower electrode 110. The capacitor dielectric film 112 is composed of a single layer film such as thermal oxide film, a multi-layer film such as composition of silicon oxide film/silicon nitride film/silicon oxide film, Ta 2 O 5 , or the like.
Then, after forming a low resistance polycrystalline silicon thin film (not shown) by CVD method, the capacitor upper electrode 113 is formed by lithographic technique and dry etching technique.
Sequentially, as shown in FIG. 19 and FIG. 25, the interlayer insulating film 114 is formed on the entire surface by CVD method. By lithographic technique and dry etching technique, afterwards, the opening 115 is formed in a region positioned above the n + impurity diffusion layer 105b of the interlayer insulating films 106 and 114. As a result, part of the n + impurity diffusion layer 105b and low resistance polycrystalline silicon residue 111 are exposed.
Finally, by CVD method, a low resistance polycrystalline silicon film (not shown) is formed so as to connect electrically with the exposed n + impurity diffusion layer 105b and extend over the interlayer insulating film 114, and the bit line electrode 116 is formed by lithographic technique and dry etching technique.
In such conventional method, however, since the low resistance polycrystalline silicon residue 111 is left over in a linear form as shown in FIG. 23, a high resistance shorting occurs between the adjacent capacitor lower electrodes 110 fabricated on the low resistance polycrystalline silicon residue, and high resistance shorting also occurs on every other bit line 116 fabricated on the interlayer insulating film 114 as shown in FIG. 25.
To remove the etching residue occurring in the semiconductor manufacturing process, a wet process for removing the etching residue by immersing the substrate in an alkaline etching solution after anisotropic etching is known, but since the usual wet etching is isotropic etching, and other portions than the etching residue are similarly etched, and the pattern size varies in the semiconductor memory device or the like using the superfine processing technology, in particular, which is inconvenient in characteristics.
In this invention, by making use of the selective chemical etching method (Japanese Laid-open Patent Sho. 61-34947) for forming a protective film by anodic oxidation of the necessary portion before removal of etching residue, and removing only the residue portion by ordinary isotropic etching while protecting this portion, it is an object to present a selective chemical etching method for selectively removing the etching residue occurring in the semiconductor manufacturing process easily and simultaneously on a plurality of silicon substrates, and a silicon substrate cassette suited to such plurality processing.
SUMMARY OF THE INVENTION
The inventors, as a result of intensive studies, discovered that, in the MOS type semiconductor device, the substrates and the portion electrically connected therewith can be protected against chemical etching employed in second etching step, while the silicon left over on the interlayer insulating film can be selectively removed by chemical etching, only by applying a positive potential to any part of the silicon substrates by employing the selective etching method because the silicon left over on the interlayer insulating film as the residue in the first etching step is non-conductive to the silicon substrates and the other portions including the capacitor electrode are conductive to the silicon substrates, thereby reaching the completion of the invention.
That is, the invention presents a manufacturing method of semiconductor device comprising a first etching step comprising a step of forming a gate electrode on a silicon substrate and an impurity diffusion layer between the gate electrodes, a step of forming an interlayer insulating film over the gate electrode and impurity diffusion layer and forming an opening on the impurity diffusion layer of the interlayer insulating film, a step of forming a silicon film on the interlayer insulating film and on the impurity diffusion layer in the bottom region of the opening through the opening, a step of anisotropically etching the silicon on the interlayer insulating film by using a resist pattern and forming a remaining silicon film as a capacitor lower electrode,
and a second etching step comprising a step of immersing the silicon substrate in a chemical etching solution and applying a positive potential to the silicon substrate, a step of forming a passive film by anodically oxidizing the contact surface of the silicon substrate and a portion electrically connected thereto, with the chemical etching solution and a step of isotropically etching to remove the residue of the first etching step in the non-conductive state left over on the interlayer insulating film.
In particular, the residue of the silicon in non-conductive state is usually composed of polycrystalline silicon.
In the invention, a positive potential of several volts to scores of volts to the chemical etching solution is applied to the silicon substrate, and the chemical etching solution is a solution composed of any one selected from the group consisting of KOH, NaOH, LiOH, CsOH, NH 4 OH, ethylene diamine pyrocatechol, hydrazine, and choline, and the temperature of the chemical etching solution is preferred to be 60° to 70° C.
Especially, as the chemical etching solution of polycrystalline silicone, 5N KOH solution is suited.
Moreover, the invention is preferred to be employed as a method of processing the etching residue on two or more silicon substrates simultaneously. In this case, the method of the invention is preferred to be executed by using a cassette made of a conductive material used for selective etching, that is, a silicon substrate cassette disposing plural silicon substrates on the cassette oppositely at a specific interval in a detachable state, so that a positive potential may be applied to the silicon substrates from the surrounding through the cassette by connecting a power source positive electrode to the cassette.
Therefore, the invention presents a silicon substrate cassette capable of processing the plural silicon substrates simultaneously.
Power feeding from the cassette may be done from around the silicon substrates through an engaging portion disposing detachably the silicon substrates, but it may be also designed to feed power from the back side to the silicon substrates disposed so as to contact with the electrodes through the substrate application electrodes by the substrate application electrodes by disposing oppositely plural flat silicon substrate application electrodes so as to be disposed in contact with the silicon substrates at specific interval on the cassette.
The grounding electrodes may be disposed outside of the cassette, but it may be also disposed parallel to the silicon substrates on the cassette. In this case, the flat grounding electrodes are mounted on the conductive cassette through insulators.
The residue on the silicon substrate is present on the substrate surface, and it is essential to dispose so that the surface of the silicon substrate may confront the grounding electrode. Therefore, the silicon substrate and grounding electrode are alternately disposed parallel, or the surfaces of the silicon substrates may be disposed oppositely across the grounding electrode.
The cassette may be a silicon substrate cassette mounting flat grounding electrodes parallel to the electrodes, between electrodes of the silicon substrate application electrodes disposed oppositely on the cassette.
The cassette may be also a silicon substrate cassette mounting flat grounding electrodes parallel at a specific interval, and oppositely disposing flat silicon substrate application electrodes so as to be disposed in contact with the silicon substrates at both sides of the grounding electrodes.
According to the invention, in addition to the conventional manufacturing process of semiconductor device comprising a first etching step comprising a step of forming a gate electrode on a silicon substrate and an impurity diffusion layer between the gate electrode, a step of forming an interlayer insulating film over the gate electrode and impurity diffusion layer and forming an opening on the impurity diffusion layer of the interlayer insulating film, a step of forming a silicon film on the interlayer insulating film and on the impurity diffusion layer in the bottom region of the opening through the opening, a step of anisotropically etching the silicon on the interlayer insulating film by using a resist pattern and forming a remaining silicon film as a capacitor lower electrode (FIGS. 1 to 4, 6 and 7), it further comprises a second etching step comprising a step of immersing the silicon substrate in a chemical etching solution and applying a positive potential to the silicon substrate, a step of forming a passive film by anodically oxidizing the contact surface of the silicon substrate and a portion electrically connected thereto, with the chemical etching solution and a step of isotropically etching to remove the residue of the first etching step in the non-conductive state left over on the interlayer insulating film (FIG. 5), whereby the silicon residue (FIG. 23) on the interlayer insulating film can be selectively removed while protective the silicon substrate surface by the passive film, and shorting between the adjacent capacitor lower electrodes or bit lines caused due to the silicon residue in the prior art can be prevented.
The silicon residue on the interlayer insulating film is usually polycrystalline silicon, but using the above method also in the polycrystalline silicon, the residue can be removed selectively, and shorting due to residue can be prevented.
In the selective etching process of the silicon residue, by defining the positive potential to be applied to the silicon substrate at several volts to scores of volts, the contact surface of the silicon substrate and its electrically connected portion with the etching solution can be favorably oxidized anodically to form a passive film, so that etching of the necessary element portions such as silicon substrate surface can be prevented.
The silicon residue can be favorably removed by a solution of any one of KOH, NaOH, LiOH, CsOH, NH 4 OH, ethylene diamine pyrocatechol, hydrazine, and choline, and especially by using 5N KOH solution. Besides, a favorable etching speed can be obtained by defining the temperature of the chemical etching solution at 60 to 70° C.
Also according to the invention, by feeding current only to part of the conductive silicon substrate in a chemical etching solution, the contact surface of the silicon substrate and its electrically connected portion with the etching solution can be favorably oxidized anodically to form a passive film so as to protect, while the non-conductive silicon on the interlayer insulating film can be selectively removed, and hence by immersing plural silicon substrates in a chemical etching solution and feeding current, selective removal of the etching residue on the plural silicon substrates can be done by one etching step.
In particular, in simultaneous etching process of plural silicon substrates, by using the conductive silicon substrate of the invention, that is, the silicon substrate cassette (FIG. 8) having plural silicon substrates mounted on the cassette oppositely at a specific interval in a detachable state, and capable of applying a positive potential simultaneously from the surrounding to one or two or more silicon substrates disposed on the cassette by applying a positive potential to the cassette main body, current feeding to the plural silicon substrates may be easy.
In such cassette, moreover, by mounting flat grounding electrodes on the cassette together with an insulators alternately and parallel to the oppositely disposed silicon substrates (FIG. 9), the intra-plane uniformity of etching of silicon residue can be enhanced.
Above all, by disposing so that the silicon substrate may be held on both sides by the grounding electrode and that the silicon substrate surface may confront the grounding electrode (FIG. 10), the intra-plane uniformity of etching of the silicon substrate may be enhanced, and the required number of grounding electrodes necessary for etching may be decreased to half of the prior art.
Moreover, according to the invention, by oppositely disposing plural flat silicon substrate application electrodes that can be disposed in contact with the silicon substrate at a specific interval on a cassette made of non-conductive material, and applying a positive potential from the back to the silicon substrates disposed in contact with the electrodes through the substrate application electrodes (FIG. 11), the contact area between the substrate application electrodes and silicon substrates becomes wider, and more uniform current application to the silicon substrates is realized, so that the intra-plane uniformity of residue etching may be enhanced.
In this cassette, by mounting flat grounding electrodes so as to be alternate and parallel to the substrate application electrodes disposed oppositely (FIG. 12), or by disposing so that the substrate application electrodes may hold the grounding electrodes on both sides and that the silicon substrate surface on the substrate application electrode may confront the grounding electrode (FIG. 13), the intra-plane uniformity of etching of the silicon residue may be enhanced, and in the latter case the number of grounding electrodes necessary for etching may be decreased to half of the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objectives and features of the present invention will become more apparent from the following description of a preferred embodiment thereof with reference to the accompanying drawings, throughout which like parts are designated by like reference numerals, and wherein:
FIG. 1 through FIG. 7 schematically illustrate sequential stages in accordance with an embodiment of the present invention;
FIG. 8 schematically illustrates etching plural substrates in accordance with an embodiment of the present invention;
FIG. 9 schematically illustrates etching plural substrates in accordance with another embodiment of the present invention;
FIG. 10 schematically illustrates another embodiment for uniformly etching plural silicon substrates in accordance with the present invention;
FIG. 11 schematically illustrates a further embodiment of the present invention for etching plural silicon substrates;
FIG. 12 schematically illustrates another embodiment of the present invention wherein the plural silicon substrates are etched;
FIG. 13 schematically illustrates yet another embodiment of the present invention wherein plural silicon substrates are etched;
FIGS. 14 through 19 schematically illustrate sequential stages of prior art methodology;
FIGS. 20 through 25 are plan views schematically illustrating sequential stages of conventional manufacturing technique.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiment 1
FIG. 1 to FIG. 7 are process sectional views showing a manufacturing method of semiconductor device according to the invention.
In the drawings, reference numeral 1 denotes a Si substrate, 2 is an element separation oxide film, 3 is a gate oxide film, 4 is a gate electrode, 5a, 5b are impurity diffusion layers, 6 is an interlayer insulating film, 7 is an opening formed by opening the interlayer insulating film 6 and exposing part of the impurity diffusion layer 5a, 8 is a polysilicon film, 9 is a resist pattern, 10 is a capacity lower electrode, 11 is a residue of low resistance polycrystalline silicon film 8, 12 is a capacitor dielectric film, 13 is a capacitor upper electrode, 14 is an interlayer insulating film, 15 is an opening formed by opening the interlayer insulating films 6 and 14 and exposing part of the impurity diffusion layer 5b, 17 is a chemical etching solution, 18 is a direct-current voltage power source, 19 is a grounding electrode, and 20 is a wet removing device having the direct-current voltage power source 18 and grounding electrode 19.
First, as shown in FIG. 1, the separation oxidation film (thick silicon oxide film) 2 is formed for element separation by LOCOS method, in a specified region on a principal surface of the p type single crystal silicon substrate 1.
Next, by thermal oxidation method, a gate oxide film layer (not shown) is formed on the entire surface, and a low resistance polycrystalline silicon layer (not shown) is deposited on the gate oxide film layer by CVD method.
Consequently, by patterning by lithographic technique and dry etching technique, the gate oxide film 3 and gate electrode 4 are formed. Using the gate electrode 4 as mask, by implanting As ions in the condition of 50 keV×4×10 15 cm -2 , a pair of n + impurity diffusion layers (source/drain region) 5a, 5b are formed by self-aligning. By heat treatment, afterwards, the n + impurity diffusion layers 5a, 5b can be activated electrically.
Then, as shown in FIG. 2, the interlayer insulating film 6 is formed on the entire surface by CVD method. Furthermore, in a region positioned on the impurity diffusion layer 5a of the interlayer insulating film 6, the opening 7 is formed by the lithographic technique and dry etching technique. As a result, part of the n + impurity diffusion layer 5a is exposed.
As shown in FIG. 3, subsequently, the low resistance polycrystalline silicon film 8 doped with phosphorus (P) is formed so as to connect electrically with the n + impurity diffusion layer 5a exposed by the CVD method and extend over the interlayer insulating film 6, the resist pattern 9 is formed by using the lithographic technique on the low resistance polycrystalline silicon layer 8.
Now, as shown in FIG. 4, by an anisotropic dry etching technique represented by RIE, the resist pattern 9 is transferred, and the capacitor lower electrode 10 is formed. By this anisotropic dry etching, the low resistance polycrystalline silicon residue 11 is formed in the step as side wall.
Further, as shown in FIG. 5, by using the wet removing device 20 comprising chemical etching solution 17, direct-current voltage power source 18, and grounding electrode 19, the low resistance polycrystalline silicon residue 11 is selectively removed by chemically etching with a direct-current voltage applied to the silicon substrate 1.
Typical examples of chemical etching solution are KOH, NaOH, LiOH, CsOH, NH4OH, ethylene diamine pyrocatechol, hydrazine, and choline.
When 5N KOH heated to 60° C. is used as chemical etching solution, by applying a direct-current voltage of several volts to scores of volts to the silicon substrates 1, the capacitor lower electrode 10 comes to be same in potential as the silicon substrates, and a passive layer for stopping electrochemical etching is formed on the surface of the silicon substrates 1 and capacitor lower electrode 10.
On the other hand, the low resistance polycrystalline silicon residue 11 does not conduct with the silicon substrates, or conducts through a high resistance element, and therefore voltage is not applied, or if applied, the voltage drops through the capacitor lower electrode 10, so that passive layer is not formed.
Therefore, the silicon substrate 1 and capacitor lower electrode 10 in which passive layer is formed are not etched, while the low resistance polycrystalline silicon residue 11 is selectively removed chemically by alkaline etching by KOH.
As shown in FIG. 6, the capacitor dielectric film 12 is formed on the capacitor lower electrode 10. This capacitor dielectric film 12 is composed of a single layer film such as thermal oxide film, a multi-layer film such as composition of silicon oxide film/silicon nitride film/silicon oxide film, or Ta 2 O 5 or the like.
After forming the low resistance polycrystalline silicon film layer (not shown) by CVD method, the capacitor upper electrode 13 is formed by lithographic technique and dry etching technique.
As shown in FIG. 7, by using the CVD method, the interlayer insulating film 14 is formed on the entire surface. Then, by lithographic technique and dry etching technique, the opening 15 is formed in the region positioned above the interlayer insulating films 6 and 14 and n + impurity diffusion layer 5b. As a result, part of the n + impurity diffusion layer 5b is exposed.
By the CVD method, a low resistance polycrystalline silicon film (not shown) is formed so as to connect electrically with the exposed n + impurity diffusion layer 5b and extend over the interlayer insulating film 14, and the bit line electrode 16 is formed by lithographic technique and dry etching technique.
Embodiment 2
FIGS. 1 to 7 and FIG. 8 are process sectional diagrams showing a manufacturing method of semiconductor device in a second embodiment of the invention.
In FIG. 8, reference numeral 17 is a chemical etching solution, 18 is a direct-current voltage power source, 19 is a grounding electrode, 21 is a silicon substrate, 22 is a principal surface of the silicon substrate 21, 23 is a conductive silicon substrate cassette, and 24 is a wet removing device comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, and conductive silicon substrate cassette 23.
FIG. 1 to FIG. 7 are as mentioned in the first embodiment, and FIG. 8 shows the process sectional view using instead of FIG. 5.
In this embodiment, as shown in FIG. 8, plural silicon substrates 21 are set on the conductive silicon substrate cassette 23, and with the conductive silicon substrate cassette 23 connected electrically to the side of the silicon substrates 21, the low resistance polycrystalline silicon residue 11 shown in FIG. 4 is selectively removed by etching chemically while applying a direct-current voltage to the silicon substrate cassette 23 by using the wet removing device 24 comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, and conductive silicon substrate cassette 23.
When the chemical etching solution is 5N KOH heated to 60° C., by applying a direct-current voltage of several volts to several 10 volts to the silicon substrate cassette 23, voltage is applied also to the silicon substrates 21, and moreover the capacitor lower electrode 10 shown in FIG. 4 is also at the same potential as the silicon substrates 21, and a passive layer for stopping electrochemical etching is formed on the surface of the silicon substrates 21 and capacitor lower electrode 10.
Since voltage is not applied to the low resistance polycrystalline silicon residue 11, or if applied, the voltage is lowered through the capacitor lower electrode 10, passive layer is not formed, so as to be removed chemically by alkaline etching by KOH, while the silicon substrate 21 and capacitor lower electrode 10 forming the passive layer is not etched.
Thus, in the embodiment, by using the conductive silicon substrate cassette, the low resistance polycrystalline silicon residue 11 can be removed simultaneously and easily from the plural silicon substrates 21.
Embodiment 3
FIGS. 1 to 7 and FIG. 9 are process sectional diagrams showing a manufacturing method of semiconductor device in a third embodiment of the invention.
In FIG. 9, reference numeral 17 is a chemical etching solution, 18 is a direct-current voltage power source, 21 is a silicon substrate, 22 is a principal surface of the silicon substrate 21, 23 is a conductive silicon substrate cassette, 25 is a grounding electrode fixed to the silicon substrate cassette 23 parallel at a specific distance from the principal surface 22 of the silicon substrate 21, 26 is an insulator for fixing the grounding electrode 25 by electrically insulating to the conductive silicon substrate cassette 23, and 27 is a wet removing device comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 25, conductive silicon substrate cassette 23, and fixing insulator 26.
FIG. 1 to FIG. 7 are as mentioned in the first embodiment, and FIG. 9 shows the process sectional view using instead of FIG. 5.
In this embodiment, as shown in FIG. 9, silicon substrates 21 are set on the conductive silicon substrate cassette 23 so that the principal surfaces 22 of the silicon substrates 21 may be in the same direction, and with the conductive silicon substrate cassette 23 connected electrically to the side of the silicon substrates 21, the low resistance polycrystalline silicon residue 11 shown in FIG. 4 is selectively removed by etching chemically while applying a direct-current voltage to the silicon substrate cassette 23 by using the wet removing device 27 comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 25, conductive silicon substrate cassette 23, and fixing insulator 26.
When the chemical etching solution is 5N KOH heated to 60° C., by applying a direct-current voltage of several volts to several 10 volts to the silicon substrate cassette 23, voltage is applied to the silicon substrates 21, and moreover the capacitor lower electrode 10 shown in FIG. 4 is also at the same potential as the silicon substrates 21, and a passive layer for stopping electrochemical etching is formed on the surface of the silicon substrates 21 and capacitor lower electrode 10. Since voltage is not applied to the low resistance polycrystalline silicon residue 11, or if applied, the voltage is lowered through the capacitor lower electrode 10, passive layer is not formed, so as to be removed chemically by alkaline etching by KOH, while the silicon substrate 21 and capacitor lower electrode 10 forming the passive layer is not etched.
Thus, in the embodiment, by using the conductive silicon substrate cassette, the low resistance polycrystalline silicon residue 11 can be removed simultaneously and easily from the plural silicon substrates 21, and moreover by positioning the grounding electrode 25 in the grounding state parallel to the silicon substrate 21, the uniformity of etching is enhanced.
Embodiment 4
FIGS. 1 to 7 and FIG. 10 are process sectional diagrams showing a manufacturing method of semiconductor device in a fourth embodiment of the invention.
In FIG. 10, reference numeral 17 is a chemical etching solution, 18 is a direct-current voltage power source, 21 is a silicon substrate, 22 is a principal surface of the silicon substrate 21, 23 is a conductive silicon substrate cassette, 25 is a grounding electrode fixed to the silicon substrate cassette 23 parallel at a specific distance from the principal surface 22 of the silicon substrate 21, 26 is an insulator for fixing the grounding electrode 25 by electrically insulating to the conductive silicon substrate cassette 23, and 27 is a wet removing device comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 25, conductive silicon substrate cassette 23, and fixing insulator 26.
FIG. 1 to FIG. 7 are as mentioned in the first embodiment, and FIG. 10 shows the process sectional view using instead of FIG. 5.
As shown in FIG. 10, silicon substrates 21 are set on the conductive silicon substrate cassette 23 so that the principal surfaces 22 of the silicon substrates 21 may confront each other, and with the conductive silicon substrate cassette 23 connected electrically to the side of the silicon substrates 21, the low resistance polycrystalline silicon residue 11 shown in FIG. 4 is selectively removed by etching chemically while applying a direct-current voltage to the silicon substrate cassette 23 by using the wet removing device 27 comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 25, conductive silicon substrate cassette 23, and fixing insulator 26.
When the chemical etching solution is 5N KOH heated to 60° C., by applying a direct-current voltage of several volts to several 10 volts to the silicon substrate cassette 23, voltage is applied to the silicon substrates 21, and moreover the capacitor lower electrode 10 shown in FIG. 10 is also at the same potential as the silicon substrates 21, and a passive layer for stopping electrochemical etching is formed on the surface of the silicon substrates 21 and capacitor lower electrode 10.
Since voltage is not applied to the low resistance polycrystalline silicon residue 11, or if applied, the voltage is lowered through the capacitor lower electrode 10, passive layer is not formed, so as to be removed chemically by alkaline etching by KOH, while the silicon substrate 21 and capacitor lower electrode 10 forming the passive layer is not etched.
Thus, in the embodiment, by using the conductive silicon substrate cassette, the low resistance polycrystalline silicon residue 11 can be removed simultaneously and easily from the plural silicon substrates 21, and moreover the uniformity of etching is enhanced, and the number of grounding electrodes 25 may be half the number of silicon substrates 21.
Embodiment 5
FIGS. 1 to 7 and FIG. 11 are process sectional diagrams showing a manufacturing method of semiconductor device in a fifth embodiment of the invention.
In FIG. 11, reference numeral 17 is a chemical etching solution, 18 is a direct-current voltage power source, 19 is a grounding electrode, 21 is a silicon substrate, 22 is a principal surface of the silicon substrate 21, 28 is a silicon substrate cassette, 29 is an electrode fixed to the silicon substrate cassette 28 so as to contact with the back side of the silicon substrate 21, and 30 is a wet removing device comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, silicon substrate cassette 28, and electrode 29.
FIG. 1 to FIG. 7 are as mentioned in the first embodiment, and FIG. 11 shows the process sectional view using instead of FIG. 5.
As shown in FIG. 11, silicon substrates 21 are set on the silicon substrate cassette 28, and with the electrode 29 electrically connected to the back side of the silicon substrates 21, the low resistance polycrystalline silicon residue 11 shown in FIG. 4 is selectively removed by etching chemically while applying a direct-current voltage to the electrode 29 fixed to the silicon substrate cassette 28 by using the wet removing device 30 comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, silicon substrate cassette 28, and electrode 29.
When the chemical etching solution is 5N KOH heated to 60° C., by applying a direct-current voltage of several volts to several 10 volts to the electrode 29, voltage is applied to the silicon substrates 21, and moreover the capacitor lower electrode 10 shown in FIG. 4 is also at the same potential as the silicon substrates 21, and a passive layer for stopping electrochemical etching is formed on the surface of the silicon substrates 21 and capacitor lower electrode 10.
Since voltage is not applied to the low resistance polycrystalline silicon residue 11, or if applied, the voltage is lowered through the capacitor lower electrode 10, passive layer is not formed, so as to be removed chemically by alkaline etching by KOH, while the silicon substrate 21 and capacitor lower electrode 10 forming the passive layer is not etched.
Thus, in this embodiment, since voltage is applied to the back side of the silicon substrates 21 from the electrode 29 fixed to the silicon substrate cassette 28, the uniformity of the voltage applied to the principal surface 22 of the silicon substrate is enhanced, and the controllability of etching is enhanced.
Embodiment 6
FIGS. 1 to 7 and FIG. 12 are process sectional diagrams showing a manufacturing method of semiconductor device in a sixth embodiment of the invention.
In FIG. 12, reference numeral 17 is a chemical etching solution, 18 is a direct-current voltage power source, 21 is a silicon substrate, 22 is a principal surface of the silicon substrate 21, 28 is a non-conductive silicon substrate cassette, 19 is a grounding electrode fixed to the non-conductive silicon substrate cassette parallel at a specific distance from the principal surface 22 of the silicon substrate 21, 29 is an electrode fixed to the non-conductive silicon substrate cassette 28 so as to contact with the back side of the silicon substrate 21, and 30 is a wet removing device comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, non-conductive silicon substrate cassette 28, and electrode 29.
FIG. 1 to FIG. 7 are as mentioned in the first embodiment, and FIG. 12 shows the process sectional view using instead of FIG. 5.
As shown in FIG. 12, silicon substrates 21 are set on the non-conductive silicon substrate cassette 28 so that the principal surfaces 22 of the silicon substrates may face in the same direction, and with the electrode 29 electrically connected to the back side of the silicon substrates 21, the low resistance polycrystalline silicon residue 11 shown in FIG. 4 is selectively removed by etching chemically while applying a direct-current voltage to the electrode 29 fixed to the non-conductive silicon substrate cassette 28 by using the wet removing device 30 comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, non-conductive silicon substrate cassette 28, and electrode 29.
When the chemical etching solution is 5N KOH heated to 60° C., by applying a direct-current voltage of several volts to several 10 volts to the electrode 29, voltage is applied to the silicon substrates 21, and moreover the capacitor lower electrode 10 shown in FIG. 4 is also at the same potential as the silicon substrates 21, and a passive layer for stopping electrochemical etching is formed on the surface of the silicon substrates 21 and capacitor lower electrode 10.
Since voltage is not applied to the low resistance polycrystalline silicon residue 11, or if applied, the voltage is lowered through the capacitor lower electrode 10, passive layer is not formed, so as to be removed chemically by alkaline etching by KOH, while the silicon substrate 21 and capacitor lower electrode 10 forming the passive layer is not etched.
Thus, in the embodiment, since the grounding electrode 19 fixed to the non-conductive silicon substrate cassette 28 is positioned parallel to the silicon substrate 21, uniformity of etching is enhanced, and moreover since voltage is applied to the silicon substrates 21 from the electrode 29 fixed to the non-conductive silicon substrate cassette 28, the uniformity of the voltage applied to the principal surfaces 22 of silicon substrates is enhanced, so that the controllability and stability of etching may be improved.
Embodiment 7
FIGS. 1 to 7 and FIG. 13 are process sectional diagrams showing a manufacturing method of semiconductor device in a seventh embodiment of the invention.
In FIG. 13, reference numeral 17 is a chemical etching solution, 18 is a direct-current voltage power source, 21 is a silicon substrate, 22 is a principal surface of the silicon substrate 21, 28 is a non-conductive silicon substrate cassette, 19 is a grounding electrode fixed to the non-conductive silicon substrate cassette 28 parallel at a specific distance from the principal surface 22 of the silicon substrate 21, 29 is an electrode fixed to the non-conductive silicon substrate cassette 28 so as to contact with the back side of the silicon substrate 21, and 30 is a wet removing device comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, non-conductive silicon substrate cassette 28, and electrode 29.
FIG. 1 to FIG. 7 are as mentioned in the first embodiment, and FIG. 13 shows the process sectional view using instead of FIG. 5.
As shown in FIG. 13, silicon substrates 21 are set on the non-conductive silicon substrate cassette 28 so that the principal surfaces 22 of the silicon substrates may confront each other, and with the electrode 29 electrically connected to the back side of the silicon substrates 21, the low resistance polycrystalline silicon residue 11 shown in FIG. 4 is selectively removed by etching chemically while applying a direct-current voltage to the electrode 29 fixed to the non-conductive silicon substrate cassette 28 by using the wet removing device 30 comprising the chemical etching solution 17, direct-current voltage power source 18, grounding electrode 19, non-conductive silicon substrate cassette 28, and electrode 29.
When the chemical etching solution is 5N KOH heated to 60° C., by applying a direct-current voltage of several volts to several 10 volts to the electrode 29, voltage is applied to the silicon substrates 21, and moreover the capacitor lower electrode 10 shown in FIG. 4 is also at the same potential as the silicon substrates 21, and a passive layer for stopping electrochemical etching is formed on the surface of the silicon substrates 21 and capacitor lower electrode 10.
Since voltage is not applied to the low resistance polycrystalline silicon residue 11, or if applied, the voltage is lowered through the capacitor lower electrode 10, passive layer is not formed, so as to be removed chemically by alkaline etching by KOH, while the silicon substrate 21 and capacitor lower electrode 10 forming the passive layer is not etched.
Thus, in the embodiment, since the grounding electrode 19 fixed to the non-conductive silicon substrate cassette 28 is positioned parallel to the silicon substrates 21, uniformity of etching is enhanced, and moreover since the voltage is applied to the silicon substrates 21 from the electrode 29 fixed to the non-conductive silicon substrate cassette 28, uniformity of voltage applied to the principal surfaces 22 of silicon substrates is enhanced, and the controllability and stability of etching are improved, and further the required number of grounding electrodes 19 may be half the number of silicon substrates 21.
As clear from the description herein, according to the invention, only by feeding current to part of the silicon substrates, the etching residue in non-conductive state of the silicon left over on the interlayer insulating film can be selectively removed while protecting the element surface fabricated on the silicon substrates, and shorting of the circuits of the semiconductor device can be prevented, and the operation of etching process is superior, and in particular it is easier to etch plural silicon substrates simultaneously, thereby contributing to enhancement of mass producibility.
When etching plural silicon substrates simultaneously, by using the conductive substrate cassette of the invention, only by connecting the power source positive electrode to the cassette main body, a positive potential can be applied to all silicon substrates disposed in conductive state on the cassette from their surrounding, so that a great number of silicon substrates can be processed easily by simultaneous etching, thereby enhancing the mass producibility of semiconductor elements.
In the silicon substrate cassette, by disposing the grounding electrodes so as to confront the silicon substrates, the intra-plane uniformity of etching is enhanced, and the manufacturing yield of the semiconductor element can be enhanced.
Moreover, using the non-conductive silicon substrate cassette of the invention, by applying a positive potential from the back side to the silicon substrates disposed in contact with the electrodes through flat silicon substrate application electrodes disposed on the cassette, and moreover by disposing the grounding electrodes so as to confront the silicon substrate, the intra-plane uniformity of etching is enhanced, and the manufacturing yield of semiconductor elements can be improved.
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The method is to selectively etch the etching residue in non-conductive state occurring in semiconductor manufacturing process. A silicon substrate cassette is used in such selective etching.
In removing the etching residue in non-conductive state occurring in semiconductor manufacturing process, by applying a positive potential to part of conductive silicon substrates in an etching solution, the contact surfaces between the silicon substrates and the portion electrically connected thereto and the chemical etching solution are anodically oxidized to protect with a passive film, while only the etching residue in non-conductive state is selectively removed by isotropic etching, thereby achieving the purpose.
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This application is a continuation-in-part of application Ser. No. 08/630,653 filed Apr. 10, 1996, now abandoned.
FIELD OF THE INVENTION
The present invention relates to a system for examining subsurface environments, and more particularly, to a microscope mounted in a soil penetrating probe for detecting visual images of subsurface geological environments.
BACKGROUND OF THE INVENTION
Increasing concern with soil and groundwater contamination and governmental mandated requirements to clean up hazardous waste sites have created a need for cost effective systems and methods for determining the characterization of subsurface environments. In response to such needs, soil penetrating probes have been developed. Soil penetrating probes generally comprise a tube having a tapered tip which is forced down into the ground. Instrumentation in the tube detects various properties of the surrounding geological environment.
U.S. Pat. No. 5,128,882, "DEVICE FOR MEASURING REFLECTANCE AND FLUORESCENCE OF IN-SITU SOIL," describes a soil penetrating probe having an optical fiber, a light source within the interior of the probe, and a transparent window which provides a light port into and out of the probe. Light passes through the transparent window to irradiate the surrounding soil immediately outside of the window as the probe passes through the soil. The irradiated soil reflects light back through the window whereupon the reflected light is collected by a fiber optic link connected to instrumentation on the surface. The collected light then is subjected to spectroanalysis for determining the chemical composition of the soil, particularly with regard to soil contamination. This system only detects the spectral characteristics of the surrounding environment; It cannot provide optical images. Therefore, information such as the porosity and grain size of surrounding soils are not discernible from the type of information provided through spectral analysis. However, porosity and grain size are important characteristics because they are important variables that control the transport of contaminants in soil.
Another soil penetrating probe system is described in U.S. Pat. No. 5,123,492, "METHOD AND APPARATUS FOR INSPECTING SUBSURFACE ENVIRONMENTS." This system includes a soil penetrating probe having a clear tube in which is suspended a video camera linked to the surface. A significant limitation of this system is that because the camera freely swings within the transparent tube, the focus of the camera with respect to the surrounding geological features is constantly changing and cannot be controlled. Furthermore, the system does not provide any means for illuminating the surrounding subsurface environment other than from ambient light which may happen to filter from the surface down through the tube.
Therefore, a continuing need exists for a system which can provide clear, sharply focused optical images of subsurface geological environments.
SUMMARY OF THE INVENTION
A microscope imaging system comprises a tube including a bore and a sidewall having an aperture; an optically transparent window positioned in the aperture; a light source for generating first light signals which are directed at diffuse angles through the window; an imaging system mounted in the bore for detecting second light signals which enter the bore through the window; and a first lens system for focusing the second light signals onto the imaging system. The system may also include a focusing system for changing the distance between the imaging system and the first lens system.
The invention provides a system that can be used to detect soil properties such as type of soil, grain size, color, porosity, presence or absence of fluid between soil particles, and volumetric density. Moreover, such properties can be detected in real time when the imaging system is implemented as a video camera. The invention advantageously images soil in contact with the probe, thereby establishing the focal distance of the image which is to be detected. Another advantage is that the invention may be used to investigate soil properties at spatial scales as small as individual soil particles. Moreover, the fact that the magnification factor and focal distance of the image are defined and fixed by the relationship of the camera to the window allows for quantification of soil particle size. An important feature of the invention is that it indirectly illuminates the soil through the window housing so as to provide sufficient light to illuminate the soil and to prevent saturation of the image detector from excessive light reflected back through the window.
In another embodiment, the invention further includes a fluid delivery system for ejecting a chemical indicator reagent from the probe as it is being deployed through the ground. The reagent is dispersed from the probe in the vicinity of the optical window so that it comes into direct contact with the soil outside the probe in the vicinity immediately adjacent to the window. The reagent reacts with the chemical constituent of interest (analyte) in the soil to produce a detectable optical response when exposed to a suitable light source. The operation of the invention is based on the fact that in the absence of the indicator reagent, no optical response is observable for certain types of chemical and/or biological species of interest. However, when a species of interest is present and reacts with the indicator reagent, a new compound is formed that may be optically detected so that the presence of the species of interest then may be ascertained. The probe may be pushed into the ground to a depth on the order of up to about 150 feet using a hydraulic ram while the indicator reagent is pumped out of the probe at a predetermined flow rate. In order to account for the possible variations in the amount of indicator reagent dispensed into the surrounding soil structure, a second chemical tracer can be added to the indicator reagent. The chemical tracer is non-reactive with the analyte and is spectroscopically distinguishable from the product of the species of interest and indicator reagent. The chemical tracer normalizes the concentration of indicator reagent added to the soil sample to correct for changes in optical response due to differences in the concentration of indicator present in the soil.
The indicator reagent delivery system extends the capabilities of the in situ sensor to detect chemical contaminants in subsurface soil environments that cannot presently be measured by direct optical methods. By continually dispensing the indicator reagent into the sample, or surrounding soil structure, problems associated with mechanical, chemical, and photochemical degradation of the indicator are simplified or eliminated.
These and other advantages of the invention will become more apparent upon review of the accompanying text taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of an in-situ microscope embodying various features of the present invention.
FIG. 2 is an enlarged view of the window housing of the microscope represented in FIG. 1.
FIGS. 3A, 3B, 3C and 3D (collectively referenced as FIG. 3) are a schematic view of an example of in-situ microscope for examining subsurface environments embodying various features of the present invention.
FIG. 4 is an enlarged view of the window housing illumination structure.
FIG. 5 is a full length view of the terminator insert.
FIG. 6 is a cross-sectional view of the terminator insert taken along line 6--6 of FIG. 5.
FIG. 7 shows another full length view of the terminator insert.
FIG. 8 is an end view of the terminator insert of FIG. 7.
FIG. 9 is a cross-sectional view taken along the length of the terminator insert.
FIG. 10 is another end view of the terminator insert of FIG. 9.
FIG. 11 is a cross-sectional view of the terminator insert taken along line 11--11 of FIG. 9.
FIG. 12 is a cross-sectional view of the terminator insert taken along line 12--12 of FIG. 9.
FIG. 13 is a cross-sectional view of the terminator insert taken along line 13--13 of FIG. 9.
FIG. 14 is a cross-sectional view of the terminator insert taken along line 14-14 of FIG. 9.
FIG. 15 is another full length view of the terminator insert.
FIG. 16 is an end view of the terminator insert shown in FIG. 15.
FIG. 17 shows the fork support.
FIG. 18 is an end view of the fork support shown in FIG. 17.
FIG. 19 is an enlarged view of the focusing system.
FIG. 20 is a side view of the jam nut.
FIG. 21 is a front view of the jam nut of FIG. 20.
FIG. 22 shows the anchor plate.
FIG. 23 is a side view of the anchor plate of FIG. 22.
FIG. 24 shows the adjusting screw.
FIGS. 25A and 25B (collectively referenced as FIG. 25 ) show an in situ optical detection system further including an indicator reagent delivery system.
FIG. 26 is a three-quarter exterior view of the system shown in FIG. 25.
FIG. 27 is a schematic diagram of the indicator reagent delivery system of FIG. 25.
FIG. 28 shows the nozzle assembly of the fluid delivery system used in conjunction with the system shown in FIG. 25.
FIG. 29 is a plan view of the nozzle depicted in FIG. 28.
FIG. 30 is a cross-sectional/block diagram of another embodiment of an optical detecting system which includes an indicator reagent agent delivery system.
FIG. 31 is a schematic illustration of an in-situ microscope where the light source is located remotely from the tube.
Throughout the several figures like elements are referenced using like reference numbers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention provides a microscope imaging system for remotely detecting optical images of subsurface geological structures such as soil particles. Imaging is accomplished by illuminating the soil in contact with the outside of an optically transparent window installed in a soil penetrating probe and then imaging the soil using a miniaturized imaging system such as a camera supported in the probe. A signal representing the images is provided by the camera and conveyed to the surface where it may be displayed on a TV monitor, recorded on a VCR and/or recorded digitally using a video frame grabber coupled to a microcomputer system.
Important features of the invention include: (1) an illumination system that provides light to illuminate geological structures of interest so that the camera may be usefully operated in what would otherwise be a dark environment; (2) a lens system optically coupled to an optically transparent window installed in the soil penetrating probe so that the magnification factor and focal distance of a detected image are both known and fixed for geological features in contact with the window. The fact that the magnification factor of the soil particles imaged by the camera is known facilitates measurement of the grain size of soil particles from analysis of the image. The use of different lenses in the magnification system makes changes readily possible in the magnification factor of the imaging system.
In FIGS. 1 and 2 there is shown an in-situ microscope imaging system 200 which includes a light source 204, an optional optical filter 208, a focusing lens 212, optical fibers 216 and 220, window housing 224, optical reflecting element 228, lens system 232, optional optical filter 236, and imaging system 240, such as a still camera or video camera, having an image detecting area 244, all mounted in a tube 248 having a throughbore 262. A conically shaped tip 252 is mounted to the penetration end 256 of the tube 248. The optical reflecting element 228 may be implemented as a prism or mirror. The window housing 224 includes an insert fitting 254 and a transparent window 242. The insert fitting is fitted through an aperture 250 of sidewall 258 of tube 248. The surface 234 of bore 238 preferably has a surface finish which when illuminated, causes light to be diffused in different directions. The light source 204 may be implemented, for example, as a laser, flash lamp, arc-lamp, or any other source of optical energy that generates light at wavelengths suitable for a particular application. When implemented as a laser, the light source 204 may be a nitrogen, xenon-chloride, Nd-YAG, or other suitable laser. Lens system 232 may have a fixed focal length or may have a motor driven "zoom" type lens to provide the lens system with an adjustable focal length. In FIG. 1, the light source 204 is shown positioned in the tube 248. However, there may be applications where it is desirable for the light source 204 is located remote from the tube 248, as shown in FIG. 31.
Referring to FIG. 1, light source 204 generates light signals 260 which are directed to focusing lens 212. In some applications, optical filter 208 optionally may be interposed between the lens 212 and light source 204 to filter out undesirable spectral components or to select specific components, having particular wavelengths, of the light signals 260. Lens 212 focuses light signals 260 onto the bare polished, and preferably bundled ends 218 and 222 of optical fibers 216 and 220, respectively. Light signals 260 propagate through optical fibers 216 and 220. Then, as shown in FIG. 2, the light signals 260 are emitted from the ends 226 and 230 of optical fibers 216 and 220, respectively. Fibers 216 and 220 may be implemented as Ensign-Bickford HCG fiber having a 365 micro meter diameter, although it is to be understood that other fibers having other diameters may also be used. The light signals 260 illuminate the sidewall, 234 of bore 238 and are directed at diffuse angles through transparent window 242 to illuminate soil particles 246 outside the window 242. In the preferred embodiment, transparent window 242 may be made of sapphire because it is optically transparent over a broad spectral range and is very hard. The hardness of the window 224 is important in order for the window to withstand the rigors of abrasion as the tube 248 penetrates the soil.
Still referring to FIG. 2, light signals 260 illuminate the soil particles 246. Light signals 270 radiating from illuminated soil particles 246 are reflected by optical reflecting element 228 and directed to lens system 232. As shown in FIG. 1, lens system 232 focuses the light signals 270 onto image gathering area 244 of imaging system 240. Optionally, optical filter 236 may be interposed between the focusing system 232 and the imaging system 240 to selectively filter undesirable spectral components or to select specific components, having particular wavelengths, of the light signals 270. The image system transforms signals 270 into an output signal 272 which represents an image of the soil particles 246. The output signal may be provided to signal processing equipment, not shown, at the earth's surface.
An example of one particular implementation of the present invention is described with reference to FIG. 3. An in-situ microscope optical imaging system 10 for examining subsurface geological environments includes a soil penetrating probe 12 comprised of a tube 14 and a hardened, conical tip 16 mounted to the penetration end 18 of the tube 14. Inside the tube are mounted a camera 20, such as a video camera which may include a charge coupled device (CCD), a lens system 24, an optically reflective element, such as a mirror 28 or a prism, and an illumination system 32. Examples of video cameras suitable for use in conjunction with the present invention are Sony Corporation Model XC777 1/3" CCD and Model XC999 1/2" CCD. Each of these Sony cameras has a 768×494 pixel array. Referring also to FIG. 4, a window housing 36, having a transparent window 40 and bore 49, is fitted through an aperture 42 in the wall 44 of the tube 14 to provide a viewing port between the interior bore 15 of the tube 14 and exterior 51 of the tube 14. The window housing is mounted to the tube 14 as explained further herein. Window housing 36 has an annular groove 76 in which is fitted O-ring 80 to provide a dirt and moisture seal between the window housing 36 and the sidewall 44 of tube 14.
In FIG. 4, light signals 48 are shown emitted from within the tube 14 at diffuse angles through transparent window 40 with respect to the longitudinal axis a--a of the penetrometer 12. Light signals 48 become scattered (i.e., diffused) after illuminating the surface 47 of bore 49 in window housing 36. The diffused light signals 48 are directed through the window 40 to illuminate the surrounding geological structures, not shown. Light signals 52 radiated from surrounding geological structures (not shown) outside transparent window 40 return through the window 40, reflect off mirror 28, and are directed to lens system 24, such as a Sony Corporation 45 mm macro lens. The surface 47 preferably has a finish which causes light signals to become diffused, and may for example, have a surface finish of 250 micro inches r.m.s. so that the surrounding geological structures are illuminated with diffused light to prevent saturation of the imaging system 20. In the preferred embodiment, light signals 48 are provided by a light source 64.
Lens system 24 focuses light signals 52 which radiate into the tube 14 through window 40 and are directed onto the image gathering area 56 of the camera 20. Image signals generated by the camera 20 represent the detected image of geological structures outside window 40 and are provided to the surface, not shown, by signal line 60. Optionally, the preferred embodiment may include a focusing system 72 for changing the relative position of the image gathering area 56 of camera 20 with respect to the lens system 24 in order to precisely focus light signals 52 onto the image-gathering area 56 of camera 20.
As shown in FIG. 4, an illumination plate 88 is mounted to a terminator insert 46 preferably by bolts 98. The distal ends 69 of optical fibers 68 are mounted within bores 70 of illumination plate 88 at an angle whereupon light signals 48 illuminate the sidewall 47 of bore 49 in window housing 36 with diffused light. The axes of the bores 70 are at an angle theta, as for example 45 degrees, with respect to the longitudinal axis a--a of the tube 14. The terminator insert 46, shown by way of example in FIGS. 5-16, slides within bore 15 of tube 14 and supports the window housing 36 in the bore 42 of the tube 14. FIG. 4 shows that the illumination plate 88 includes a center bore 96 having a longitudinal axis b--b which preferably is coaxially aligned with bore 49 of the window housing 36 to provide a light port into and out of the bore 15 of tube 14. The opposite ends of illumination plate 88 include apertures 95 through which threaded connecting elements 98 are fitted to attach the illumination plate 88 to the terminator insert 46.
As shown in FIG. 3, the mirror 28 is mounted to mirror support 104 of the terminator insert 46 so that when terminator insert 46 is fitted in bore 15 of the tube 14: 1) the reflecting surface 108 of mirror 28 reflects light signals 52 through lens system 24 to the image gathering surface 56 of the camera 20; and 2) the window housing 36, attached to terminator insert 46, fits through aperture 42.
By way of example, the camera 20 is fixedly mounted between two tines 115 of fork support 116, as shown in FIG. 3, preferably using an adhesive, not shown. The fork support 116 may be implemented as shown in FIGS. 17-18. Then the fork support 116 and camera 20 are slid inside bore 15 of tube 14 to precisely position the image gathering area 56 of camera 20 with respect to the lens system 24. The end 120 of fork support 116 includes a threaded aperture 128 and a bore 124.
As shown in FIG. 3, light signals 52 are focused onto the image-gathering surface 56 of camera 20 by adjusting the distance between the image-gathering area 56 and the lens system 24 using focus system 72. Focus system 72, shown in FIG. 19, includes a jam nut 140 [FIGS. 20-21], anchor plate 142 [FIGS. 22-23], adjusting screw 144 [FIG. 24], retaining ring 146, and set screw 149. Adjustment of the position of camera 20 is accomplished by placing anchor plate 142 against land 148 of bore 112 in tube 14 so that pin 152, which is staked to anchor plate 142, extends into bore 124 of fork support 116. Pin 152 prevents fork support 116 from rotating in bore 15 of tube 14. Adjusting screw 144 is inserted through aperture 156 of anchor plate 142 and then retaining ring 146 is fitted in slot 158 of adjusting screw 144 so that the adjusting screw cannot slip out of aperture 156 of anchor plate 142. Then jam nut 140 is threaded into bore 112 of tube 14 using a spanner wrench (not shown) fitted into bores 143 so that the jam nut tightly seats against anchor plate 142 thereby fixing the anchor plate 142 relative to tube 14. Adjusting screw 144 may then be turned to vary the distance between video camera 20 and lens system 24 until light signals 52 are sharply focused onto image-gathering area 56 of video camera 20. The set screw 149 is then advanced against surface 120 of fork support 116 to fix the distance between the image gathering area 56 of camera 20 with respect to the lens system 24.
In FIG. 25 there is shown microscope imaging system 200 further including an indicator reagent delivery system comprising a pump system 264 which pumps a reactive fluid 271 through a preferably flexible tube 266 connected through the end 267 of the tube 248 to a nozzle 268. The tube 268 preferably may be implemented as 1/8 inch diameter polypropylene tubing and have an inside cross-sectional area of about 0.005 in 2 . Such tubing has a working pressure of 350 psig and a burst pressure of 1400 psig. The nozzle 268 is mounted through the sidewall 258 of tube 248 so that the indicator reagent 271 may be dispensed or pumped from the nozzle 268 into the surrounding soil strata. The indicator reagent 271 is selected to chemically react with certain types of chemicals or micro-biological organisms of interest that may be present in the soil so that they may more easily be detected when illuminated due to a fluorescence or colorometric response of the complex. The nozzle 268 is preferably mounted through the sidewall 258 of tube 248 between the conically shaped tip 252 and window 224 so that, as shown in FIG. 26, the window 224 and nozzle 268 are generally located on a line a--a located on the surface of the tube 248 which is parallel to the longitudinal axis b--b of the tube 248. Therefore, indicator reagent is present in the soil by the time the reagent impregnated soil is viewed through the window 224 as the tube 248 is driven through the soil.
Pump circuit 264, shown in FIG. 27, includes a pump 272 which draws indicator reagent 271 from reservoir 274 through supply line 276 and outputs pressurized indicator reagent 271 through pump output line 278 to pressure regulator 280. The pressure regulator 280 regulates the pressure of indicator reagent agent 271 by, inter alia, returning some indicator reagent 271 back to reservoir 274 through bypass flow return line 282. The pressure regulator outputs indicator reagent 271 having a predetermined pressure, via line 284, to flow meter 286 which controls the volume flow of the pressurized indicator reagent 271. The flow regulated output of indicator reagent 271 is delivered to nozzle 228 via conduit 266. The pump may be a Neptune Model 535-S-N3 positive displacement piston/diaphragm pump having stainless steel internal elements, a Teflon™ diaphragm, and inert Viton™ seals so that the pump is chemically resistant to the indicator reagent 271. Like the pump 272, the pressure regulator 280 and flow meter 286 should be corrosion and chemically resistant to the indicator reagent 271. An example of a flow meter suitable for many applications of the invention is a polypropylene bellows type flow meter of the type manufactured by Gorman-Rupp which can accurately regulate the flow of indicator reagent 271 through nozzle 268 from 1.9 ml/min to 5200 ml/min.
By way of example, as shown in FIG. 28, the nozzle 268 may be implemented as a Prestolok Fitting No. 68PL-2-1-X32 which is positioned through the tube wall 258 using a threaded check housing 288 which includes an O-ring seal 290 that prevents leakage into the tube 248. A contoured washer 292 is positioned between the nozzle 268 and the interior surface 269 of the tube 248 to maintain a tight surface interface between the interior surface 269 and nozzle 268. The nozzle is partially bored out to receive a stainless steel check-ball 294 between the nozzle and the check housing 288. The check-ball 294 prevents external hydrodynamic pressure from forcing fluids from the soil from entering the tube 248. However, the check-ball 294 allows indicator reagent 271 to be pumped out of the nozzle 268. The face 289 of the check housing may include one or more bores 290 through which agent 271 may be pumped. As shown in FIG. 29 by way of example, the check housing may include four bore 290 each having a diameter of about 0.047 inches to provide a combined flow area of 0.007 in 2 . The slightly larger cross-sectional area of the bores 290 compared to that of the tube 266 allows any excessive external ground water pressure to force the check ball 294 to seal off the nozzle 268 from ground water contamination. It is to be understood, however, that the number, pattern, and size of the bores 290 through the face 288 of the check housing 288 may be configured to assure adequate diffusion of the indicator reagent 271 into the surrounding soil at for example, a pressure which preferably is greater than about 100 psig.
The indicator reagents employed in conjunction with the present invention are compounds that form either colored or fluorescent complexes with the analyte (chemical or biological) to be analyzed. The indicator reagents chemically react (or in chemical terms "complex") the chemical species (e.g., a metal ion) or some compound contained in the biological material (e.g., the DNA) of interest to form a new species (e.g., the indicator reagent and metal ion, or indicator reagent and DNA) having an optical response different from that of the uncomplexed analyte or indicator reagent by itself. An example of a common indicator reagent is the pH indicator "phenolphthalein." When a drop of phenolphthalein (which is clear in color) is added to water, the phenolphthalein molecule forms a red colored complex with the hydrogen ions in the water. Since the hydrogen ion concentration in water determines the pH, the intensity of color generated from the complex formed by the phenolphthalein and hydrogen is a direct indicator of the pH of the water.
A suitable class of indicator reagents 271 are fluorescent indicator reagents that form fluorescent complexes with analytes such as heavy metals and cations such as Na+, K+ and Ca++. Examples of other fluorescent indicator reagents 271 are specific for the nucleic acids contained in microbiological organisms. Common examples of fluorescent indicator reagents may based on the quinolines such as hydroxyquinoline-5-sulfonic acid, 8-hydroxyquinoline, 2-methyl-8-hydroxyquinoline, N-(6-methoxy-8-quinoyl)-para-toluene sulfonamide and p-tosyl-8-amino quinoline. Molecules of these examples form fluorescent complexes with metals such as zinc, cadmium, magnesium, etc. Also, there are a wide range of fluorescent nucleic acid stains that form fluorescent complexes with the nucleic acids contained in the cells of the microbiological organisms. Specific examples of such fluorescent indicators, or nucleic acid stains, include the cell-permeant SYTO® indicator reagents for labeling DNA and RNA in living cells including mammalian cells, fungi and bacteria. Other examples of florescent indicator reagents include cell-impermeant SYTOX® Green nucleic acid stains that penetrate cells with compromised plasma membranes. SYTO® indicator reagents and SYTOX® Green nucleic acid stains are available from Molecular Probes, Inc. of Eugene, Oreg. Fluorescent indicators that may be used to detect the presence of nucleic acids include, by way of example, hexidium iodide (a lipophilic phenthridiium dye) and hydroxystilbamidine.
In addition to fluorescent indicator reagents, there is also a family of "indicator reagents" based on the formation of colored coordination compounds. These compounds form "colored" rather than fluorescent complexes with a suitable analyte of interest. Ethylenediaminetetraacetic acid (EDTA) is an example of an indicator reagent that forms colored complexes with metals such as copper. Nitrilotriacetic acid (NTA) is an example of an indicator reagent that forms colored complexes with metals such as nickel and copper.
In order to account for the possible variations in the amount of indicator reagent which may be dispensed into the surrounding soil structure, a chemical tracer 273 which is non-reactive with the analyte can be added to the indicator reagent. Thus, both an indicator reagent 271 and chemical tracer 273 may be dispensed from pump system 264 of FIG. 25 and pump 272 of FIG. 30. The non-reactive (chemical tracer is spectroscopically distinguishable from the indicator reagent and analyte (species of interest) and is used to normalize the optical response due to differences in the concentration of indicator reagent present in the soil. Such normalization may be determined from the ratio of the intensities of the spectral responses of the complex (the chemical product of the analyte and indicator reagent) and the chemical tracer 273. Examples of tracer chemicals are rhodamine 6G and quinine sulfate.
Another embodiment of an optical detecting system 300 which includes a reactive agent delivery system is described with reference to FIG. 30. The system includes a cone penetrometer 301 comprising a generally cylindrical body 302, preferably made of a hardened steel, to which is mounted a conically shaped hardened tip 306. The cylindrical body 302 has a tube wall 304 and a bore 305. An optical window 308 and fluid nozzle 314 are mounted through the tube wall 302 such that the nozzle 314 is positioned between the conical tip 306 and the window 308. By way of example, the window 308 may be made of sapphire, a relatively hard material, so that abrasion damage to the window 308 is minimized as the penetrometer is driven into the surrounding subsoil environment, not shown. An optical fiber 312 optically interconnects the window 308 and an optical detecting system 310. Pump system 316 pumps indicator reagent 315 through tube 318 and out of nozzle 302 into the surrounding soil structure. In some application, it may be desirable for pump system 316 to further dispense a chemical tracer 320 along with the indicator reagent for the reasons described above with reference to chemical tracer 273. Any light signals 320 which pass through window 308 propagate via optical fiber 312 to optical detecting system 310 which may include, for example, a CCD camera, a photo detector such as a photo diode array, or a photo multiplier tube.
Although the invention has been described with reference to specific embodiments, numerous variations and modifications of the invention may become readily apparent to those skilled in the art in light of the above teachings. For example, the light source 64 shown in FIG. 3 may be mounted within tube 14 or may be located remotely from the tube. Moreover, the invention may employ chemical indicator reagents that produce either a decrease or increase in an optical signal for an analyte of interest. Examples of alternative indicators include: (1) reagents that produce chemiluminescent signals without external optical stimulation; and (2) reagents that quench the specific fluorescence of the analyte of interest. Furthermore, the light source and/or pump system, including the reservoir may be mounted within the probe, or externally with respect to the probe. Further, the reagent could be pumped from the surface to outlet ports on the probe, or be contained in a reservoir mounted within the probe itself. Additonally, the pump system may be used to dispense one or more indicator reagents in combination or serially, as well as one or more tracer compounds. Therefore, it is to be understood that the invention may be practiced other than as specifically described.
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A microscope imaging system comprises a tube including a bore and a sidewall having an aperture; an optically transparent window positioned in the aperture; a light source for generating first light signals which are directed at diffuse angles through the window; an imaging system mounted in the bore for detecting second light signals which enter the bore through the window; and a first lens system for focusing the second light signals onto the imaging system. The system may also include a focusing system for changing the distance between the imaging system and the first lens system, and a fluid delivery system for ejecting a chemical indicator reagent from the probe as it is being deployed through the ground. The reagent is dispersed from the tube in the vicinity of the optical window so that it comes into direct contact with the soil outside the tube near the window. The reagent reacts with a chemical or biological constituent of interest that may be present in the soil to produce a detectable optical response when exposed to a suitable light source.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present invention claims the benefit of U.S. Provisional Patent Application No. 62/212,154 filed Aug. 31, 2015, the contents of which are incorporated herein by reference.
FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] N/A
FIELD OF THE INVENTION
[0003] The present invention generally relates to a system and method for dynamically adjusting the speed of a dryer belt of a textile dryer for optimal performance.
BACKGROUND OF THE INVENTION
[0004] Textile dryers typically include conveyor belts that transport a textile item, such as a shirt that has been in a silk screening or other printing operation, through a heated drying chamber. The conveyor belt, configured as an endless loop, travels at a constant speed through the heated chamber to allow the ink in the textile to set or cure.
[0005] The drying chamber can take a significant amount of time at start-up to come up to the appropriate drying temperature. This is due in part because too much heat is exhausted by the conveyor belt running at its normal speed. Similarly, the chamber can take a significant amount of time cooling down at the end of a run. Again, this is due in part to the exhaust rate of the conveyor belt at normal operating speeds.
[0006] During a drying run, the heat chamber can sometimes vary in temperature. In such situations, textiles traveling on a conveyor belt at normal operating speeds can potentially burn or insufficiently dry depending on whether the temperature increased or decreased, respectively.
[0007] The present invention provides a textile dryer that is configured to modify the conveyor belt speed to optimize conditions in the heated drying chamber. The present dryer saves time and energy, and provides a more consistently finished product.
SUMMARY OF THE INVENTION
[0008] The present invention provides a dynamically adjustable textile dryer and a method for controlling the dryer belt speed for optimal performance and temperature control of the dryer. The speed of the belt can be adjusted at start-up, shut-down, or during the middle of a drying run to more efficiently and quickly change the temperature in the dryer.
[0009] At start-up, the textile dryer is configured to run the conveyor belt at a slower than normal speed. In this mode, less heat is exhausted with the belt than when the belt is running at its normal (faster) operating speed used for curing printed textile items (e.g., decorated garments). This slower speed enables the dryer's heat chamber to come up to operating temperature more quickly. This expedites production by reducing the time and cost of dryer pre-heating, and saves energy.
[0010] At shut-down the belt is adjusted in the opposite direction. Before a dryer can be shut down, the heat chamber must be cooled or the portion of the belt which would be stopped in the chamber would melt—ruining the (expensive) belt. The present dryer is configured to increase the belt speed during this time. This introduces more fresh air into the heat chamber and pulls (exhausts) more heated air out of the chamber, thus reducing the temperature quickly (i.e., in a time period less than that of keeping the belt at its normal operating speed or slowing it down during this period).
[0011] The present textile dryer is also configured to adjust the belt speed during normal operation. During a run the heat chamber can sometimes vary in temperature (this can occur for a number of reasons, e.g., increase in load, change of ambient conditions around the dryer, etc.). Accordingly, the textile dryer increases the belt speed (if the temperature increases) or decreases the belt speed (if the temperature decreases).
[0012] In accordance with one embodiment of the invention, a textile dryer that can dynamically and quickly adjust temperature in the drying chamber is provided. The textile dryer comprises a controller (such as a PLC), a drying chamber, a temperature probe for sensing a temperature of the drying chamber operatively coupled to the controller and a moveable belt for transporting textile items through the drying chamber. The moveable belt is configured to draw ambient air into the drying chamber through an opening in a first end of the chamber and exhaust air from the drying chamber through an opening in a second end of the drying chamber. The dryer also includes a belt drive for moving the belt operatively coupled to the controller. The belt drive adjustably moves the belt at speeds set by the controller in response to a sensed temperature to more quickly adjust the temperature of the drying chamber to either increase the temperature (i.e., by slowing the belt speed and thus slowing the cooler ambient air being drawn in and the hotter chamber air from being exhausted due to the belt) or decrease the temperature (i.e., by increasing the belt speed and thus increasing the cooler ambient air being drawn in and the hotter air in the chamber being exhausted by the belt). A belt motion sensor can also be operatively coupled to the controller.
[0013] The controller can be configured (e.g., programmed) to operate the dryer to control the speed of the belt depending the condition of the dryer. For example, the controller at start-up of the dryer can be configured to initially run the belt at an initial first speed and to then run the belt at a second (i.e., normal) speed upon the dryer reaching a predetermined temperature where the first speed is slower than the second speed. This slower initial speed allows the heating chamber to come up to temperature more quickly than utilizing the normal (second) speed initially at start-up.
[0014] Additionally, the controller at shut-down of the dryer can be configured to increase the speed of the belt. This increased speed allows the drying chamber to cool more rapidly.
[0015] Moreover, the controller can be configured to monitor a temperature of the drying chamber and to adjust a speed of the belt based on the monitored temperature. Specifically, the controller can be configured to increase the speed of the belt if the monitored temperature goes above a predetermined temperature. Similarly, the controller can be configured to decrease the speed of the belt if the monitored temperature goes below a predetermined temperature. The predetermined value can be, for example, plus or minus 10° F.
[0016] In accordance with another embodiment, a method of operating a textile dryer with a controller is provided. The method comprises the steps of controlling a heating element to initiate heating a drying chamber of the textile dryer at start-up, controlling a conveyor belt to move at a first speed, sensing a temperature of the drying chamber, and controlling the conveyor belt to move at a second speed faster than the first speed upon sensing a predetermined temperature.
[0017] Additionally, the method can include controlling the heating element to shut down, and controlling the conveyor belt to move at a third speed faster than the second speed.
[0018] Additionally, the method can include sensing an increase in the temperature in the drying chamber and controlling the conveyor belt to move at a third speed faster than the second speed when the sensed temperature increases a predetermined value. Similarly, the method can include sensing a decrease in the temperature in the drying chamber and controlling the conveyor belt to move at a third speed slower than the second speed when the sensed temperature increases a predetermined value.
[0019] The step of sensing an increase in the temperature in the drying chamber can comprise sensing a first temperature and sensing a second temperature 10° F. greater than the first temperature. Similarly, the step of sensing an increase in the temperature in the drying chamber can comprise sensing a first temperature and sensing a second temperature 10° F. less than the first temperature.
[0020] In accordance with yet another aspect of the invention, a method of operating a textile dryer at shut down with a controller is provided. The method comprises the steps of controlling a heating element in a drying chamber of the textile dryer to shut down and increasing a conveyor belt speed.
[0021] In accordance with yet another embodiment of the invention, another method of operating a textile dryer with a controller is provided. The method comprises the steps of sensing a first temperature of a drying chamber of the textile dryer, sensing a second temperature of the drying chamber different from the first temperature, and one of increasing a conveyor belt speed of a conveyor belt if the second temperature is greater than the first temperature and decreasing the conveyor belt speed if the second temperature is less than the first temperature. The second temperature can be one of 10° F. higher than the first temperature and 10° lower than the first temperature.
[0022] Further aspects of the invention are disclosed in the Figures, and are described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] To understand the present invention, it will now be described by way of example, with reference to the accompanying drawings in which:
[0024] FIG. 1 is a schematic view of a textile dryer in accordance with the present invention;
[0025] FIG. 2 is a process flow chart for controlling aspects of the textile dryer of FIG. 1 in accordance with the present invention;
[0026] FIG. 3 is a process flow chart for sensing the temperature of the drying chamber of the textile dryer of FIG. 1 ;
[0027] FIG. 4 is a process flow chart for sensing motion of the belt of the textile dryer of FIG. 1 .
DETAILED DESCRIPTION
[0028] While this invention is susceptible of embodiments in many different forms, there is shown in the drawings, and will herein be described in detail preferred embodiments of the invention with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the broad aspect of the invention to the embodiments illustrated.
[0029] The present invention is directed to a textile dryer and method of operation for optimally heating and cooling a drying chamber by modifying the speed of a conveyor belt. Modification of the belt speed adjusts the amount of heat exhausted from the system.
[0030] FIG. 1 shows a textile dryer 10 having a conveyor belt 12 that is used to advance textiles through a drying or heated chamber 14 . The belt 12 and drying chamber 14 are supported by legs 16 .
[0031] The belt 12 is part of an endless loop that is moved by a belt drive 18 . Textiles are placed on the belt 12 at a first end 20 and are moved through an opening 22 to the drying chamber 14 and out of an exit 24 to a second end 26 . A belt motion sensor 40 is positioned proximate the first end 20 of the belt 12 .
[0032] The dryer 10 includes a heating element, such as propane or natural gas burner 28 , and a main exhaust 30 . The dryer 10 can also include an end hood 32 and an end hood exhaust 34 . In addition to the main exhaust 30 and end hood exhaust 34 , heat is also exhausted by the belt 12 moving through the drying chamber 14 and through the exit 24 . The belt 12 also draws in cooler air through the opening 22 from outside the chamber 14 .
[0033] A temperature probe 36 is mounted for sensing the temperature of the drying chamber 14 . More than one temperature probe—measuring different areas of the dryer 10 or chamber 14 —can also be used. Additionally, other types of probes or sensors (e.g., humidity sensors) can be utilized with the dryer 10 .
[0034] A controller 38 , such as a PLC, is mounted to the side of the dryer 10 . The controller 38 is electrically coupled to the relevant components of the dryer (e.g., heating elements, belt drive, temperature probe, etc.). The controller 38 is programmed to modify the belt speed for optimal performance of the dryer 10 .
[0035] Specifically, in accordance with one embodiment of the invention, the controller 38 is programmed to initiate a slower than normal belt speed during start-up of the dryer 10 . This is partially illustrated in FIG. 2 . The slower belt speed allows the drying chamber to heat up faster than normal because heat is not being exhausted from the chamber (due to belt speed) at the same rate as the normal (i.e., higher) belt speed. Similarly, cool air is also not being drawn into the chamber at the same rate as the normal belt speed. This slower belt speed more efficiently (and therefore cost effectively) allows the dryer to warm up faster than normal. Once the drying chamber is near or at its typical drying temperature, the controller 38 increases the belt 12 to its normal or typical speed. The “normal” speed may depend on various factors, such as the type of textile being dried, type of ink used or other material(s) applied to the textile that requires drying, ambient moisture, etc.
[0036] In accordance with another embodiment of the invention, the controller 38 is programmed to increase the belt speed (above its normal or typical drying speed) during shut-down of the dryer 10 . Again, as partially illustrated in FIG. 2 , the increased speed increases the amount of heat exhausted through the exit 24 of the drying chamber 14 by the belt 12 , as well as increases the amount of cool outer air drawn through the opening 22 . The chamber 14 must be cooled prior to stopping the belt 12 . Otherwise, the portion of the belt 12 left in the chamber 14 could melt if it is not moving.
[0037] In accordance with another embodiment of the invention, the controller is configured to increase or decrease the temperature during a drying run—by either increasing or decreasing the belt speed—depending on fluctuations of temperature in the drying chamber 14 . Such fluctuations may occur, for example, by fluctuations of the heating elements, or changes in the ambient conditions, etc. The controller 38 monitors the temperature of the chamber 14 using the temperature probe 36 . When the temperature moves a predetermined amount (e.g., 10° up or down), then the controller 38 signals the belt drive to increase or decrease the belt speed as appropriate. The controller 38 can concurrently adjust the heating elements in addition to adjusting the belt speed. Specifically, the controller can turn up the heating elements to increase the temperature in the chamber, or turn down the heating elements to decrease the temperature in the chamber. This control of the heating elements, combined with adjustments of the belt speed, decreases the amount of time to adjust the chamber temperature than use of either method alone.
[0038] FIG. 3 illustrates an information flow for sensing temperature of the drying chamber 14 by the controller 38 from the temperature probe 36 . FIG. 4 illustrates an information flow of the motion proximity sensor 40 communicating with the controller 38 .
[0039] Many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood within the scope of the appended claims the invention may be protected otherwise than as specifically described.
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A dynamically adjustable textile dryer and method of controlling a conveyor belt speed of the textile dryer is provided. The speed of the belt is utilized to more quickly adjust the temperature of the drying chamber.
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BACKGROUND OF THE INVENTION
The present invention is directed to a device for feeding sheets or blanks into a processing machine, which is designed for converting the sheet or blank into a product, for example, a folding and gluing machine.
A feeding device is already known, which has a front stop and a conveying arrangement for feeding the bottom sheet of a pile underneath the front stop into a folder gluer, which operation is to be determined by a controllable rhythm. Such a device is described in detail in U.S. Pat. No. 3,907,278, whose disclosure is incorporated by reference thereto. In the patent, the sheet infeed arrangement consists of a transmission pulley provided with a unidirectional coupling which enables the driving of the conveyor belts in one direction only. The necessary drive occurs from a control shaft actuated intermittently by a connecting rod-and-crankshaft arrangement.
The device of the patent, however, has a serious drawback in that the stroke required by the sheet to be fed cannot be adapted to the particular length of the sheet. Thus, the device results in an inadequate shift for the infeed control.
In fact, if such a device is used, the sheet is moved forward through a distance corresponding to the conveyor belt movement caused by the connecting rod and crankshaft arrangement until the sheet will be nipped by the drive rollers which are actually in charge of terminating the infeed movement. The sheet infeed action is, thus, carried out in two consecutive steps by two interacting appliances, which can jeopardize a reliable control of the advance for the sheet during the step of being fed into the processing machine.
SUMMARY OF THE INVENTION
The present invention is directed to overcome the above-mentioned drawbacks and its objects are achieved by allowing the feed of sheets into a sheet converting or processing machine by an improvement in the device designed for feeding sheets into a processing machine, said device having a frame, means for mounting one or more conveyor devices or units which includes at least one endless belt, a front stop for positioning a pile on the belt, said belt taking the bottom-most sheet of the pile beneath the front stop in the direction of feed. The improvement comprises the conveyor means including single drive means for driving the continuous belt of each conveyor unit, control means for sequentially operating the drive means, and said mounting means adjustably mounting the conveyor units in selected lateral positions in a direction transverse to the direction of movement of the sheets through the device.
The benefits obtained from this invention consist essentially in that the infeed of the sheets into the foldergluer is achieved without any slipping on the belts of the conveyor device. Moreover, the user has the possibility to adapt the forward movement of the belts of the conveyor device as required by the actual length of the sheets or blanks to be fed, which provides the operator with the possibility of determining at will the interval between two consecutive sheets. This will provide the advantage of increased efficiency in the use of the folder-gluer and assures the sequential infeed of the sheets with a high accuracy.
Other features and advantages of the present invention will be readily apparent from the following description of the preferred embodiments, the drawings and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side view, with portions broken away for purposes of illustration, of the infeed device of the present invention;
FIG. 2 is a cross sectional view, with portions in elevation for purposes of illustration, taken along the lined II --II of FIG. 1;
FIG. 3 is a cross sectional view, with portions in elevation for purposes of illustration, taken along the lines III --III of FIG. 1;
FIG. 4 is a partial cross sectional view, with portions in elevation for purposes of illustration, taken along the lines IV--IV of FIG. 1;
FIG. 5 is a cross sectional view, with portions in elevation for purposes of illustration, taken along the lines V--V of FIG. 1;
FIG. 6 is a cross sectional view, with portions in elevation for purposes of illustration, taken along the lines VI --VI of FIG. 1;
FIG. 7 is a side view, with portions broken away for purposes of illustration of the sheet conveyor unit in accordance with the present invention;
FIG. 8 is a cross sectional view, with portions in elevation for purposes of illustration, taken along the lines VIII--VIII of FIG. 7;
FIG. 9 is a cross sectional view, with portions in elevation for purposes of illustration, taken along the lines IX --IX of FIG. 7;
FIG. 10 is a cross sectional view, with portions in elevation, taken along the lines X--X of FIG. 7;
FIG. 11 is a cross sectional view, with portions in elevation for purposes of illustration, taken along the lines XI --XI of FIG. 7; and
FIG. 12 is a schematic illustration showing the control circuit for the device of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The principles of the present invention are particularly useful when incorporated in an infeeding device, generally indicated at 1, which is used for infeeding blanks or sheets into a processing machine for further converting the sheets or blanks, such as a folder-gluer. As illustrated in FIGS. 1 and 2, the device 1 has side frames 2 and 3. The sheet infeed station or device includes a front stop 4 for retaining a pile of sheets or blanks (not shown) to be introduced, and is designed for joint operation with a view of feeding the sheets or blanks one at a time by means of a certain number of conveying units or belts 5, which are situated to extend side-by-side in a direction perpendicular or transverse to the direction of feed for the sheets, which is indicated by arrow 201 in FIG. 12. The infeed devices 5 are driven by a transverse arranged shaft 6 (FIG. 1), which has a drive portion with a hexagonal cross section. The sheets fed into the machine by the conveyor appliances or units 5 are then moved forward with more or less equal speed by a lower and upper infeed rollers 7 and 8 to lower and upper conveyors 9 and 10 of the processing machine, such as a folder and gluer. A photoelectric cell 11 is fitted on a support 12 in a position to detect the leading or front edge of a sheet prior to entering between the rollers 7 and 8. The photoelectric cell is located at a fixed distance form the front stop or gate 4 and is, thus, positioned between the stop 4 and a nipping point between the infeed rollers 7 and 8.
The drive of the infeed rollers 7 and 8 occurs by a double face tooth belt 13, which runs around a tooth pinion 14, and 15, which are attached to the ends of the shaft 16 and 17 for the infeed rollers 7 and 8, respectively. The belt 13 is driven in the following manner. A pulley 20 is secured on a shaft 19 and driven by a belt 21, which extends to the drive system or main drive (not illustrated) of the folder and gluer. The shaft 19 also supports a toothed pinion 18 (see FIG. 2), which drives the belt 13. The belt 13 also passes around a toothed pulley 22, which is part of an automatic tightener that maintains a steady tension on the belt 13. The upper feed roller 8 is supported for rotation between two pivoting levers 23 and 24, which can be pivoted by a setting appliance 25 to compensate for changes in the thickness of the sheets which are to be fed. The arrangement of the appliance 25 and the levers 23 are best illustrated in FIGS. 4 and 5.
The cross shaft 6, which is part of the drive means for the conveyors, also obtains its drive from the main drive of the folder-gluer. In order to accomplish this, a toothed pinion 26 is mounted on the shaft 19 and is connected through a toothed belt 27 to a toothed wheel 28, which is secured by screws 72 on an inlet flywheel 29 (best illustrated in FIG. 2) of an electronic-pneumatic brake-and-clutch assembly 30. The clutch assembly 30 has an output shaft 31, which is provided with another toothed pulley or wheel 32 that is connected through a toothed belt 33 to a pinion 34 which is keyed on the end of the crosswise shaft 6. The end of the crosswise shaft 6 is also provided with a toothed pinion 35, which is connected by a toothed belt 36 to a toothed drive wheel 37 that is connected to a pulse generator 38, as best illustrated in FIG. 3. Each of the conveying appliances or units 5 can be laterally shifted and locked in the required position by means of a tightening device, generally indicated at 39, which will be described in greater detail with regard to FIGS. 6 and 7.
The drive shaft 19, as illustrated in FIG. 2, extends crosswise between the two side frames 2 and 3. The drive shaft 19 consists of two half-axles 40 and 41, which are connected together by means of a sleeve 42, which is provided with a groove designed to take up the keys 43 and 44 of the two half-axles 40 and 41. The half-axle 41 is held by a support 45, which is secured against the outside of the side frame 3 by means of screws 46. The support consists of two ball bearings 47 and 48, which are held by retaining rings 49 and 50. The half-axle 41 has the toothed pulley 20 at one of its ends. The other half-axle 40 is supported in the side frame member 2 by a support 51 which is secured on the outer surface of the frame 2 by screws 52.
As illustrated, the half-axle 40 carries the toothed pulley 18 and also the toothed pinion 26. The support 51 consists of two ball bearings 53 held by a retaining ring 54. The toothed pulley 18 and the toothed pinion 26 are keyed on the half-axle 40, and their lateral position is controlled by the bushings 55 and 56. The rotation of the shaft 19 is transmitted to both the infeed rollers 7 and 8 by the double-sided toothed belt 13 and to the brake-and-clutch assembly 30 by the toothed belt 27.
The lower infeed roller 7 is provided with a toothed pinion 14 and extends between the side frames 2 and 3. It is held within the side frame 2 by a ball bearing support 57, which is secured by a washer and screw combination 59. The other end of the lower infeed roller 7 engages a pivot 60, which is provided with a ball and roller thrust bearing 61. The pivot 60 is fitted against the inner surface of the side frame 3 by means of screws 62.
The upper infeed roller 8 is provided with a toothed pinion 15 and is supported at its ends within the pivoting levers 23 and 24 by ball and roller bearings 63 and 64. The upper infeed roller 8 is, preferably, coated with an elastomer coating 65 to increase its adhesion to the sheets or blanks.
The automatic tightener consists of a pulley 22, which is mounted on an axle 66 by a ball bearing 67, and the axle is mounted on a lever 68, which is mounted on a support 69, shown in dot-dash lines. The support 69 is secured on the inside of the frame 2.
The electro-pneumatic brake-and-clutch assembly 30 is held by a base plate 70 on a cradle 71, which is permanently secured between the side frames 2 and 3. The toothed wheel 28 is secured on the inlet flywheel 29 of the assembly 30 by means of screws 72. The toothed wheel 32 is on the ouput shaft 31, which is provided with a key 73. In addition, the wheel 32 has a hub which is supported by a ball bearing 74 on a support 75 of the cradle 71. The crosswise or transverse shaft 6 extends equally between the side frames 2 and 3 and its end, which has the toothed pinions 34 and 35, is supported within the side frame 2 by a support 76, which is composed of two ball bearings 77, which are held in place by two retaining rings 78 and a bushing 79. The support 76 is secured against the outer surface of the side frame 2 by means of screws. The shaft 6 has a drive portion, which has a hexagonal cross section and a cylindrical portion 138, which is a non-drive portion. The other end of the transverse shaft 6, which is adjacent the non-drive portion 168, is provided with a dismantling device 80, which is secured within a strap 81 that, in turn, is held against the outer side of the side frame 3. This dismantling device 80 includes a threaded pipe 82 equipped with a thrust and roller bearing arrangement 83, which receives the end of the cross or transverse shaft 6. The threaded part of the threaded pipe 82 is engaged in a nut 84, which is secured by means of screws 85 within the strap 81. The threaded end of the threaded pipe is extended by a cylindrical piece 86, which has a retaining ring 87 and a cylindrical pin 88 on which a crankshaft (not illustrated) can be engaged.
As best illustrated in FIG. 3, the pulse generator 38, which can be a standard type of pulse generator, is secured by screws 93 onto a strap or front plate 91 of a support which is secured onto a side frame 2. As illustrated, the front plate 91 is attached to a pad 92 by means of screws 94, and the pad is secured by screws 95 on the outer side of the side plate 2. An axle 96 of the pulse generator 38 is equipped with a sleeve 97, on which the toothed drive wheel 38 is held by a key 98 and by retaining rings 99. The sleeve 97 is secured on the axle by a set screw 100, which acts on a flat space 101 provided on the axle 96.
As mentioned hereinabove, the ends of the upper infeed roller 8 are supported on levers 24 and 25. As best illustrated in FIGS. 4 and 5, the lever 24 is mounted on one of the side frames 2, while the lever 25 is mounted in a similar manner (not illustrated) on the side frame 3. The lever 24 is mounted to pivot on its one end around a stud 102, which is threaded into a block 103, which, in turn, is held on the inside of the side frame 2 by means of a screw 104. At the other end, the lever 24 has a roller support 105 holding a stud 106, which is screwed into a pull rod 107. For purposes of clarification, the upper conveyor 10 of the machine is shown by its shaft 108. The vertical movement of the pull rod 107 is obtained by rotating a transverse shaft 109, which, as illustrated in FIGS. 4 and 5, has a disk 110 and 111, which are mounted in an eccentric fashion on the shaft 109. The pull rods are connected to the disk in an eccentric manner so that rotation of the shaft by means of a handle 112 (FIG. 4) will cause a reciprocation of the shafts 107. The shaft 109 can be locked in any position by means of a locking appliance 113 of the setting device 25 (see FIG. 1).
As best illustrated in FIG. 5, the shaft 109 rotates within a bushing 114, which is mounted in a support 115 which is, in turn, secured on the side frame 2. The disk 110 is connected eccentrically to a pull rod 107 by means of the screw 116, which extends through a bushing 117, which is located in the lower part of the connecting rod 107. The disk 111, at the other end of the shaft 109, is connected to the other rod 107 in a similar manner. Thus, rotation of the rod 109 will pivot the levers 24 and 25 about their pivot point to change the spacing between the roller 8 and 7.
The tightening device or clamping means for securing each of the appliances or unit 5 in a given axial position along the drive shaft 6, is best illustrated in FIGS. 6 and 7. This device includes a square pipe 120, the ends of which are welded onto two plates 121 and 122, which are fitted on two pivots 123 and 124, which, in turn, are located on the side frames 2 and 3, respectively. The square pipe 120 contains a cylindrical shaft 125, which is secured within bushings 126 and 127. Both ends of the cylindrical shaft 125 are equipped with levers 128 and 129, respectively, and each of these levers holds a roller, such as 130, which is designed to engage within a linear cam formed by two sliding pieces 131 and 132, which are secured against the inner side of both side frames 2 and 3 by means of screws 133 and 134. In the Figure, only the linear cam and the cam follower of the side frame 3 have been illustrated, but the cams and followers on the other side are connected to the side frame 2 would be the same and are symmetrical. Only the end of lever 128 is equipped with the handle 135. The connection between the lever 128 and 129 and the cylindrical shaft 125 is achieved by means of screws 136 and 137.
Construction of the conveying device or unit is best illustrated in FIG. 7. Several of these devices or units 5 can be put side-by-side, as required by a job to be processed. One of the ends of the cross shaft 6 is arranged in such a way as to provide the cylindrical non-driving portion 138 (see FIG. 2), on which the conveying unit 5 can be put if they are to be placed out of operation temporarily. On account of the difference of the shape existing between the cylindrical part 138 and the hexagonal drive portions or part of the cross shaft 6, any conveyor unit placed in the area of the cylindrical part 138 will not be driven.
The conveying unit 5, as shown in FIGS. 7 and 8, has two side plates or guides 140 and 141 between which are mounted a toothed belt 142 running around a toothed drive pulley 143 and also around a toothed tightening pulley 144. In the course of its travel along the upper track, the toothed belt 142 is held by two toothed supporting pulleys 145 and 146, as well as by a smooth, vibratory pulley 147, which confers vibrations to the toothed belt 142 each time the belt's teeth run over the circumferential roller 147. The vibratory roller 147 can be moved in and out of operation by shifting it into a countersinking space 148, which is formed by a U-shaped slot on both side guides 140 and 141. The toothed belt 142 is guided laterally by means of roller devices 149, which are best illustrated and described in FIG. 8. The toothed tightening pulley 144 is held in a position by tightening screws 150 and 151, which extend through grooves 152 made in both side guides 140 and 141.
The side guide 140, on its lower part, has a supporting pad 153, which is attached to the inside of the guide by screws 154 (best shown in FIG. 11). This supporting pad 153 has a front shoulder 156 and is adapted to press against a crossbar 155 with the shoulder engaging the crossbar. In a rear section, the supporting pad 153 has a rear shoulder 158 and is adapted to rest on a rear crossbar 157, with the shoulder 158 engaging a portion of the crossbar 157.
The support pad 153 has a downwardly extending member or stop 159, which is secured by screws 160 (best illustrated in FIG. 9). This member or stop 159 includes a bumper 161 of hard rubber. When the lever 128 (FIGS. 1 and 6) is actuated in order to have the roller 130 move into the position it occupies, as illustrated in FIG. 7, a tightening action will take place between the square pipe 120 and the bumper 161 due to the movement of the roller 130 within the linear cam. This is due to the geometric arrangement between the levers and the plates 121 and 122, which actually cause the supporting pad 153 and its shoulders 156 and 158 to be clamped against the crossbars 155 and 157, respectively. A motion of the levers 128 in the opposite direction to that illustrated in FIG. 1 will cause the rollers 130 to move into the space 162 of the sliding piece 132, whereby the plate 121 and 122 are caused to pivot in the direction shown by the arrow 163. The square pipe 120 will then occupy the position 164, which is shown in dot-dash lines, and this action will result in relieving the pressure holding the support pad 153 against the crossbars 155 and 157. The square pipe 120 will also lift the conveyor units 5 so that it will rest both on the cross shaft 6 and a ball 165, which is mounted in the supporting pad 153 and will be in contact with one of the sides of the square pipe 120.
As best illustrated in FIG. 8, the drive pulley 143 is secured on the cross shaft 6 and is held between the side guides 140 and 141 by two ball bearings 166 and 167. The side guides 140 and 141 are connected together and secured to a tie 168 by means of screws 169 and 170. The roller device 149 consists of ball bearing pairs 171 and 172 and are mounted on the lower side of the tie 168 by means of screws 173 and 174. The side guide 141 has a lesser height than the side guide 140, and this allows for an easy dismantling of the toothed belt 142 after its slackened and after the actuation of the dismantling device 80 of the cross shaft 6 has occurred. The pressing ball 165, which is mounted in the pad 153, as illustrated, is secured in a bore and is held in place by a set screw 175.
As best illustrated in FIG. 9, the supporting pulley 145 is mounted by two ball bearings 176 and 177 on a bushing 178. The side guides 140 and 141 are held tightly against the ends of the bushing 178 by screws 179 and 180. The lateral position of the ball bearings 176 and 177 is obtained by bushings 181 and 182. The mounting of the other supporting pulley 146 is exactly the same as that illustrated in FIG. 9 for the mounting of the pulley 145. FIG. 9 also illustrates the connection of the lever or member 159 by screws 160 to the supporting pad 153 and also illustrates that the side guide 141 has a lesser height than the guide 140.
In FIG. 10, the vibratory roller 147 is illustrated as consisting of four ball bearings 185, which are arranged side-by-side on an axle 186, which has ends 187 and 188, which have a square cross section, as best illustrated in FIG. 7. The ends 187 and 188 are engaged in grooves or slots 148 which are cut or formed in the side guides 140 and 141. As illustrated in FIG. 7, the slots 148 have a U-shape, with one leg longer than the other so that by being positioned, as illustrated in FIG. 7, in the short leg, the roller is engaging the belt 142. However, if moved laterally to the other long leg of the U-shaped slot, then the roller will be moved to a position out of engagement with the bottom surface of the belt.
As mentioned earlier, the roller 144 is adjustable in the side guides or members 140 and 141. As best illustrated in FIG. 11, the roller 144 is mounted by two ball bearings 189 and 190 on a bushing or sleeve 191. The sleeve 191 is clamped between the two side guides 140 and 141 by screws 192 and 193, which extend through the slots 152. To position the ball bearings 189 and 190 on the sleeve 191, a bushing 195 and a pair of washers 196 are provided.
As mentioned hereinabove, one of the features of the present invention is the fact that the device can be adjusted to handle sheets or blanks of different lengths, and the spacing between the blanks can be adjusted. As illustrated in FIG. 12, sheets, such as 197, are placed in a pile behind a gate or stop 4 and are fed by the conveying unit 5 from the bottom of the pile underneath the stop into the rolls 7 and 8, which then feed the blank or sheet between the upper conveyor 10 and the lower conveyor 9 of the processing device, such as a folder-gluer.
Before starting up the folder-gluer represented by the upper and lower conveyors, the operator is to put in a setting for a value Lc, which corresponds to a length L of the sheet to be fed, as well as a rate or value Wc, which corresponds to a distance W between the rear or trailing edge of two consecutive sheets, such as the sheets 197a and 197b FIG. 12. The spacing between the rear or trailing edge and the front or leading edge of the two consecutive sheets 197a and 197b is represented by the distance A. With the values Lc and Wc determined, the folder-gluer will be started up and a first pulse generator 198, which is illustrated as being associated with the roller 7, will create pulses to represent the angular rotation of the roller and transmit these pulses to a first counter 199. The counter 199 will then transmit its count to the computer or device 200. When the count corresponds or compares to the set value Wc, the computer will emit a control signal to the electro-pneumatic clutch-and-brake assembly 30, which will be switched on and, thus, cause the rotation of the transverse shaft 6. At this instance, a sheet 197 will be moved in a direction of the arrow 201 beneath the gate or stop 4. A second pulse generator 202, which is associated with the shaft 6, will transmit pulses to a second counter 203. The second counter transmits the recorded pulses to the computer 200, which, when the number of pulses is compared to the inserted value Lc, will emit a second control signal to the electro-pneumatic clutch-and-brake assembly 30 to switch it off and, thus, stop rotation of the transverse shaft 6 and, therefore, the feeding of blanks 197. When the blank 197 is moving past the stop 4 in the direction of arrow 201, it will interrupt a beam of light directed to the photo cell 11, which has been positioned a distance B corresponding to a determined number of pulses, which has been memorized by the computer 200. The computer will take this number into consideration when calculating the switching off command to be emitted for the clutch-and-brake assembly 30. The signal originating from the photo cell 11 is transmitted to the computer and coacts with the signal from the counter 203 for this off control signal. With the folder-gluer continuing to operate, the first pulse generator 128 will continue to emit pulses and a new feed cycle will begin, as soon as the number of pulses corresponding to the set value Wc is obtained. In this regard, it is possible to set various counters and inputs so that the blank 197 is engaged in the feed rollers 7 and 8 as the conveying unit 5 stops conveying so that there is no possibility of misallignment of the blank.
Although various minor modifications may be suggested by those versed in the art, it should be understood that I wish to embody within the scope of the patent granted hereon all such modifications as reasonably and properly come within the scope of my contribution to the art.
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A device for feeding blanks from a pile into an infeed arrangement for a blank processing machine, such as a folder or gluer, characterized by a frame having a plurality of conveyor units with an arrangement for laterally positioning the units in the frame depending on the width of the blank being processed, an arrangement for driving each of the units utilizing a single drive shaft and an arrangement for driving each of the conveyor units for a selected period of time during each feed cycle.
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The United States Government has rights in this invention pursuant to Contract No. W-7405-ENG-48 between the U.S. Department of Energy and the University of California, for the operation of Lawrence Livermore National Laboratory.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is related to an optical projection reduction system for use with short wavelength radiation in photolithography equipment used in the manufacture of semiconductor devices.
2. Background of the Invention
Photolithography is a well known manufacturing process used to create devices upon substrates. The process typically involves exposing a patterned mask to collimated radiation thereby producing patterned radiation, which is passed through an optical reduction system. The reduced patterned radiation or mask image is projected onto a substrate coated with photoresist. Radiation exposure changes the properties of the photoresist, allowing subsequent processing.
Exposure tools used in photolithography have two common methods of projecting a patterned mask onto a substrate: "step and repeat" and "step and scan." The step and repeat method sequentially exposes portions of a substrate to a mask image. The step and repeat optical system has a projection field that is large enough to project the entire mask image onto the substrate. After each image exposure, the substrate is repositioned and the process is repeated.
In contrast, the step and scan method scans the mask or reticle onto a wafer substrate over an annular field or a slit field that is the full height of one or more of the chips. Referring to FIG. 1, a ring field lithography system 100 for use in the step and scan method is shown. A moving mask 101 is illuminated by a radiation beam 103, which reflects off the mask 101 and is directed through a reduction ring field optical system 107. Within the optical system 107, the image is inverted and the arcuate shaped ring field 109 is projected onto a moving substrate 111. The arcuate shaped reduced image ring field 109 can only project a portion of the mask 101, thus the reduced image ring field 109 must scan the complete mask 101 onto the substrate 111. Because the mask 101 and substrate 111 move synchronously, a sharp image is scanned onto the substrate 111. Once the complete mask 101 is scanned onto the substrate, the mask 101 and substrate 111 are repositioned and the process is repeated. The dimensions of the slit are typically described by a ring field radius and a ring field width.
As manufacturing methods improve, the minimum resolution dimension or critical dimension (CD) which can be achieved decreases, thereby allowing more electronic components to be fabricated within a given area of a substrate. The number of devices that can be fabricated within an area of substrate is known as device density. For example, a common measure of device density is the amount of memory that can be fabricated on a single DRAM chip. As resolution dimension or CD decreases, DRAM memory size increases dramatically. With existing technology, 0.25 μm resolution is possible.
One well-known means of improving the resolution dimension and increasing device density is to use shorter exposure wavelength radiation during photolithography processes. The relationship between resolution dimension and radiation wavelength is described in the formula: R=(K 1 λ)/(NA), wherein R is the resolution dimension, K 1 is a process dependent constant (typically 0.7), λ is the wavelength of the radiation, and NA is the numerical aperture of the optical system projecting the mask image. Either reducing the wavelength or increasing the NA will improve the resolution of the system.
Improving the resolution by increasing the numerical aperture (NA) has several drawbacks. The most prevalent drawback is the concomitant loss of depth of focus with increased NA. The relationship between NA and depth of focus is described in the formula: DOF=(K 2 λ)/NA 2 , wherein DOF is depth of focus, and K 2 is a process dependent constant (typically close to unity). This simple relationship shows the inverse relationship between DOF and NA. For several reasons, including practical wafer flatness and scanning stage errors, a large depth of focus is on the order of ±1.0 micrometers is desirable.
Immediately, the shortcomings of resolution improvement via numerical aperture increase can be seen. As lithography technologies evolve toward shorter wavelengths, projection systems operate in different regions of wavelength-NA space. For EUV lithography at an operational wavelength of 13.4 nm, 0.1 μm resolution can be achieved with a projection system that has a numerical aperture of 0.10 (assuming K 1 =0.7). A depth of focus of at least ±1.0 μm results from this low numerical aperture. This large depth of focus will enhance the robustness of a particular lithographic process. In contrast, deep ultraviolet (DUV) lithography at a wavelength, l , of 193 nm requires a projection system with a numerical aperture of 0.75 to achieve 0.18 μm features (assuming K 1 =0.7). At this NA, the depth of focus has been reduced to ±0.34 μm. This reduction in depth of focus leads to a loss in available process window, which will adversely impact process yield. As the process shrinks, it becomes more difficult to maintain the CD control that is critical to the lithographic process.
As is known in the art, short l radiation (less than about 193 nm) is not compatible with many refractive lens materials due to the intrinsic bulk absorption. To reduce the radiation absorption within an optical system, reflective elements may be used in place of refractive optical elements. State of the art DUV systems use catadioptric optical systems that utilize a combination of refractive and reflective optical elements. Since the mirrors provide the bulk of the optical power, the use of refractive lens elements is minimized
To produce devices with smaller critical dimensions and higher device density than is possible with DUV systems, optical systems compatible with even shorter wavelength radiation are required. Extreme ultraviolet (EUV) radiation (l less than about 20 nm) offers the potential to reduce the critical dimension from the current state of the art of 0.18 mm to below 0.05 mm. This radiation cannot be focused refractively. However, EUV radiation can be focused reflectively using optical elements with near normal incidence multilayer coatings.
Early development of optical systems for EUV projection lithography concentrated on projection of two-dimensional (2D) image formats at low numerical apertures. One example of a step and repeat optical system is disclosed in U.S. Pat. No. 5,063,586. The '586 patent discloses coaxial and tilted/decentered configurations with aspheric mirrors that project approximately a 10 mm×10 mm image field. The '586 patent system achieves an resolution of approximately 0.25 μm across this field, but suffers from unacceptably high distortion, on the order of 0.8 μm. The optical system described by the '586 patent is impractical because the mask would have to pre-distorted in order to compensate for the distortion in the projection optics.
More advanced optical systems for EUV projection lithography evolved using the step and scan image partitioning method in response to the unacceptable distortion found in the large format step and repeat optical systems. Step and scan systems have inherently less distortion than step and repeat systems due to the reduced field size in the scan dimension. The distortion can be readily corrected to acceptable levels over the field in the scan dimension. Step and scan optical systems typically utilize ring fields. Referring to FIG. 2, in a step and scan optical system an image is projected by the optical system onto the wafer through an arcuate ring field slit 201 which is geometrically described by a ring field radius 203, a ring field width 205 and a length 207. Ring field coverage is limited to 180 i in azimuth.
One example of a step and scan optical system is disclosed in U.S. Pat. No. 5,315,629. Although the '629 patent optical system has low distortion, it does so at the expense of ring field width. The ring field slit width is only 0.5 mm at the wafer. High chief ray angles at mirror M1 make it difficult to widen the ring field width at a usable numerical aperture. The 0.5 mm ring field width of the '629 patent limits the speed at which the wafer can be scanned, restricting throughput. The ring field radius of the optical system described in the '629 patent is 31.5 mm, which limits the field width in the cross scan dimension. Like the '586 patent, the '629 patent is best suited for critical dimensions on the order of 0.1 mm. The numerical aperture of the optical system in the '629 can be scaled up to achieve higher resolution. However, the ability to control distortion is lost as the numerical aperture is scaled to larger values.
Another example of a step and scan optical system is U.S. Pat. No. 5,353,322. The '322 patent discloses 3-mirror and 4-mirror optical systems for EUV projection lithography. An optical system with an odd number of reflections necessitates that the mask and wafer be located on the same side of the optical system. Thus, the motion of the stages that carry the mask and wafer are limited. An extra fold mirror added to the 3-mirror embodiment found in the '322 patent creates a 4-mirror system that enables unlimited stage travel since the wafer and mask are now on opposite sides of the optical system. However, this extra fold mirror does not provide any optical power and thus provides no aberration correction. The principle drawback of the '322 optical system is that its aperture stop is physically inaccessible. Although the stop location allows for a numerical aperture of up to 0.125, the projected imagery could vary substantially across the ring field as the various hard apertures vignette light diffracted by the mask features in the optical system. This is due to the fact that these systems have no physically accessible hard aperture stop to define the imaging bundles from each field point in a like manner. If this vignetting is field dependent, it can lead to loss of CD control across the projected ring field.
Clearly, state of the art optical systems for EUV projection lithography can be used to resolve features sizes that are on the order of 0.1 mm (100 nm). As demonstrated, these systems are coaxial 3- and 4-mirror reflective anastigmats that are optimized to operate over a narrow ring field. Since it is difficult to control both the field and pupil dependence of the aberrations simultaneously, the numerical aperture of these systems is necessarily restricted to approximately 0.10 for ring field of any substantial width (0.5 mm to 1.5 mm).
Prior art offers no concrete examples of multi-mirror systems that achieve higher NAs (>0.15) with low static distortion (<CD/10). Examples of optical systems for EUV projection lithography with numerical apertures in excess of 0.10 are disclosed in U.S. Pat. No. 5,212,588. The '588 patent demonstrates a multi-bounce projection system that incorporates 2 coaxial aspheric mirrors in a 4-bounce configuration. Mirror M1 is convex and mirror M2 is concave. Both mirrors have substantially the same radius of curvature to obtain a near zero Petzval sum. This ensures that high resolution imagery will be obtained on a flat imaging surface. While the '588 patent describes a number of embodiments with excellent performance over a range of numerical aperture up to 0.17 at EUV wavelengths, all the systems suffer one common flaw: the exit pupil is centrally obscured by mirror M1. This central obscuration suppresses the MTF response of the system at the mid-spatial frequencies relative to the cut-off frequency. Since the obscuration is large (on the order of 40%), this loss of contrast will yield unacceptable lithographic imaging performance.
One path to higher resolution is to add an extra mirrored surface in such a manner as to enhance the simultaneous correction of both the field and pupil dependence of the aberrations. An examples of a 5-mirror EUV projection system is disclosed in U.S. Pat. No. 5,153,898. However, only three of the mirrored surfaces provide aberration correction, and the extra two mirrors only act to fold or redirect the incoming radiation. The '898 patent does not enable high numerical optical systems for EUV projection lithography.
In view of the foregoing, there is a need for an optimized optical system which is compatible with short wavelength radiation and has a high numerical aperture for improved resolution.
SUMMARY OF THE INVENTION
The present invention is directed to a five mirror reflective optical projection system that allows a reduced mask image to be projected onto a wafer with short wavelength radiation. The present invention allows for higher device density because the optical system has improved resolution that results from the high numerical aperture, which is at least 0.14. An inventive optical system having a numerical aperture of 0.18 with extreme ultraviolet radiation of approximately 13.1 nm, and assuming a process dependent constant k 1 of 0.7, yields a resolution on the order of 50 nm.
The present invention also includes a physically accessible aperture stop which allows the imagery to be stationary across the ring field. This aperture stop is imaged to infinity in image space, making the imaging bundles telecentric at the mask. This ensures that the local magnification remains constant as the image plane is moved through the depth of focus of the projection system.
All five mirrors of the inventive optical system are aspheric. The aspheric surfaces provide enough degrees of freedom to enable the correction of both astigmatism and distortion across the ring field format. This high level of optical correction allows diffraction-limited performance at a numerical aperture greater than about 0.14, with the distortion being reduced to less than one-tenth of the critical dimension (CD) at any point in the ring field.
Other advantages and features of the present invention will become apparent from a reading of the following description when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view of a ring field lithography system.
FIG. 2 is a view of a ring field slit.
FIG. 3 is a schematic depiction of the main elements of the exemplary EUV lithography apparatus according to the present invention.
FIG. 4 is a view of the optical system according to the present invention.
FIG. 5 is a graph showing distortion v. position across the ring field width.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following is a detailed description of the presently preferred embodiments of the present invention. However, the present invention is in no way intended to be limited to the embodiments discussed below or shown in the drawings. Rather, the description and the drawings are merely illustrative of the presently preferred embodiments of the invention.
The present invention is a photolithography optical system designed for use with extreme ultraviolet (EUV) radiation. FIG. 3 schematically depicts the exemplary inventive apparatus for semiconductor EUV lithography. The apparatus comprises a radiation source 301 that emits EUV radiation 303. The EUV radiation 303 may be processed by a condenser 305 to produce a EUV beam 307 to uniformly illuminate a portion of a mask 309. The radiation reflected from the mask 309 produces a patterned EUV beam 311, which is introduced into an optical system 313. The optical system 313 projects a reduced image 315 of the mask 309 onto a wafer 317.
EUV radiation has a wavelength (λ) between about 4 to 20 nm and may be produced by any suitable means including a laser produced plasma, synchrotron radiation, electric discharge sources, high-harmonic generation with femto-second laser pulses, discharge-pumped x-ray lasers, and electron-beam driven radiation devices. Laser-produced plasma (LPP) sources focus an intense pulsed laser beam onto a target. Suitable targets are metals and noble gases. Targets of noble gas molecule clusters in a supersonic jet produce a bright "spark" with a broad emission spectrum ranging from visible light to EUV radiation. High-repetition-rate (3,000-6,000 Hz) pulsed laser drivers deliver 1,500 W of focused power to the target regions. A LLP gas source converts the incident laser power into EUV light in the required spectral bandwidth.
Condenser optics typically collect EUV radiation from the LLP source and condition the radiation to uniformly illuminate the mask. The condenser illuminates a narrow ring field at the mask with the EUV radiation, the illumination having a spatial nonuniformity of less than 1% in the cross scan dimension. The condenser further directs the EUV beam into the entrance pupil of the optical system with a partial coherence of approximately 0.7. Separate collection channels each act in concert to direct radiation across the entire ring field and the optical system entrance pupil.
Since EUV radiation is absorbed by all materials, reflective optical elements are best suited for EUV optical systems. The inventive optical system comprises five reflective optical elements (mirrors) listed in order from mask to substrate: M1, M2, M3, M4, and M5. The optical system is placed in a vacuum or other suitable atmosphere.
In the lithographic process, the EUV radiation is collected and illuminates a mask, producing an object that can be projected to the wafer. The object end of the inventive optical system departs enough from the telecentric condition so that the light rays incident upon the reflective mask have sufficient clearance to prevent vignetting or clipping by mirror edges. Referring to FIG. 4, there is shown an exemplary optical system for EUV semiconductor lithography. Because this is a ring field optical configuration, only off-axis sections of the parent mirrors are used. Thus, the off-axis section of the first optical element (M1) 505, the off-axis section of the second optical element (M2) 509, the off-axis section of the third optical element (M3) 513, and the off-axis section of the fifth optical element (M5) 521 are exposed to EUV radiation. The entire aspheric parent of the fourth optical element (M4) 517 is used. The use of off-axis sections, rather than full parent mirrors, facilitates the multilayer coating process by allowing the use substantially small deposition chambers, thus ensuring that very uniform coatings can be applied. Although off-axis mirror sections are used in practice, the optical elements are all arranged in a coaxial configuration such that the vertex of each surface of revolution lies on a common mechanical centerline.
Referring to FIG. 4, EUV Beam 1 501 diverges from a reflective mask 503 onto concave aspheric mirror 505. Beam 2 507 is reflected from mirror 505 in a divergent cone to a convex aspheric mirror M2 509. Beam 3 511 is reflected from mirror M2 509 in a divergent cone to a concave aspherical mirror M3 513. Beam 4 515 is reflected from mirror M3 513 in a convergent cone to a convex aspheric mirror M4 517, which also functions as the aperture stop of the system. Beam 5 519 is reflected from mirror M4 517 in a divergent cone to a concave aspheric mirror M5 521. Beam 6 523 is reflected from mirror M5 521 in a convergent cone forming a reduced image of the mask 503 pattern onto a wafer 525. The projected EUV aerial image enables a chemical reaction in a photoresist layer on the wafer 525 forming the latent image in the photoresist. This latent image is then subsequently processed by well-known means to form the patterned wafer.
Concave mirrors have positive optical power and convex mirrors have negative optical power. Using this convention, the optical power configuration of the inventive system from object to image can be described as: positive, negative, positive, negative and positive, corresponding to mirrors M1 505, M2 509, M3 513, M4 517, and M5 521, respectively. This grouping of separated positive and negative optical power allows the optical system to achieve a Petzval sum that is substantially zeroed, while enabling correction of both astigmatism and distortion.
Since the focal length of the inventive optical system can be scaled to accommodate a variety of packaging concepts, it is useful to describe the inventive optical system relative to this quantity. The absolute radii of the mirrors M 1 505, M 2 509, M 3 513, M 4 517, and M 5 521, relative to the system focal length, are listed in Table 1 below. The relative positions of the mirrors M1 505, M2 509, M3 513, M4 517, and M5 521 are listed in Table 2 below. For a 4-to-1 reduction, the distance of the mask to M1 505 is 744.35 mm.
TABLE 1______________________________________ Mirror radii from object plane to image plane asMirror a fraction of the system focal length ±5%______________________________________ -1.1962b.1M.sub.2 -0.3911M.sub.3 -0.7092M.sub.4 -0.4196M.sub.5 -0.3671______________________________________
TABLE 2______________________________________ Axial separations of the mirrors as a fraction ofSurface the system focal length______________________________________ ±10%M.sub.1 to M.sub.2 -0.2738M.sub.2 to M.sub.3 - 0.4727M.sub.3 to M.sub.4 -0.4649M.sub.4 to M.sub.4 - 0.1813M.sub.5 to image -0.2441______________________________________
Multilayer coated EUV optical systems require that the EUV radiation have low angles of incidence at each of the mirror surfaces. EUV multilayers are constructed using alternating layers of two materials with different optical properties. These materials need to have low intrinsic absorption at EUV wavelengths and provide an optical impedance mismatch at the layer interface so that a reflected wave can be generated. Common material pairs with desirable characteristics include molybdenum/silicon (Mo/Si) for wavelengths near 13.4 nm and molybdenum/beryllium (Mo/Be) for near wavelengths near 11.3 nm. Since the optical impedance between these material pairs is low, the bandwidth of the spectral reflectivity about the peak reflectivity is relatively small. This narrow bandwidth means that the multilayer reflectivity will, for a fixed angle of incidence, be sensitive to shifts in wavelength. Shifts in radiation wavelength are equivalent to changes in the incidence angle in the sense that both factors shift multilayer performance away from its optimum resonance condition. For a fixed wavelength, the multilayer reflectivity will degrade as a function of incidence angle.
The high system transmission is a key feature of this inventive optical system, which is achieved by using shallow incidence angles on each of the mirrored surfaces. Keeping the mean angle of incidence low at each surface ensures that the optical system transmission, which described by the formula T sys =R 1 ×R 2 ×R 3 ×R 4 , where Ri represents the reflectivity of the i th mirror, will be maximized for a range of incident angles and range of wavelengths. Low angles of incidence also helps to ensure that multilayer amplitude and phase effects measured in the exit pupil of the projection system are minimized. These amplitude and phase effects could substantially alter the partially coherent imaging characteristic of the system, thus limiting robust lithographic performance.
Table 3 shows the mean angle of incidence at each mirror surface. Multilayer coatings that have either a uniform or graded thickness can be designed and applied to each of the mirror surfaces in such a manner as to maximize the transmission of this inventive five mirror system. The transmission of the projection optics is greater than 17%, considering that the maximum theoretical reflectivity for a Mo/Si multilayer at 13.4 nm is over 70%.
TABLE 3______________________________________Mirror Average Angle of Incidence______________________________________M1 11.34°M2 7.72°M3 5.28°M4 15.52°M5 7.76°______________________________________
Table 4 shows the maximum aspheric departure from a best-fit spherical surface centered on the off-axis section of the parent asphere for each mirror. The inventive optical system is designed using mirrors with low aspheric departure across the off-axis section of the parent to facilitate mirror metrology using visible wavelengths. If the projection system can be designed so that the aspheric departure is small relative to a visible wavelength, the off-axis sections can be tested at their center of curvature without the need for null optics that adversely impact the absolute accuracy of the metrology test. The aspheric departure of prior art systems typically is limited to a maximum of 12 mm. However, a natural consequence of the increased numerical aperture in the present invention is the increased beam footprint on each of the mirror surfaces. The aspheric departure across a mirror surface will increase as the beam footprint is increased.
TABLE 4______________________________________ Mirror Maximum aspheric departure______________________________________ <5.1 mb.1M.sub.2 <8.5 mM.sub.3 <3.5 mM.sub.4 <0.1 mM.sub.5 <18.8 m______________________________________
Another advantage of the inventive optical system is that the design has a physically accessible, real aperture stop on mirror M4. More specifically, this physical aperture stop ensures that imaging bundles from each field point within the ring field are not clipped or vignetted and are formed in the small manner. This makes the projected imagery, setting aside the effects of the field dependent aberrations and variations in illumination from the condenser across the ring field, independent of position within the ring field. Fundamentally this means that the aerial images from different field points in the ring field will look the same and that variations in projected feature size will be minimized. Such imagery is termed stationary imagery.
The larger arcuate slit dimensions of the inventive optical system also help to increase wafer throughput. Prior art optical systems typically produce an arcuate slit with a ring field width of less than about 1.0 mm. The ring field width of the present invention is 1.5 mm, which is significantly wider than that of the prior art. The present invention improves the unit area coverage within a single field on the wafer because the ring field width of the present invention is larger than that of the prior art. This means that more area on the photoresist-coated wafer may be exposed per unit time. Since more area per unit time can be exposed, the lithographic tool can process more wafers per hour. Thus, the inventive optical system can expose a substrate to radiation more efficiently than an optical system with a narrow ring field width.
Tables 5 to 7 contain constructional data and other relevant information for the currently preferred configuration of mirrors M1, M2, M3, M4, and M5. The inventive optical system has a 4:1 reduction ratio, a numerical aperture of 0.18, and a 1.5 mm ring field width that is capable of 50 nm resolution and 1.0 μm depth of focus. Table 7 below describes the mirror surfaces of the inventive optical system.
TABLE 5______________________________________Element Radius of Elementnumber Curvature Thickness Definition______________________________________Object Infinite 351.141510 Mask1 A(1) -292.381122 M12 A(2) 504.794891 M23 A(3) -496.445439 M34 A(4) 193.582965 M45 A(5) -260.692804 M5Image Infinite Wafer______________________________________
Referring to Table 5, the radius of curvature refers to the radius of curvature of each optical element, and the thickness refers to the vertex-to-vertex thickness between the optical surfaces. For example, the thickness of the object is 351.14151 mm and represents distance from the mask to the vertex of mirror M1. The aspheric parameters A(1)-A(5) for the optical elements M1, M2, M4, and M5 are set forth in Table 6. Table 7 gives first order data on a preferred embodiment.
TABLE 6__________________________________________________________________________AsphericCURV K A B C D__________________________________________________________________________-0.00078289 1.62611100 0.00 3.498200E-16 -7.101160E-22 0.00A(2) -0.00239444 0.33946500 0.00 5.759030E-15 9.512560E-20 0.00A(3) -0.00132043 0.02617400 0.00 1.143970E-17 7.746320E-23 0.00A(4) -0.00223166 2.59276100 0.00 -9.009250E-15 -2.722770E-19 0.00A(5) -0.00255085 0.34659500 0.00 -9.701720E-16 -1.567560E-20 0.00__________________________________________________________________________
TABLE 7______________________________________ Center of ring field (mask, mm) -211.OEffective focal iength (mm) -1067.797Paraxial reduction ratio 0.25Finite F/N.sub.0 1/2.78Total track (mm) 0.0______________________________________
The aspheric profile of each mirror is uniquely determined by its K, A, B, C, and D values, such as given in Table 6. The sag of the aspheric surface (through 10th order) as a function of radial coordinate (h) given by Equation 1: ##EQU1## Wherein, h is the radial coordinate; c is the curvature of the surface (1/R); and A, B, C, and D are the 4th, 6th, 8th, and 10th order deformation coefficients, respectively. Mirrors M1, M2, M3, M4, and M5 are all oblate spheroids with 6th and 8th order polynomial deformations.
Another advantage of the present invention is that the centroid distortion magnitude is balanced across the ring field width. This balanced distortion curve results in a minimization of dynamic (scanning) distortion. In scanning lithography, the mask and wafer are synchronously scanned so that the projected ring field at the mask will cover the entire wafer field. The scanning process has a substantial effect on the image aberrations, particularly distortion. The image distortion due to the relative movement of the image and the substrate during radiation exposure is dynamic distortion, which can smear an image out along a field dependent trajectory as the image crosses the ring field width.
Table 8 shows the performance of the system as described by the root mean square (RMS) wavefront error and corresponding Strehl ratio. Table 9 shows the deviation (distortion) of the image centroid at the wafer from its ideal location.
TABLE 8______________________________________ RMS wavefrontRingfield Radius error Strehl ratio______________________________________52.000 mm 0.015 0.99152.375 mm 0.007 0.99852.750 mm 0.011 0.99653.125 mm 0.009 0.99653.500 mm 0.013 0.993______________________________________
TABLE 9______________________________________Ideal image Chief ray Centroidpoint (mm) distortion (nm) distortion (nm)______________________________________-52.000 -3.48 -4.83-52.150 -2.35 -3.46-52.300 -1.42 -2.28-52.450 -0.71 -1.29-52.600 -0.23 -0.53-52 750 0.00 0.00-52.900 -0.04 0.26-53.050 4).38 0.26-53.200 -1.03 -0.05-53.350 -2.O1 -0.67-53.500 -3.34 -1.63______________________________________
Since the inventive optical projection system has an odd number of reflections, the mask and wafer are located of the same side of the imaging system. This introduces a limitation on the wafer travel. In the preferred configuration, the separation of the mask and wafer in the scan plane is 263.75 mm. The skilled artisan will readily appreciate that the entire optical system can be scaled by a constant greater than 1.0 to increase the separation between the mask and wafer. For example, the preferred configuration can be scaled by a factor of 1.5×, making the mask to wafer separation almost 400 mm. When the optical system is scaled, the chief ray angles (less than about 10°) remain the same, so that the multilayer coatings are unaffected. However, the distortion, wavefront error measured in waves, and the mirror asphericity scale with the scale factor. The limits imposed by mirror fabrication technology and the associated mirror metrology set a practical limit to the scale factor that can be used.
While the present invention has been described in terms of preferred embodiments above, those skilled in the art will readily appreciate that the present ring field optical system with such low distortion can be redesigned to accommodate a two-dimensional image format at a lower numerical aperture. Numerous modifications, substitutions and additions may be made to the disclosed embodiment without departing from the spirit and scope of the present invention. Although an optical system has been described above for use with a semiconductor photolithography system, those skilled in the art will readily appreciate that the inventive optical system may be utilized in any similar lithography device and that the present invention is in no way limited to the mechanisms described above. It is intended that all such modifications, substitutions and additions fall within the scope of the present invention which is best defined by the claims below.
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An optical system is described that is compatible with extreme ultraviolet radiation and comprises five reflective elements for projecting a mask image onto a substrate. The five optical elements are characterized in order from object to image as concave, convex, concave, convex, and concave mirrors. The optical system is particularly suited for ring field, step and scan lithography methods. The invention uses aspheric mirrors to minimize static distortion and balance the static distortion across the ring field width which effectively minimizes dynamic distortion. The present invention allows for higher device density because the optical system has improved resolution that results from the high numerical aperture, which is at least 0.14.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority from an earlier filed provisional application Ser. No. 61/657,944, filed Jun. 11, 2012, entitled “Synthesis of P-Chiral Compounds,” by the same inventors.
ACKNOWLEDGEMENT OF GOVERNMENT SUPPORT
This invention was made partly with Government support under contract 0953368 awarded by the National Science Foundation. The Government has certain rights in this invention.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the simple and inexpensive preparation of optically active phosphorus (P-chiral) building blocks based on (−)-menthol as the chiral auxiliary. The P-chiral building blocks can be elaborated in many ways through known as well as novel reactions, for example, the stereospecific cleavage of the P(O)CH 2 OH motif through oxidation.
2. Description of the Prior Art
Molecular chirality plays an important role in a variety of industrial processes. Many chiral and enantiometrically pure compounds are widely used in the preparation of pharmaceuticals, cosmetics, flavors and agricultural chemicals, to name several common uses. Manufacturers of such compounds are often challenged to produce the desired enantiomer in both high yield and purity. There are several approaches to achieve these goals, including effective, but often wasteful, separations and resolutions of the desired compound or through asymmetric catalysis via the creation of chiral centers through complex chiral auxiliaries that are difficult to prepare.
The most common P-chiral compound is PhP(O)(OMen)H. This compound was first described by Mislow in the early 1970's (Farnham, W. B.; Murray, R. K.; Mislow, K. J. Am. Chem. Soc. 1970, 92, 5808). The compound was used extensively much later on by Han and coworkers (see J. Am. Chem. Soc. 2008, 130, 12648-12655, and references cited therein). Although the latter paper claims a modified preparation, the authors do not report any yield and purify the compound twice by crystallization at −30° C. Clearly, the preparation is inconvenient, expensive, and only applicable to one diastereoisomer of PhP(O)(OMen)H.
At the present time, asymmetric catalysis has proved to be the most effective method to prepare both naturally occurring and synthetic chiral compounds in large quantities. Among the most important compounds utilized for asymmetric catalysis reactions are so-called “P-chiral” ligands. Typically, these phosphine ligands have chirality in the carbon chain (C-chiral) and the phosphorous atom is symmetrical with two identical substituents RP(R 1 ) 2 . Chirality at the phosphorous (P-chiral) remains the most desirable because the phosphorous is in direct contact with the metal that is actually involved in the catalysis. More selective and efficient catalysis can be attained through this proximity. To date, only a limited number of P-chiral compounds have been reported in the literature.
Because the preparation of P-chiral compounds is truly a “Holy Grail” of organophosphorus chemistry, many relevant works could be mentioned. The following reviews are exemplary of the present state of the art:
1) Grabulosa, A.; Granell, J.; Muller, G. Coord. Chem. 2007, 251, 25-90. 2) Johansson, M. J.; Kann, N. C. Mini Rev. Org. Chem. 2004, 1, 233-247. 3) Pietrusiewicz, K. M.; Zablocka, M. Chem. Rev. 1994, 94, 1375-1411.
SUMMARY OF THE INVENTION
The synthesis of P-chiral compounds is important to many applications, especially in the preparation of phosphine ligands for asymmetric catalysis (impacting both the synthesis of “fine” chemicals and industrial intermediates). As has been briefly mentioned, the vast majority of chiral phosphine ligands have chirality in the carbon chain, whereas the phosphorus atom is symmetrical with two identical substituents RP(R 1 ) 2 (such as R 1 =Ph, i-Pr, t-Bu, etc.). Yet, chirality at phosphorus is most desirable because it is directly in contact with the metal actually involved in the catalysis. Perhaps the best known example of a P-chiral ligand is diPAMP [(R,R)-1,2-Bis[(2-methoxyphenyl)(phenylphosphino)]ethane, currently selling for about $ 77.70 for 100 mg from a commercially available source.
The present invention concerns the preparation (and subsequent elaboration) of RP(O)(OR*)CH 2 OH, with R=H, Ph, alkyl, aryl, cinnamyl, etc; and R*=menthyl (and other chiral alcohol-derived moieties), especially HP(O)(OMen)CH 2 OH (where Men is menthol). Most preferably, R is independently selectable from among H and Ph and R* is L-menthol. This versatile building block is easily synthesized via the reaction of inexpensive starting materials, H 3 PO 2 , menthol and para-formaldehyde. The compound is easily crystallized at room temperature or in a simple freezer. From this starting compound, virtually any final product can be prepared with on the crystallization step being required as the source of chirality.
The invention offers a number of advantages, including the following, among others:
The power of the invention is multifold: 1) menthol is very inexpensive, 2) HP(O)(OMen)CH 2 OH is a very versatile building block, 3) the synthesis is inexpensive, for example, involving H 3 PO 2 , menthol, para-formaldehyde), 4) the compound can be crystallized very easily at room temperature or −18° C. (actually a simple freezer), in two cases to be described, 5) the method does not rely on any PCl-containing reagent, 6) large quantities can be prepared, and 6) virtually any final product can be prepared with only the initial crystallization step required as the source of chirality. This avoids tedious resolutions or crystallizations near the end of a multiple-step synthesis. L-Menthol is probably the most inexpensive alcohol available ($ 129 for 1 kg, or $1,000 for 25 kg from Sigma-Aldrich at the present time); and the enantiomer is also available, although much more expensive ($ 184 for 50 g). However, this enantiomer is not necessary for the practice of the present invention.
While the chemical yield for the preparation of highly optically-enriched HP(O)(OMen)CH 2 OH has not been completely optimized, a routine 10% yield can be obtained at present, and improvements are being examined in keeping with the principles of the invention, described more fully in the Detailed Description which follows. Because of the inexpensive and simple nature of the reaction, nothing remotely close has been found by Applicants to exist in the literature.
Although not absolutely required, another aspect of the invention is the stereospecific cleavage of the P(O)CH 2 OH moiety via oxidative cleavage. Methods for the oxidation of alcohols to aldehydes are available, and especially either “Swern oxidation (DMSO/oxalyl chloride)” and “Corey-Kim oxidation (Me 2 S/N-chlorosuccinimide)” are most appropriate. Although various P—H protecting groups have been reported, to the best of Applicant's knowledge, none involve P(O)CH 2 OH under oxidative conditions.
Additional objects, features and advantages will be apparent in the written description which follows.
DETAILED DESCRIPTION OF THE INVENTION
The preferred version of the invention presented in the following written description and the various features and advantageous details thereof are explained more fully with reference to the non-limiting examples and as detailed in the description which follows. Descriptions of well-known components and processes and manufacturing techniques are omitted so as to not unnecessarily obscure the principle features of the invention as described herein. The examples used in the description which follows are intended merely to facilitate an understanding of ways in which the invention may be practiced and to further enable those skilled in the art to practice the invention. Accordingly, the examples should not be construed as limiting the scope of the claimed invention.
As has been briefly discussed, preparing P-chiral compounds remains a frontier in organophosphorus chemistry. Whereas various methods have been reported for the preparation of specific P-chiral building blocks, based on kinetic resolution, or on chiral auxiliaries, typically these have severe limitation in the scope of their application. More than 40 years ago, Mislow and others pioneered the field of P-chiral compounds and the study of their reactivities. A case in point is menthyl phenyl-H-phosphinates PhP(O)(OMen)H 1, which have since been employed in various reactions such as cross-coupling substitution, or hydrophosphinylation. However, enriched diastereoisomers of 1 remain difficult to prepare as the isolation requires low-temperature recrystallization (multiple crystallizations below −30° C. or −70° C.). Analogous chemistry (PhPCl 2 +R*OH or R*OPCl 2 ) has been reported recently using other chiral alcohols. In the final analysis, these methods still require cumbersome crystallization procedures and are limited in terms of the phosphorus compounds that are accessible and therefore the final products that can be derived from them.
In one aspect, Applicants have discovered a novel P-chiral building block useful in the preparation of a variety of P-chiral organophosphorus compounds without using halogenated phosphorus starting materials, the building block having the formula:
wherein the P-chiral building block is made from -(−) menthol as a starting material.
In another aspect of the invention, the P-chiral building block can take the form:
wherein the P-chiral building block is made from -(−) menthol as a starting material.
In one preferred form, the building blocks so produced are used to produce compounds of the formula:
RP(O)(OR*)CH 2 OH
where R=H, Ph, aryl, alkyl, cinnamyl and R*=menthol or derived from any other chiral alcohol. The starting blocks of the invention can be used to make a P-chiral compound of the formula:
RP(O)(OR*)CH 2 OH
where R=H, Ph, aryl, alkyl, cinnamyl and R*=menthyl or derived from any other chiral alcohol; wherein the compound is made from a starting material having the formula:
the starting material being crystallized at about −18° C.
In another aspect of the invention, the building blocks are used to produce a P-chiral compound of the formula:
RP(O)(OR*)CH 2 OH
where R=H, Ph, aryl, alkyl, cinnamyl and R*=menthol or derived from any other chiral alcohol;
wherein the compound is made from a starting material having the formula:
the starting material being crystallized at room temperature.
A process is also shown for the synthesis of asymmetric non-racemic P-chiral compound of the formula:
RP(O)(OR*)CH 2 OH
where R=H, Ph, aryl, alkyl, cinnamyl and R*=menthol;
wherein the P-chiral compound is made by reacting (−)-menthol, H 3 PO 2 and paraformaldehyde as reactants, followed by crystallization between room temperature and about −18° C. to produce a given yield for the process.
The process is characterized by the absence of halogenated phosphorus starting materials. Unlike the prior art processes, the P-chiral starting blocks are crystallized at room temperature or in a simple freezer. In another aspect of the process, the initial reactants make up a mother liquor, and wherein the yield of the process is improved by cross-coupling the mother liquor followed by crystallization. Other candidate chiral alcohols include: (1R)-endo-(+)-fenchy alcohol; (−)-borneol; and D-(−)-pantolactone. However, for preparing the chiral building blocks, in the most preferred aspects, R=H and R*=CH 2 OH or R=Ph and R*=CH 2 OH.
Thus, in one aspect, the present invention involves the description of an extremely simple approach for the preparation of two versatile P-chiral building blocks, easily produced inexpensively on a multigram scale, and without the need for RPCl 2 precursors. These intermediates also allow much more flexibility for their functionalization into useful P-chiral compounds. The two building blocks 2 and 3 are crystallized in high (>95%) diastereoisomeric purities at −18° C. (in a regular freezer) in the case of 2, or at room temperature in the case of 3, respectively.
Compound 2 is prepared from hypophosphorous acid, paraformaldehyde and (−)-menthol in 9% yield (>6 g), and compound 3 is prepared from phenyl-H-phosphinic acid, (−)-menthol, and paraformaldehyde in 26% yield (>16 g) (Scheme 1). While the isolated yields are low, these still compare to literature methods and multigrams quantities are available in a single preparation. The structures of the diastereoisomers were determined by single X-ray crystallography (FIG. 1).
The hydroxymethyl handle also provides a way to functionalize these P-chiral building blocks (Scheme 2). We recently reported the Corey-Kim oxidation of (hydroxymethyl)phosphinates into the corresponding H-phosphinates. Thus, compound 2 can be viewed as a protected chiral equivalent of alkyl phosphinates ROP(O)H 2 , since it can be stereospecifically alkylated to form 4, or cross-coupled to form 5 (Scheme 3).
For example, cross-coupling of 2 with bromobenzene gives (R P )-5a (=(R P )-3) in 62% yield, and subsequent oxidative cleavage delivers (S P )-1 in 81% yield. Compound 3 can be oxidized to form (R P )-1 stereospecifically, in 76% yield. Therefore, cross-coupling/oxidation of 2 leads to the stereocomplementary isomer obtained by the direct oxidation of 3, so that either diastereoisomer of 1 is easily obtained using inexpensive (−)-menthol in both cases. Because of the ease of obtaining 2 and 3, and then 1 this approach is competitive with the direct but complicated synthesis of 1 from PhPCl 2 or MenOPCl 2 . Furthermore, these literature syntheses of the (S P ) stereoisomer require the use of expensive D-(+)-menthol. The usefulness of compound 1 in asymmetric organophosphorus synthesis is well-established. However, it is obviously limited to phenyl-containing products. Therefore the novel building block 2 offers much flexibility previously unavailable. Also, the presence of the hydroxymethyl group in both 2 and 3 provides further opportunities for functionalization since the carbon can be preserved if desired.
Another example of exploitation of the CH 2 OH moiety is the [2,3]-Wittig rearrangement (Scheme 4). Compound 3 is allylated to intermediate 9. Subsequent treatment of 9 with s-BuLi delivers the rearranged products 10. In all instances, a single diastereoisomer is obtained. At this time, the configuration of the stereocenters in the side-chain has not been assigned.
The preparation of a variety of P-chiral organophosphorus compounds from 1 (secondary and tertiary phosphine oxides) and from other menthyl esters is well-known in the literature (Scheme 5). For example, displacement of menthyl H-phosphinates with organometallic reagents gives the corresponding secondary phosphine oxide stereoselectively (inversion). Similarly, disubstituted menthyl phosphinates are also displaced with inversion of configuration. Finally, several methods are available to convert tertiary phosphine oxides into the corresponding P-chiral phosphine (or its borane complex) through either retention or inversion of configuration.
Initial Experimental Work: Procedures for the Menthyl Derivatives:
The following section will detail the procedures initially used to prepare several menthyl derivatives of the type under consideration.
General Chemistry:
1 H NMR spectra were recorded on a 300-MHz spectrometer. Chemical shift for 1 H NMR spectra (in parts per million) relative to internal tetramethylsilane (Me 4 Si, δ=0.00 ppm) with CDCl 3 . 13 C NMR spectra were recorded at 75 MHz. Chemical shifts for C NMR spectra are reported (in parts per million) relative to CDCl 3 (δ=77.0 ppm). 31 P NMR spectra were recorded at 121 MHz, and chemical shifts reported (in parts per million) relative to external 85% phosphoric acid (δ=0.0 ppm). TLC plates were visualized by UV or immersion in anisaldehyde stain (by volume: 93% ethanol, 3.5% sulfuric acid, 1% acetic acid, and 2.5% anisaldehyde) followed by heating.
Reagent and Solvents:
All starting materials were purchased from commercial sources and used as received. The solvents were distilled under N 2 and dried according to standard procedures (THF from Na/benzophenone ketyl; DMF from MgSO 4 ; CH 3 CN, toluene and dichloromethane from CaH 2 ).
31 P NMR Yield Measurements:
The NMR yields are determined by integration of all the resonances in the 31 P spectra, an approach which is valid if no phosphorus-containing gas (i.e. PH 3 ) evolves, or if the precipitate in a heterogeneous mixture does not contain phosphorus. The yields determined by NMR are generally accurate within ˜10% of the value indicated, and are reproducible.
L-menthyl(hydroxymethyl)phenyl-(S p )phosphinate (3)
In a flask equipped with a Dean-Stark trap were introduced phenyl-H-phosphinic acid (28.99 g, 204 mmol, 1.02 equiv), L-menthol (31.25 g, 200 mmol, 1.0 equiv) and toluene (200 mL). After 24 h at reflux under N 2 , the reaction was cooled down to rt. Paraformaldehyde (6.61 g, 200 mmol, 1.0 equiv) was added and the reaction was stirred for 24 h at reflux. The solvent was evaporated and the residue was dissolved into Et 2 O (100 mL). Hexanes (200 mL) were then added. The solution was then left at rt to allow the slow recrystallization of the desired compound as a white crystals (16.1 g, 26%, de>95%). 31 P NMR (121.47 MHz, CDCl 3 ): δ=37.2 (s); 1 H NMR (300 MHz, CDCl 3 ): δ=7.77-7.87 (m, 2H), 7.52-7.60 (m, 1H), 7.42-7.51 (m, 2H), 4.29-4.43 (m, 2H), 3.93-4.10 (m, 2H), 2.26 (dquint., J=2.6 and 7.0 Hz, 1H), 1.80-1.91 (m, 1H), 1.57-1.73 (m, 2H), 1.26-1.47 (m, 2H), 0.96 (d, J=7.1 Hz, 3H), 0.74-1.13 (m, 3H), 0.89 (d, J=7.0 Hz, 3H), 0.78 (d, J=6.4 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): δ=132.3 (d, J PCCCC =2.8 Hz), 131.7 (d, J PCCC =9.9 Hz, 2C), 130.6 (d, J PC =123 Hz), 128.3 (d, J PCC =12.1 Hz, 2C), 77.1 (d, J POC =8.3 Hz), 60.2 (d, J PC =117 Hz), 48.7 (d, J POCC =6.1 Hz), 43.2, 34.0, 31.4, 25.5, 22.8, 21.9, 21.1, 15.7; HRMS (EI+) m/z calcd for C 16 H 28 O 3 P ([M+H] + ) 311.1776. found 311.1766
L-menthyl(hydroxymethyl)-H—(R p )phosphinate
In a round bottom flask were introduced H 3 PO 2 (39.6 mL, 300 mmol, 1.0 equiv, 50% in water) and paraformaldehyde (11.9 g, 360 mmol, 1.2 equiv). The mixture was stirred for 20 h at 80° C. under N 2 . The reaction was then allowed to cool down to rt. The residue obtained was diluted in toluene (300 mL) and then transferred in a bigger flask equipped with a Dean-Stark trap. L-menthol (46.9 g, 300 mmol, 1.0 equiv) was added and the reaction was stirred for 24 h at reflux. The solvent was then evaporated and the residue obtained was dissolved into Et 2 O (100 mL). Hexanes (200 mL) was then added and the solution was left in the freezer (−18° C.) to allow the slow recrystallization of the desired compound as a white crystals (6.33 g, 9%, de>99%). Mp=101-102° C.; 31 P NMR (121.47 MHz, CDCl 3 ): δ=34.9 (dm, J=542 Hz); 1 H NMR (300 MHz, CDCl 3 ): δ=7.16 (dm, J=542 Hz, 1H), 4.04-4.23 (m, 2H), 3.82-4.00 (m, 2H), 2.14-2.24 (m, 1H), 1.98-2.11 (m, 1H), 2.04 (dquint., J=2.4 and 7.0 Hz, 1H), 1.62-1.73 (m, 2H), 1.34-1.52 (m, 2H), 1.24 (q, J=12.0 Hz, 1H), 0.93 (d, J=6.7 Hz, 6H), 0.76-1.10 (m, 2H), 0.80 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): δ=79.3 (d, J POC =8.3 Hz), 59.7 (d, J PC =111 Hz), 48.5 (d, J POCC =5.5 Hz), 43.3, 33.8, 31.5, 25.6, 22.9, 21.8, 20.8, 15.7; [α] D =−61.37°
L-menthyl(hydroxymethyl)phenyl (R p )phosphinate
In a tube for multisynthetizer were introduced L-menthyl(hydroxymethyl)-H—(R p )phosphinate (234.3 mg, 1.0 mmol, 1.0 equiv), Pd(OAc) 2 (4.5 mg, 0.02 mmol, 2 mol %) and Xantphos (12.7 mg, 0.022 mmol, 2.2 mol %). The tube was placed under N 2 . Toluene (4.5 mL) was then added followed by ethylene glycol (0.5 mL), DIPEA (0.23 mL, 1.3 mmol, 1.3 equiv) and bromobenzene (0.11 mL, 1.0 mmol, 1.0 equiv). After 24 h at reflux, the reaction was allowed to cool down to rt. Ethanol was then added to allow us to do 31 PNMR by forming a homogeneous mixture. After removing the solvents under vacuum, EtOAc was added and the organic layer was washed with NaHCO 3 and brine, dried over MgSO 4 , filtered and concentrated. The residue obtained was purified by column chromatography (Hexanes/EtOAc 7:3) to afford the product as a white solid (192 mg, 62%, de>99%). 31 P NMR (121.47 MHz, CDCl 3 ): δ=37.4 (s); 1 H NMR (300 MHz, CDCl 3 ): δ=7.80-7.91 (m, 2H), 7.45-7.62 (m, 3H), 4.09-4.21 (m, 1H), 4.02-4.08 (m, 2H), 2.77-2.87 (m, 1H), 2.29-2.39 (m, 1H), 1.90-2.05 (m, 1H), 1.58-1.69 (m, 3H), 1.22-1.50 (m, 2H), 0.93 (d, J=6.2 Hz, 3H), 0.85 (d, J=7.0 Hz, 3H), 0.76-1.02 (m, 2H), 0.47 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): δ=132.3 (d, J PCCCC =2.7 Hz), 131.8 (d, J PCCC =9.9 Hz, 2C), 129.4 (d, J PC =124 Hz), 128.4 (d, J PCC =12.1 Hz, 2C), 77.4 (d, J POC =8.3 Hz), 60.4 (d, J PC =115 Hz), 48.6 (d, J POCC =6.0 Hz), 43.6, 34.0, 31.5, 25.4, 22.6, 22.0, 21.0, 15.2; HRMS (EI+) m/z calcd for C 17 H 27 O 3 P ([M+H] + ) 311.1776. found 311.1773
L-menthyl phenyl-H—(R p )phosphinate
To a solution of N-chlorosuccinimide (1.0 g, 7.5 mmol, 1.5 equiv) in dichloromethane (80 mL) at −78° C. and under N 2 was added dropwise a solution of dimethyl sulfide (0.55 mL, 7.5 mmol, 1.5 equiv) in dichloromethane (10 mL). After 10 minutes at −78° C., a solution of L-menthyl(hydroxymethyl)phenyl (S p )phosphinate 3 (1.55 g, 5.0 mmol, 1.0 equiv) in dichloromethane (10 mL) was added over 20 minutes. After 1 h at −78° C., triethylamine (3.48 mL, 25.0 mmol, 5.0 equiv) was added over 15 minutes and the reaction was allowed to warm to rt. After 1 h at rt, water was added and the two layers were separated. The aqueous layer was then washed with dichloromethane (2×). The combined organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The residue obtained was dissolved into EtOAc and washed with brine. The combined organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The residue obtained was purified by column chromatography (Hexanes/CH 2 Cl 2 5:5 to 0:10) to afford the product as a colorless oil (1.07 g, 76%, de>99%). 31 P NMR (121.47 MHz, CDCl 3 ): δ=24.7 (dm, J=553 Hz); 1 H NMR (300 MHz, CDCl 3 ): δ=7.73-7.84 (m, 2H), 7.66 (d, J=553 Hz, 1H), 7.46-7.64 (m, 3H), 4.22-4.36 (m, 1H), 2.14-2.27 (m, 2H), 1.62-1.75 (m, 2H), 1.38-1.54 (m, 2H), 1.24 (q, J=11.2 Hz, 1H), 0.78-1.13 (m, 2H), 0.96 (d, J=7.0 Hz, 3H), 0.90 (d, J=6.4 Hz, 3H), 0.86 (d, J=7.0 Hz, 3H)
L-menthyl(o-anisole)phenyl-H—(S p )phosphinate
In a tube for multisynthetizer were introduced L-menthyl phenyl-H—(R p )phosphinate (280.3 mg, 1.0 mmol, 1.0 equiv), Pd(OAc) 2 (4.5 mg, 0.02 mmol, 2 mol %) and Xantphos (12.7 mg, 0.022 mmol, 2.2 mol %). The tube was placed under N 2 . Toluene (4.5 mL) was then added followed by ethylene glycol (0.5 mL), DIPEA (0.23 mL, 1.3 mmol, 1.3 equiv) and 2-bromoanisole (0.13 mL, 1.0 mmol, 1.0 equiv). After 24 h at reflux, the reaction was allowed to cool down to rt. Ethanol was then added to allow us to do 31 PNMR by forming a homogeneous mixture. After removing the solvents under vacuum, EtOAc was added and the organic layer was washed with NaHCO3 and brine, dried over MgSO 4 , filtered and concentrated. The residue obtained was purified by column chromatography (Hexanes/EtOAc 9:1 to 8:2) to afford the product as a yellow oil (347 mg, 90%, de>99%). 31 P NMR (121.47 MHz, CDCl 3 ): δ=27.6 (s); 1 H NMR (300 MHz, CDCl 3 ): δ=7.99-8.11 (m, 1H), 7.76-7.88 (m, 2H), 7.35-7.54 (m, 4H), 7.02-7.11 (m, 1H), 6.77-6.86 (m, 1H), 4.15-4.28 (m, 1H), 3.61 (s, 3H), 2.10-2.25 (m, 2H), 1.56-1.71 (m, 2H), 1.30-1.51 (m, 2H), 1.21 (q, J=11.2 Hz, 1H), 0.78-1.03 (m, 2H), 0.87 (d, J=7.1 Hz, 3H), 0.84 (d, J=6.4 Hz, 3H), 0.48 (d, J=6.7 Hz, 3H)
L-menthyl(hydroxymethyl)phenyl (S p )phosphinate (620.7 mg, 2.0 mmol, 1.0 equiv), phthalimide (382.5 mg, 2.6 mmol, 1.3 equiv) and diphenyl-2-pyridylphosphine (684.5 mg, 2.6 mmol, 1.3 equiv) were introduced in a flask, placed under N 2 and solubilized in CH 2 Cl 2 (20 mL). Diisopropyl azodicarboxylate (0.51 mL, 2.6 mmol, 1.3 equiv) was then added and the reaction was stirred for 24 h at rt. Water and brine (1:1) were added and the two layers were separated. The aqueous layer was then extracted with CH 2 Cl 2 (2×). The combined organic layers was dried over MgSO 4 , filtered and concentrated under vacuum. The residue obtained was purified by column chromatography (hexanes/EtOAc 9:1 to 7:3) to afford the product as a white solid (612 mg, 70%, de=95%). 31 P NMR (121.47 MHz, CDCl 3 ): δ=31.4 (s); 1 H NMR (300 MHz, CDCl 3 ): δ=7.79-7.91 (m, 4H), 7.68-7.75 (m, 2H), 7.52-7.60 (m, 1H), 7.42-7.51 (m, 2H), 4.33-4.46 (m, 1H), 4.10-4.30 (m, 2H), 2.17 (dquint., J=2.3 and 6.7 Hz, 1H), 1.78-1.88 (m, 1H), 1.55-1.69 (m, 2H), 1.20-1.46 (m, 2H), 0.94-1.12 (m, 2H), 0.72-0.88 (m, 1H), 0.84 (d, J=7.0 Hz, 3H), 0.79 (d, J=7.0 Hz, 3H), 0.75 (d, J=6.8 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): δ=166.6 (2C), 134.0 (2C), 132.5 (d, J PCCCC =2.8 Hz), 131.7 (2C), 131.6 (d, J PCCC =8.8 Hz, 2C), 131.3 (d, J PC =130 Hz), 128.3 (d, J PCC =12.7 Hz, 2C), 123.2 (2C), 77.6 (d, J POC =7.7 Hz), 48.5 (d, J POCC =6.1 Hz), 42.9, 38.1 (d, J PC =107 Hz), 33.8, 31.3, 25.3, 22.5, 21.8, 20.9, 15.4; HRMS (EI+) m/z calcd for C 25 H 31 NO 4 P ([M+H] + ) 440.1991. found 440.1985
Further Experimental Work:
Since the initial experimental work described above, Applicants have performed additional work which verifies the earlier findings, as well as introducing certain new and novel aspects of the invention. With respect to the initial compounds 2 and 3:
1) Applicants have not changed the scales for the preparation of 2 and 3, but these multigram scales have been repeated successfully. An additional aspect of the invention was to “recycle” the mother liquor for compound 2. In this process, after the amount of crystals 2 (9% yield, >6 g) have been obtained, Applicants carried out a “cross-coupling” on the mother liquor and crystallizing the product 3-(R P ) in 24% yield, at room temperature. Note that the product is stereocomplementary to 3-(S p ) which is obtained from PhP(O)(OH)H as described in the previous discussion (26% yield, >16 g). Thus, we have a way to increase the yield of valuable compounds in the preparation of 2.
The stereocomplementarity characteristic is important because it means that either chirality can be made at phosphorus using the same L-menthol (which is the less expensive starting material, the other menthol costing on the order of 50× more). The same stereocomplementarity characteristic also means that is possible to make, for example, PhP(O)(OMen)H with either chirality at phosphorus. This compound has been made before in unreported yield and through difficult crystallizations (see Han and Mislow cited above), and only one chirality can be obtained from L-menthol. This compound has been used to make chiral phosphines as sold, for example, by Katayama Chemical Industries.
2) In another aspect of the invention, the concept of making RP(O)(OMen)CH 2 OH was extended to R=cinnamyl, again on multigram scale and with crystallization at room temperature. Cleavage of the CH 2 OH group was also done.
Transformations of the Building Blocks.
Some of the original transformations in the provisional have been improved in terms of yield, and a few new ones have been added, showing the synthetic flexibility of the compounds.
As mentioned in the literature background, the stereospecific transformation of phosphinates R 1 R 2 P(O)(OMen) into chiral phosphines is well precedented in the literature.
Two X-ray crystal structures have been obtained for the Wittig rearrangement.
Further Experimental Examples
(R p )-Menthyl(hydroxymethyl)-H-phosphinate 1
Paraformaldehyde (9.91 g, 330 mmol, 1.1 equiv) and hypophosphorous acid (39.6 g, 300 mmol, 1 equiv, 50% in water) were introduced in a round bottom flask and the reaction mixture was stirred for 20 h at 75° C. The reaction mixture was cooled down to rt and the residue was diluted in toluene (300 mL). L-menthol (46.9 g, 300 mmol, 1 equiv) was added and the reaction mixture was stirred for 24 h at reflux under N 2 in a flask equipped with a Dean-Stark trap. The solvent was then removed under vacuum and the residue obtained was dissolved in a mixture of diethyl ether/hexane (50 mL:200 mL) and the flask was placed in the freezer for 2 h (−18° C.). The solid obtained was filtered and solubilized in diethyl ether (200 mL) and placed in the fridge (2° C.) for 3 h to afford the product as white needles (6.33 g, 9%, de=98%). Mp=101-102° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=34.9 (dm, J=542 Hz); 1 H NMR (300 MHz, CDCl 3 ): □=7.16 (dm, J=542 Hz, 1H), 4.04-4.23 (m, 2H), 3.82-4.00 (m, 2H), 2.14-2.24 (m, 1H), 1.98-2.11 (m, 1H), 2.04 (dquint., J=2.4 and 7.0 Hz, 1H), 1.62-1.73 (m, 2H), 1.34-1.52 (m, 2H), 1.24 (q, J=12.0 Hz, 1H), 0.93 (d, J=6.7 Hz, 6H), 0.76-1.10 (m, 2H), 0.80 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=79.3 (d, J POC =8.3 Hz), 59.7 (d, J PC =111 Hz), 48.5 (d, J POCC =5.5 Hz), 43.3, 33.8, 31.5, 25.6, 22.9, 21.8, 20.8, 15.7; [α] D =−61.37°
(R p )-Menthyl(hydroxymethyl)methylphosphinate 2a
To a solution of 1 (234 mg, 1 mmol, 1 equiv) in dichloromethane (10 mL) at 0° C. and under N 2 was added bis(trimethylsilyl)acetamide (0.49 mL, 2 mmol, 2 equiv) followed by iodomethane (0.062 mL, 1 mmol, 1 equiv). The ice-bath was removed and the reaction mixture was then stirred for 20 h at rt. Methanol was added (0.08 mL, 2 mmol, 2 equiv) and the reaction mixture was then concentrated under vacuum. The residue obtained was dissolved in ethyl acetate and the organic layer was washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (dichloromethane/acetone 10:0 to 7:3) to afford the product as white solid (188 mg, 76%, de>99%). Mp=82-83° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=51.9 (s); 1 H NMR (300 MHz, CDCl 3 ): □=4.15-4.28 (m, 1H), 3.73-3.90 (m, 2H), 3.07-3.16 (m, 1H), 2.08-2.18 (m, 1H), 2.06 (dquint., J=2.3 and 7.0 Hz, 1H), 1.62-1.73 (m, 2H), 1.52 (d, J=13.7 Hz, 3H), 1.40-1.58 (m, 1H), 1.24-1.38 (m, 1H), 1.15 (q, J=11.1 Hz, 1H), 0.93 (d, J=6.7 Hz, 3H), 0.91 (d, J=6.7 Hz, 3H), 0.78-1.08 (m, 2H), 0.82 (d, J=6.7 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=76.2 (d, J POC =7.8 Hz), 60.6 (d, J PC =111 Hz), 48.4 (d, J POCC =5.5 Hz), 43.4, 33.9, 31.4, 25.6, 22.7, 21.9, 20.9, 15.6, 11.8 (d, J PC =91.2 Hz); HRMS (EI+) m/z calcd for C 12 H 26 O 3 P ([M+H] + ) 249.1620. found 249.1621; [α] D =−60.55°
(R p )-Menthyl(hydroxymethyl)allylphosphinate 2b
To a solution of 1 (117 mg, 0.5 mmol, 1 equiv) in dichloromethane (5 mL) at 0° C. and under N 2 was added bis(trimethylsilyl)acetamide (0.25 mL, 1 mmol, 2 equiv) followed by allyl bromide (0.09 mL, 1 mmol, 2 equiv). The ice-bath was removed and the reaction mixture was then stirred for 36 h at rt. Methanol was added (0.04 mL, 1 mmol, 2 equiv) and the reaction mixture was then concentrated under vacuum. The residue obtained was dissolved in ethyl acetate and the organic layer was washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (ethyl acetate/acetone 100:0 to 96:4) to afford the product as white solid (88 mg, 64%, de=95%). Mp=69-71° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=48.4 (s); 1 H NMR (300 MHz, CDCl 3 ): □=5.74-5.93 (m, 1H), 5.19-5.32 (m, 2H), 4.18-4.32 (m, 1H), 3.81-3.89 (m, 2H), 3.53-3.64 (m, 1H), 2.64-2.77 (m, 2H), 2.06-2.18 (m, 2H), 1.61-1.72 (m, 2H), 1.40-1.54 (m, 1H), 1.24-1.39 (m, 1H), 1.15 (q, J=11.5 Hz, 1H), 0.92 (d, J=7.0 Hz, 6H), 0.78-1.08 (m, 2H), 0.81 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=127.2 (d, J PCCC =9.4 Hz), 120.3 (d, J PCC =12.7 Hz), 76.7 (d, J POC =8.3 Hz), 59.1 (d, J PC =107 Hz), 48.5 (d, J POCC =5.5 Hz), 43.4, 34.0, 32.4 (d, J PC =86.8 Hz), 31.5, 25.5, 22.7, 22.0, 21.0, 15.6; HRMS (EI+) m/z calcd for C 14 H 27 O 3 P ([M] + ) 274.1698. found 274.1694; [α] D =−71.31°
(R p )-Menthyl(hydroxymethyl)phenylphosphinate 3a
In a round bottom flask was introduced 1 (117 mg, 0.5 mmol, 1 equiv), Pd(OAc) 2 (2.3 mg, 0.01 mmol, 2.0 mol %), xantphos (6.4 mg, 0.011 mmol, 2.2 mol %), a mixture of DMF and 1,2-dimethoxyethane (2.25 mL:0.25 mL), DIPEA (0.11 mL, 0.65 mmol, 1.3 equiv) and bromobenzene (0.05 mL, 0.5 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in EtOAc and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 5:5 to 3:7) to afford the product as a white solid (106 mg, 68%, de=95%). Mp=103-105° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=37.4 (s); 1 H NMR (300 MHz, CDCl 3 ): Q=7.80-7.91 (m, 2H), 7.45-7.62 (m, 3H), 4.09-4.21 (m, 1H), 4.02-4.08 (m, 2H), 2.77-2.87 (m, 1H), 2.29-2.39 (m, 1H), 1.90-2.05 (m, 1H), 1.58-1.69 (m, 3H), 1.22-1.50 (m, 2H), 0.93 (d, J=6.2 Hz, 3H), 0.85 (d, J=7.0 Hz, 3H), 0.76-1.02 (m, 2H), 0.47 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=132.3 (d, J PCCCC =2.7 Hz), 131.8 (d, J PCCC =9.9 Hz, 2C), 129.4 (d, J PC =124 Hz), 128.4 (d, J PCC =12.1 Hz, 2C), 77.4 (d, J POC =8.3 Hz), 60.4 (d, J PC =115 Hz), 48.6 (d, J POCC =6.0 Hz), 43.6, 34.0, 31.5, 25.4, 22.6, 22.0, 21.0, 15.2; HRMS (EI+) m/z calcd for C 17 H 27 O 3 P ([M+H] + ) 311.1776. found 311.1773; [α] D =−69.04°
(R p )-Menthyl(hydroxymethyl)p-anisylphosphinate 3b
In a round bottom flask was introduced 1 (117 mg, 0.5 mmol, 1 equiv), Pd(OAc) 2 (2.3 mg, 0.01 mmol, 2.0 mol %), xantphos (6.4 mg, 0.011 mmol, 2.2 mol %), a mixture of DMF and 1,2-dimethoxyethane (2.25 mL:0.25 mL), DIPEA (0.11 mL, 0.65 mmol, 1.3 equiv) and 4-bromoanisole (0.06 mL, 0.5 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in EtOAc and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 5:5 to 0:10) to afford the product as a white solid (90 mg, 53%, de=81%). Mp=110-112° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=37.8 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.74-7.84 (m, 2H), 6.96-7.03 (m, 2H), 4.05-4.18 (m, 1H), 3.96-4.05 (m, 2H), 3.87 (s, 3H), 2.60-2.71 (m, 1H), 2.29-2.39 (m, 1H), 2.01 (dquint., J=2.6 and 7.3 Hz, 1H), 1.58-1.69 (m, 3H), 1.20-1.48 (m, 2H), 0.93 (d, J=6.5 Hz, 3H), 0.87 (d, J=6.7 Hz, 3H), 0.76-1.02 (m, 2H), 0.51 (d, J=6.8 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=162.8 (d, J PCCCC =2.8 Hz), 133.7 (d, J PCCC =11.1 Hz, 2C), 120.5 (d, J PC =131 Hz), 114.0 (d, J PCC =13.2 Hz, 2C), 77.2 (d, J POC =7.7 Hz), 60.5 (d, J PC =117 Hz), 55.3, 48.7 (d, J POCC =6.0 Hz), 43.6, 34.0, 31.5, 25.4, 22.7, 22.0, 21.0, 15.3; HRMS (EI+) m/z calcd for C 18 H 29 O 4 P ([M] + ) 340.1803. found 340.1801; [α] D =−68.27°
(R p )-Menthyl(hydroxymethyl)-1-naphtylphosphinate 3c
In a round bottom flask was introduced 1 (117 mg, 0.5 mmol, 1 equiv), Pd(OAc) 2 (2.3 mg, 0.01 mmol, 2.0 mol %), xantphos (6.4 mg, 0.011 mmol, 2.2 mol %), a mixture of DMF and 1,2-dimethoxyethane (2.25 mL:0.25 mL), DIPEA (0.11 mL, 0.65 mmol, 1.3 equiv) and 1-bromonaphthalene (0.06 mL, 0.5 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in EtOAc and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 5:5 to 0:10) to afford the product as a white solid (152 mg, 84%, de=94%). Mp=102-103° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=38.6 (s); 1 H NMR (300 MHz, CDCl 3 ): □=8.54-8.60 (m, 1H), 8.20-8.30 (m, 1H), 8.03-8.10 (m, 1H), 7.88-7.96 (m, 1H), 7.52-7.64 (m, 3H), 4.29-4.43 (m, 1H), 4.08-4.27 (m, 2H), 2.35-2.44 (m, 1H), 1.88-2.00 (m, 1H), 1.59-1.74 (m, 3H), 1.35-1.54 (m, 3H), 0.96 (d, J=6.2 Hz, 3H), 0.84-1.04 (m, 2H), 0.74 (d, J=7.0 Hz, 3H), 0.44 (d, J=6.8 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=134.3 (d, J PCCC =7.7 Hz), 133.6 (d, J PCCC =9.4 Hz), 133.5 (d, J PCCCC =2.7 Hz), 133.0 (d, J PCC =11.6 Hz), 129.0, 127.3, 126.2, 126.2 (d, J PCCC =3.3 Hz), 126.1 (d, J PC =121 Hz), 124.7 (d, J PCC =13.8 Hz), 78.0 (d, J POC =8.3 Hz), 61.8 (d, J PC =111 Hz), 48.7 (d, J POCC =5.0 Hz), 43.6, 34.0, 31.7, 25.4, 22.7, 22.1, 20.9, 15.2; HRMS (EI+) m/z calcd for C 21 H 29 O 3 P ([M] + ) 360.1854. found 360.1860; [α] D =−52.26°
(S p )-Menthyl phenyl-H-phosphinate 4a
To a solution of N-chlorosuccinimide (110 mg, 0.82 mmol, 1.5 equiv) in dichloromethane (5 mL) at −78° C. and under N 2 was added dropwise a solution of dimethyl sulfide (0.06 mL, 0.82 mmol, 1.5 equiv) in dichloromethane (1 mL). After 10 minutes at −78° C., a solution of 3a (170 mg, 0.55 mmol, 1 equiv) in dichloromethane (2 mL) was added over 20 minutes. After 1 h at −78° C., triethylamine (0.38 mL, 2.74 mmol, 5 equiv) was added over 15 minutes and the reaction was allowed to warm to rt. After 1 h at rt, water was added and the two layers were separated. The aqueous layer was then washed with dichloromethane (×2). The combined organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 6:4) to afford the product as a colorless oil (125 mg, 81%, de>99%). 31 P NMR (121.47 MHz, CDCl 3 ): □=22.4 (d, J=557 Hz); 1 H NMR (300 MHz, CDCl 3 ): □=7.67-7.82 (m, 2H), 7.68 (d, J=557 Hz, 1H), 7.42-7.62 (m, 3H), 4.18-4.32 (m, 1H), 2.25-2.35 (m, 1H), 2.02-2.16 (m, 1H), 1.62-1.75 (m, 2H), 1.22-1.58 (m, 3H), 0.80-1.14 (m, 2H), 0.95 (d, J=6.4 Hz, 3H), 0.88 (d, J=7.0 Hz, 3H), 0.67 (d, J=7.0 Hz, 3H)
(S p )-Menthyl-1-naphtyl-H-phosphinate 4b
To a solution of N-chlorosuccinimide (100 mg, 0.75 mmol, 3 equiv) in dichloromethane (15 mL) at −78° C. and under N 2 was added dropwise a solution of dimethyl sulfide (0.055 mL, 0.75 mmol, 3 equiv) in dichloromethane (2 mL). After 10 minutes at −78° C., a solution of 3c (90 mg, 0.25 mmol, 1 equiv) in dichloromethane (2 mL) was added over 20 minutes. After 1 h at −78° C., triethylamine (0.38 mL, 2.74 mmol, 5 equiv) was added over 15 minutes and the reaction was stirred for 30 minutes at −78° C. After warming up to rt, water was added and the two layers were separated. The aqueous layer was then washed with dichloromethane (×2). The combined organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 7:3) to afford the product as a colorless oil (72 mg, 87%, de=94%). 31 P NMR (121.47 MHz, CDCl 3 ): □=23.3 (dm, J=557 Hz); 1 H NMR (300 MHz, CDCl 3 ): □=8.45-8.51 (m, 1H), 7.99-8.10 (m, 2H), 8.05 (d, J=557 Hz, 1H), 7.90-7.96 (m, 1H), 7.54-7.67 (m, 3H), 4.31-4.44 (m, 1H), 2.34-2.44 (m, 1H), 2.05 (dquint., J=2.6 and 7.0 Hz, 1H), 1.61-1.74 (m, 2H), 1.24-1.56 (m, 3H), 0.97 (d, J=6.4 Hz, 3H), 0.75-1.10 (m, 2H), 0.80 (d, J=7.0 Hz, 3H), 0.61 (d, J=6.7 Hz, 3H); [α] D =−73.97°
(S p )-Menthyl methyl-H-phosphinate 4c
To a solution of N-chlorosuccinimide (470 mg, 3.5 mmol, 3 equiv) in dichloromethane (35 mL) at −78° C. and under N 2 was added dropwise a solution of dimethyl sulfide (0.26 mL, 3.5 mmol, 3 equiv) in dichloromethane (3 mL). After 10 minutes at −78° C., a solution of 2a (290 mg, 1.17 mmol, 1 equiv) in dichloromethane (5 mL) was added over 20 minutes. After 1 h at −78° C., triethylamine (0.81 mL, 5.84 mmol, 5 equiv) was added over 15 minutes and the reaction was stirred for 30 minutes at −78° C. After warming up to rt, water was added and the two layers were separated. The aqueous layer was then washed with dichloromethane (×2). The combined organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 8:2 to 4:6) to afford the product as a colorless oil (134 mg, 61%, de=96%). 31 P NMR (121.47 MHz, CDCl 3 ): □=28.5 (dm, J=537 Hz); 1 H NMR (300 MHz, CDCl 3 ): □=7.33 (d, J=537 Hz, 1H), 4.15-4.29 (m, 1H), 2.06-2.20 (m, 2H), 1.62-1.73 (m, 2H), 1.52 (d, J=15.2 Hz, 3H), 1.24-1.58 (m, 2H), 1.14 (q, J=11.4 Hz, 1H), 0.93 (d, J=6.2 Hz, 6H), 0.78-1.10 (m, 2H), 0.83 (d, J=7.1 Hz, 3H)
(S p )-Menthyl(hydroxymethyl)phenylphosphinate 5
To a solution of phenylphosphinic acid (42.6 g, 300 mmol, 1 equiv) in toluene (300 mL) was added L-menthol (46.9 g, 300 mmol, 1 equiv). The reaction mixture was then stirred at reflux for 24 h under N 2 and in a flask equipped with a Dean-stark trap. After cooling down the reaction to rt, paraformaldehyde (9.01 g, 300 mmol, 1 equiv) was added and the reaction mixture was stirred at reflux for 24 h under N 2 . The solvent was then removed under vacuum and the crude obtained was recrystallized at rt in diethyl ether (200 mL) to afford the product as colorless crystals (24.2 g, 26%, de=95%). Mp=138-139° C.; 31 P NMR (121.47 MHz, CDCl 3 ): H=37.2 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.77-7.87 (m, 2H), 7.52-7.60 (m, 1H), 7.42-7.51 (m, 2H), 4.29-4.43 (m, 2H), 3.93-4.10 (m, 2H), 2.26 (dquint., J=2.6 and 7.0 Hz, 1H), 1.80-1.91 (m, 1H), 1.57-1.73 (m, 2H), 1.26-1.47 (m, 2H), 0.96 (d, J=7.1 Hz, 3H), 0.74-1.13 (m, 3H), 0.89 (d, J=7.0 Hz, 3H), 0.78 (d, J=6.4 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=132.3 (d, J PCCCC =2.8 Hz), 131.7 (d, J PCCC =9.9 Hz, 2C), 130.6 (d, J PC =123 Hz), 128.3 (d, J PCC =12.1 Hz, 2C), 77.1 (d, J POC =8.3 Hz), 60.2 (d, J PC =117 Hz), 48.7 (d, J POCC =6.1 Hz), 43.2, 34.0, 31.4, 25.5, 22.8, 21.9, 21.1, 15.7; HRMS (EI+) m/z calcd for C 16 H 28 O 3 P ([M+H] + ) 311.1776. found 311.1766; [α] D =−46.74°
(R R )-Menthyl phenyl-H-phosphinate 6
To a solution of N-chlorosuccinimide (1.6 g, 12 mmol, 3 equiv) in dichloromethane (80 mL) at −78° C. and under N 2 was added dropwise a solution of dimethyl sulfide (0.88 mL, 12 mmol, 3 equiv) in dichloromethane (5 mL). After 10 minutes at −78° C., a solution of 5 (1.24 g, 4 mmol, 1 equiv) in dichloromethane (10 mL) was added over 20 minutes. After 1 h at −78° C., triethylamine (2.8 mL, 20 mmol, 5 equiv) was added over 15 minutes and the reaction was stirred for 30 minutes at −78° C. After warming up to rt, water was added and the two layers were separated. The aqueous layer was then washed with dichloromethane (×2). The combined organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 8:2) to afford the product as a colorless oil (1.03 g, 91%, de=95%). 31 P NMR (121.47 MHz, CDCl 3 ): □=24.7 (dm, J=553 Hz); 1 H NMR (300 MHz, CDCl 3 ): □=7.73-7.84 (m, 2H), 7.66 (d, J=553 Hz, 1H), 7.46-7.64 (m, 3H), 4.22-4.36 (m, 1H), 2.14-2.27 (m, 2H), 1.62-1.75 (m, 2H), 1.38-1.54 (m, 2H), 1.24 (q, J=11.2 Hz, 1H), 0.78-1.13 (m, 2H), 0.96 (d, J=7.0 Hz, 3H), 0.90 (d, J=6.4 Hz, 3H), 0.86 (d, J=7.0 Hz, 3H); [α] D =−35.48°
(S p )-Menthyl(p-anisyl)phenylphosphinate 7a
In a round bottom flask was introduced 6 (280.3 mg, 1 mmol, 1 equiv), Pd(OAc) 2 (4.5 mg, 0.02 mmol, 2.0 mol %), xantphos (12.7 mg, 0.022 mmol, 2.2 mol %), a mixture of toluene and ethyl glycol (4.5 mL:0.5 mL), DIPEA (0.23 mL, 1.3 mmol, 1.3 equiv) and 4-iodoanisole (234 mg, 1 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in ethyl acetate and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 8:2 to 7:3) to afford the product as a yellow oil (325 mg, 84%, de=97%). 31 P NMR (121.47 MHz, CDCl 3 ): □=29.7 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.67-7.86 (m, 4H), 7.38-7.54 (m, 3H), 6.90-6.98 (m, 2H), 4.15-4.28 (m, 1H), 3.84 (s, 3H), 2.06-2.23 (m, 2H), 1.58-1.70 (m, 2H), 1.30-1.51 (m, 2H), 1.21 (q, J=11.1 Hz, 1H), 0.78-1.04 (m, 2H), 0.89 (d, J=7.0 Hz, 3H), 0.85 (d, J=6.5 Hz, 3H), 0.55 (d, J=6.8 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): i=162.4 (d, J PCCCC =3.3 Hz), 133.5 (d, J PCCC =11.6 Hz, 2C), 133.4 (d, J PC =139 Hz), 131.6 (d, J PCCCC =2.8 Hz), 131.4 (d, J PCCC =10.5 Hz, 2C), 128.2 (d, J PCC =12.7 Hz), 123.4 (d, J PC =143 Hz), 113.8 (d, J PCC =13.8 Hz), 76.9 (d, J POC =7.2 Hz), 55.1, 48.8 (d, J POCC =6.6 Hz), 43.5, 34.0, 31.5, 25.5, 22.6, 21.9, 21.1, 15.3; HRMS (EI+) m/z calcd for C 23 H 31 O 3 P ([M] + ) 386.2012. found 386.2015; [α] D =−68.41°
(S p )-Menthyl(o-anisyl)phenylphosphinate 7b
In a round bottom flask was introduced 6 (280.3 mg, 1 mmol, 1 equiv), Pd(OAc) 2 (4.5 mg, 0.02 mmol, 2.0 mol %), xantphos (12.7 mg, 0.022 mmol, 2.2 mol %), a mixture of toluene and ethyl glycol (4.5 mL:0.5 mL), DIPEA (0.23 mL, 1.3 mmol, 1.3 equiv) and 2-bromoanisole (0.125 mL, 1 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in ethyl acetate and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 7:3) to afford the product as a white solid (339 mg, 88%, de>99%). Mp=91-93° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=27.6 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.99-8.11 (m, 1H), 7.76-7.88 (m, 2H), 7.35-7.54 (m, 4H), 7.02-7.11 (m, 1H), 6.77-6.86 (m, 1H), 4.15-4.28 (m, 1H), 3.61 (s, 3H), 2.10-2.25 (m, 2H), 1.56-1.71 (m, 2H), 1.30-1.51 (m, 2H), 1.21 (q, J=11.2 Hz, 1H), 0.78-1.03 (m, 2H), 0.87 (d, J=7.1 Hz, 3H), 0.84 (d, J=6.4 Hz, 3H), 0.48 (d, J=6.7 Hz, 3H); [α] D =−90.31°
(S p )-Menthyl(o-anisyl)phenylphosphinate 7c
In a round bottom flask was introduced 6 (280.3 mg, 1 mmol, 1 equiv), Pd(OAc) 2 (4.5 mg, 0.02 mmol, 2.0 mol %), xantphos (12.7 mg, 0.022 mmol, 2.2 mol %), a mixture of toluene and ethyl glycol (4.5 mL:0.5 mL), DIPEA (0.23 mL, 1.3 mmol, 1.3 equiv) and 1-bromonaphthalene (0.14 mL, 1 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in ethyl acetate and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 8:2) to afford the product as a white solid (378 mg, 93%, de=93%). Mp=85-87° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=29.6 (s); 1 H NMR (300 MHz, CDCl 3 ): □=8.41-8.47 (m, 1H), 8.24-8.34 (m, 1H), 7.99-8.06 (m, 1H), 7.76-7.89 (m, 3H), 7.52-7.60 (m, 1H), 7.36-7.52 (m, 5H), 4.33-4.47 (m, 1H), 2.07-2.17 (m, 1H), 1.91-2.04 (m, 1H), 1.56-1.68 (m, 3H), 1.33-1.52 (m, 2H), 1.26 (q, J=10.8 Hz, 1H), 0.78-1.03 (m, 2H), 0.85 (d, J=6.2 Hz, 3H), 0.73 (d, J=7.1 Hz, 3H), 0.39 (d, J=6.7 Hz, 3H)
(R p )-Menthyl methylphenylphosphinate 8a
To a solution of 6 (280 mg, 1 mmol, 1 equiv) in dichloromethane (10 mL) at 0° C. and under N 2 was added bis(trimethylsilyl)acetamide (0.49 mL, 2 mmol, 2 equiv) followed by iodomethane (0.125 mL, 2 mmol, 2 equiv). The ice-bath was removed and the reaction mixture was stirred for 2 h at rt. Methanol was added (0.08 mL, 2 mmol, 2 equiv) and the reaction mixture was concentrated under vacuum. The residue obtained was dissolved in ethyl acetate and the organic layer was washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 8:2) to afford the product as white solid (265 mg, 90%, de=94%). Mp=82-84° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=39.5 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.47-7.57 (m, 2H), 7.14-7.29 (m, 3H), 3.92-4.06 (m, 1H), 1.91 (dquint., J=2.6 and 6.7 Hz, 1H), 1.47-1.57 (m, 1H), 1.36 (d, J=14 Hz, 3H), 1.27-1.42 (m, 2H), 0.95-1.14 (m, 2H), 0.46-0.82 (m, 3H), 0.67 (d, J=7.0 Hz, 3H), 0.60 (d, J=7.0 Hz, 3H), 0.48 (d, J=6.4 Hz, 3H); [α] D =−36.40°
(R p )-Menthyl allylphenylphosphinate 8b
To a solution of 6 (520 mg, 1.85 mmol, 1 equiv) in dichloromethane (20 mL) at 0° C. and under N 2 was added bis(trimethylsilyl)acetamide (0.91 mL, 3.71 mmol, 2 equiv) followed by allyl bromide (0.32 mL, 3.71 mmol, 2 equiv). The ice-bath was removed and the reaction mixture was stirred for 4 days at rt. Methanol was added (0.15 mL, 3.71 mmol, 2 equiv) and the reaction mixture was concentrated under vacuum. The residue obtained was dissolved in ethyl acetate and the organic layer was washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 7:3) to afford the product as yellow oil (336 mg, 57%, de=96%). 31 P NMR (121.47 MHz, CDCl 3 ): □=37.7 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.71-7.84 (m, 2H), 7.40-7.58 (m, 3H), 5.64-5.82 (m, 1H), 4.96-5.14 (m, 2H), 4.24-4.39 (m, 1H), 2.62-2.87 (m, 2H), 2.18-2.33 (m, 1H), 1.72-1.84 (m, 1H), 1.54-1.72 (m, 2H), 1.23-1.46 (m, 2H), 0.68-1.10 (m, 3H), 0.95 (d, J=7.0 Hz, 3H), 0.88 (d, J=6.7 Hz, 3H), 0.75 (d, J=6.5 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=132.4 (d, J PC =126 Hz), 131.8 (d, J PCCCC =2.8 Hz), 131.4 (d, J PCCC =10.0 Hz, 2C), 128.1 (d, J PCC =12.7 Hz, 2C), 127.3 (d, J PCCC =9.4 Hz), 120.0 (d, J PCC =13.2 Hz), 76.4 (d, J POC =7.2 Hz), 48.7 (d, J POCC =6.0 Hz), 43.0, 36.6 (d, J PC =97.3 Hz), 33.9, 31.3, 25.5, 22.7, 21.8, 21.0, 15.6; HRMS (EI+) m/z calcd for C 19 H 29 O 2 P ([M] + ) 320.1905. found 320.1912; [α] D =−36.65°
(R p )-Menthyl octylphenylphosphinate 9
To a solution of 6 (375 mg, 1.34 mmol, 1 equiv) in hexane (5 mL) was added 1-octene (0.21 mL, 1.34 mmol, 1 equiv) followed by the addition of triethylborane (1.34 mL, 1.34 mmol, 1 equiv, 1.0M in THF). The reaction mixture was stirred for 20 h at rt under air. Ethyl acetate and an aqueous solution of NaHSO 4 at 1M were added and the two layers were separated. The organic layer was washed with NaHCO 3 and brine, dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 90:15 to 85:15) to afford the product as yellow oil (384 mg, 73%, de=95%).
In a round bottom flask was introduced 6 (280 mg, 1 mmol, 1 equiv) 1-octene (0.39 mL, 2.5 mmol, 2.5 equiv) and Mn(OAc) 2 (9 mg, 0.05 mmol, 5 mol %). The reaction mixture was stirred for 16 h at 100° C. under air. Ethyl acetate and an aqueous solution of Na 2 S 2 O 4 at 0.5M were added and the two layers were separated. The organic layer was washed with brine, dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 8:2) to afford the product as yellow oil (309 mg, 79%, de=95%). 31 P NMR (121.47 MHz, CDCl 3 ): □=42.4 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.73-7.84 (m, 2H), 7.41-7.56 (m, 3H), 4.22-4.35 (m, 1H), 2.25 (dquint., J=2.4 and 7.0 Hz, 1H), 1.48-1.98 (m, 5H), 1.13-1.48 (m, 14H), 0.70-1.10 (m, 3H), 0.96 (d, J=7.1 Hz, 3H), 0.88 (d, J=7.0 Hz, 3H), 0.86 (t, J=6.8 Hz, 3H), 0.74 (d, J=6.5 Hz, 3H); [α] D =−27.42°
(S p )-Menthyl(N-methylphthalimide)phenylphosphinate 10
To a solution of 5 (621 mg, 2 mmol, 1 equiv), phtalimide (382.5 mg, 2.6 mmol, 1.3 equiv) and diphenyl-2-pyridylphosphine (684.5 mg, 2.6 mmol, 1.3 equiv) in dichloromethane (20 ml) was added diisopropyl azodicarboxylate (0.51 mL, 2.6 mmol, 1.3 equiv). The reaction mixture was stirred for 24 h at rt under N 2 . Water and brine (1:1) were added and the two layers were separated. The aqueous layer was then extracted with dichloromethane (×2). The combined organic layers was dried over MgSO 4 , filtered and concentrated under vacuum. The residue obtained was purified by column chromatography (hexanes/ethyl acetate 9:1 to 7:3) to afford the product as a white solid (612 mg, 70%, de=95%). Mp=106-107° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=31.4 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.79-7.91 (m, 4H), 7.68-7.75 (m, 2H), 7.52-7.60 (m, 1H), 7.42-7.51 (m, 2H), 4.33-4.46 (m, 1H), 4.10-4.30 (m, 2H), 2.17 (dquint., J=2.3 and 6.7 Hz, 1H), 1.78-1.88 (m, 1H), 1.55-1.69 (m, 2H), 1.20-1.46 (m, 2H), 0.94-1.12 (m, 2H), 0.72-0.88 (m, 1H), 0.84 (d, J=7.0 Hz, 3H), 0.79 (d, J=7.0 Hz, 3H), 0.75 (d, J=6.8 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=166.6 (2C), 134.0 (2C), 132.5 (d, J PCCCC =2.8 Hz), 131.7 (2C), 131.6 (d, J PCCC =8.8 Hz, 2C), 131.3 (d, J PC =130 Hz), 128.3 (d, J PCC =12.7 Hz, 2C), 123.2 (2C), 77.6 (d, J POC =7.7 Hz), 48.5 (d, J POCC =6.1 Hz), 42.9, 38.1 (d, J PC =107 Hz), 33.8, 31.3, 25.3, 22.5, 21.8, 20.9, 15.4; HRMS (EI+) m/z calcd for C 25 H 31 NO 4 P ([M+H] + ) 440.1991. found 440.1985; [α] D =−21.18°
(S p )-Menthyl[(tosyloxy)methyl]phenylphosphinate 11
To a solution of 5 (3.1 g, 10 mmol, 1 equiv) in dichloromethane (60 ml) under N 2 was added N,N-diisopropylethylamine (4.35 mL, 25 mmol, 2.5 equiv). The mixture was cooled down to 0° C. and a solution of tosyl chloride (2.89 g, 20 mmol, 2 equiv) in dichloromethane (45 ml) was added over 1 h. The ice-bath was removed and the solution was stirred for 20 h at rt. A saturated aqueous solution of NaHCO 3 was added and the two layers were separated. The aqueous layer was extracted with dichloromethane (2×). The combined organic layers was dried over MgSO 4 , filtered and concentrated under vacuum. The residue obtained was purified by column chromatography (hexanes/ethyl acetate 9:1 to 7:3) to afford the product as colorless crystals (4.42 g, 95%, de=92%). Mp=68-70° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=29.3 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.72-7.82 (m, 2H), 7.56-7.64 (m, 3H), 7.42-7.52 (m, 2H), 7.23-7.29 (m, 2H), 4.09-4.42 (m, 3H), 2.44 (s, 3H), 2.14 (dquint., J=2.6 and 7.0 Hz, 1H), 1.90-2.00 (m, 1H), 1.57-1.73 (m, 2H), 1.26-1.48 (m, 2H), 1.11 (q, J=11.1 Hz, 1H), 0.76-1.06 (m, 2H), 0.93 (d, J=7.1 Hz, 3H), 0.80 (d, J=6.5 Hz, 3H), 0.80 (d, J=7.0 Hz, 3H); HRMS (EI+) m/z calcd for C 24 H 34 O 5 PS ([M+H] + ) 465.1865. found 465.1857; [α] D =−29.575°
(S p )-Menthyl(iodomethyl)phenylphosphinate 12
To a solution of 11 (2.32 g, 5 mmol, 1 equiv) in acetone (35 ml) was added sodium iodide (3.0 g, 20 mmol, 4 equiv). The reaction mixture was stirred for 24 h at reflux. The solvent was removed under vacuum and the residue obtained was dissolved in dichloromethane. The organic layer was washed with brine, dried over MgSO 4 , filtered and concentrated under vacuum. The solid obtained was purified by column chromatography (dichloromethane/ethyl acetate 10:0 to 9:1) to afford the product as a yellow solid (1.612 g, 77%, de=91%). Mp=66-68° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=32.1 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.79-7.90 (m, 2H), 7.44-7.64 (m, 3H), 4.33-4.47 (m, 1H), 3.05-3.28 (m, 2H), 2.30-2.45 (m, 1H), 1.80-1.91 (m, 1H), 1.57-1.74 (m, 2H), 1.23-1.51 (m, 2H), 0.76-1.10 (m, 3H), 0.97 (d, J=7.1 Hz, 3H), 0.90 (d, J=7.1 Hz, 3H), 0.76 (d, J=6.8 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=132.6 (d, J PCCCC =2.7 Hz), 131.9 (d, J PCCC =9.9 Hz, 2C), 130.3 (d, J PC =136 Hz), 128.4 (d, J PCC =13.2 Hz, 2C), 78.2 (d, J POC =7.2 Hz), 48.7 (d, J POCC =6.1 Hz), 43.1, 34.0, 31.4, 25.6, 22.9, 21.9, 21.2, 15.9, −6.5 (d, J PC =102 Hz); HRMS (EI+) m/z calcd for C 17 H 27 IO 2 P ([M+H] + ) 421.0793. found 421.0793; [α] D =−29.46°
(R p , R p )-Menthyl(methyl)phenylphosphinate 13
To a solution of 12 (420.3 mg, 1 mmol, 1 equiv) in THF (8 mL) at −78° C. under N 2 was slowly added isopropyl magnesium chloride (0.55 mL, 1.1 mmol, 1.1 equiv, 2.0M in THF). After 1 h of stirring at −78° C., CuCl 2 (403 mg, 3 mmol, 3 equiv) was added. The ice-bath was removed and the reaction mixture was stirred for 2 h at rt. A saturated solution of NH 4 Cl was added and the two layers were separated. The aqueous layer was extracted with dichloromethane (3×). The combined organic layers was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 8:2 to 6:4) to afford the product as a white solid (237 mg, 81%, de=92%). Mp=84-85° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=39.7 (m); 1 H NMR (300 MHz, CDCl 3 ): □=7.77-7.87 (m, 4H), 7.44-7.59 (m, 6H), 4.23-4.36 (m, 2H), 2.21 (dquint., J=2.3 and 7.0 Hz, 2H), 1.78-1.87 (m, 2H), 1.66 (d, J=14.4 Hz, 4H), 1.56-1.72 (m, 4H), 1.25-1.44 (m, 4H), 0.74-1.11 (m, 6H), 0.97 (d, J=7.1 Hz, 6H), 0.90 (d, J=7.0 Hz, 6H), 0.78 (d, J=6.4 Hz, 6H); [α] D =−24.825°
General Wittig-Rearrangement Procedure:
To a suspension of NaH (120 mg, 3 mmol, 1.5 equiv, 60% in mineral oil) in THF (15 mL) at 0° C. under N 2 was added a solution of 5 (621 mg, 2 mmol, 1 equiv) in THF (5 mL). After 30 minutes of stirring at 0° C., a solution of the appropriate allyl bromide (2.4 mmol, 1.2 equiv) in THF (3 mL) was added. The reaction mixture was stirred for 16 h at rt. A saturated solution of NH 4 Cl was added and the two layers were separated. The aqueous layer was extracted with dichloromethane (3×). The combined organic layers was dried over MgSO 4 , filtered and concentrated under vacuum. The pure intermediate was obtained directly after extraction or after purification by column chromatography (hexane/ethyl acetate).
To a solution of the purified intermediate (1 equiv) in THF at −78° C. under N 2 was slowly added a solution of sec-BuLi (2 equiv, 1.4M in cyclohexane). After 24 hours at −78° C., a saturated solution of NH 4 Cl was added and the two layers were separated. The aqueous layer was extracted with dichloromethane (3×). The combined organic layers was dried over MgSO 4 , filtered and concentrated under vacuum. The crude was purified by column chromatography (hexane/ethyl acetate) to afford the appropriate product.
General wittig-rearrangement procedure using allyl bromide (0.21 mL, 2.4 mmol, 1.2 equiv). The pure intermediate was obtained as a colorless oil directly after extraction (455 mg, 65%, de>99%). 31 P NMR (121.47 MHz, CDCl 3 ): □=34.3 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.79-7.92 (m, 2H), 7.41-7.62 (m, 3H), 5.71-5.84 (m, 1H), 5.17-5.23 (m, 2H), 4.32-4.43 (m, 1H), 3.74-4.06 (m, 4H), 2.14-2.38 (m, 2H), 1.92-2.03 (m, 2H), 0.64-1.75 (m, 5H), 0.93 (d, J=7.0 Hz, 3H), 0.91 (d, J=6.4 Hz, 3H), 0.81 (d, J=6.7 Hz, 3H).
The second step was performed using the intermediate (350 mg, 1 mmol, 1 equiv) and sec-BuLi (1.43 mL, 2 mmol, 2 equiv, 1.4M in cyclohexane). The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 7:3) to afford the product as a white solid (192 mg, 55%, de>99%). Mp=109-110° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=38.0 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.79-7.90 (m, 2H), 7.54-7.62 (m, 1H), 7.45-7.54 (m, 2H), 5.73-5.90 (m, 1H), 5.05-5.15 (m, 2H), 4.33-4.47 (m, 1H), 3.89-3.99 (m, 1H), 2.12-2.50 (m, 4H), 1.83-1.93 (m, 1H), 1.56-1.74 (m, 2H), 1.23-1.52 (m, 2H), 0.74-1.14 (m, 3H), 0.96 (d, J=6.7 Hz, 3H), 0.89 (d, J=6.8 Hz, 3H), 0.78 (d, J=6.5 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=134.4 (d, J PCC =14.4 Hz), 132.4 (d, J PCCC =9.4 Hz, 2C), 132.3 (d, J PCCCC =2.3 Hz), 130.0 (d, J PC =120 Hz), 128.2 (d, J PCC =12.2 Hz, 2C), 117.4, 77.4 (d, J POC =8.3 Hz), 70.2 (d, J PC =115 Hz), 48.8 (d, J POCC =6.0 Hz), 43.3, 35.7 (d, J PCC =5.0 Hz), 34.0, 31.4, 25.7, 22.8, 21.9, 21.1, 15.7; HRMS (EI+) m/z calcd for C 20 H 31 O 3 P ([M+H] + ) 351.2089. found 351.2091; [α] D =−34.00°
General wittig-rearrangement procedure using cinnamyl bromide (0.36 mL, 2.4 mmol, 1.2 equiv). The crude was purified by column chromatography (hexane/ethyl acetate 9:1 to 7:3) to afford the intermediate as a yellow oil (726 mg, 85%, de>99%). 31 P NMR (121.47 MHz, CDCl 3 ): □=35.0 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.83-7.93 (m, 2H), 7.53-7.60 (m, 1H), 7.43-7.53 (m, 2H), 7.22-7.36 (m, 5H), 6.50 (d, J=15.8 Hz, 1H), 6.07-6.19 (m, 1H), 4.32-4.45 (m, 1H), 4.19 (d, J=6.2 Hz, 2H), 3.81-3.99 (m, 2H), 2.24-2.36 (m, 1H), 1.93-2.03 (m, 1H), 1.57-1.74 (m, 2H), 1.22-1.50 (m, 2H), 1.11 (q, J=11.7 Hz, 1H), 0.74-1.06 (m, 2H), 0.95 (d, J=7.0 Hz, 3H), 0.87 (d, J=7.0 Hz, 3H), 0.80 (d, J=6.5 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=136.5, 133.5, 132.5 (d, J PCCC =2.3 Hz), 132.0 (d, J PCCC =9.4 Hz, 2C), 131.4 (d, J PC =149 Hz), 128.7 (2C), 128.5 (d, J PCC =13.3 Hz, 2C), 128.0, 126.7 (2C), 125.0, 77.4 (d, J POC =7.5 Hz), 73.8 (d, J PCOC =11.8 Hz), 67.3 (d, J P c=119 Hz), 48.9 (d, J POCC =6.0 Hz), 43.7, 34.2, 31.7, 25.8, 23.1, 22.1, 21.3, 16.0
The second step was performed using the intermediate (700 mg, 1.64 mmol, 1 equiv) and sec-BuLi (2.34 mL, 3.28 mmol, 2 equiv, 1.4M in cyclohexane). The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 7:3) to afford the product as a white solid (532 mg, 76%, de>99%). Mp=103-105° C.; HRMS (EI+) m/z calcd for C 26 H 36 O 3 P ([M+H] + ) 427.2409. found 427.2401; [α] D =−14.525°
General wittig-rearrangement procedure using prenyl bromide (0.31 mL, 2.4 mmol, 1.2 equiv). The crude was purified by column chromatography (hexane/ethyl acetate 9:1 to 8:2) to afford the intermediate as a colorless oil (734 mg, 97%, de=97%). 31 P NMR (121.47 MHz, CDCl 3 ): □=34.1 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.82-7.91 (m, 2H), 7.42-7.59 (m, 3H), 5.15-5.24 (m, 1H), 4.29-4.43 (m, 1H), 4.02 (d, J=6.7 Hz, 2H), 3.73-3.92 (m, 2H), 2.28 (dquint., J=2.4 and 7.0 Hz, 1H), 1.93-2.02 (m, 1H), 1.71 (s, 3H), 1.57-1.74 (m, 2H), 1.60 (s, 3H), 1.28-1.48 (m, 2H), 1.10 (q, J=11.1 Hz, 1H), 0.74-1.06 (m, 2H), 0.95 (d, J=7.0 Hz, 3H), 0.87 (d, J=6.8 Hz, 3H), 0.80 (d, J=6.5 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=137.9, 132.1 (d, J PCCCC =2.8Hz), 131.6 (d, J PCCC =10.0 Hz, 2C), 131.2 (d, J PC =128 Hz), 128.0 (d, J PCC =12.7 Hz, 2C), 120.1, 76.9 (d, J POC =7.7 Hz), 69.2 (d, J PCOC =11.6 Hz), 66.5 (d, J PC =119 Hz), 48.6 (d, J POCC =6.1 Hz), 43.3, 33.9, 31.3, 25.6, 25.4, 22.7, 21.8, 21.0, 17.8, 15.6
The second step was performed using the intermediate (378.5 mg, 1 mmol, 1 equiv) and sec-BuLi (1.43 mL, 2 mmol, 2 equiv, 1.4M in cyclohexane). The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 8:2) to afford the product as a white solid (244 mg, 64%, de>99%). Mp=130-131° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=34.7 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.82-7.92 (m, 2H), 7.51-7.59 (m, 1H), 7.41-7.50 (m, 2H), 5.88 (dd, J=10.7 and 17.3 Hz, 1H), 4.87-4.97 (m, 2H), 4.22-4.35 (m, 1H), 3.68 (s, 1H), 2.75 (s, 1H), 2.36 (dquint., J=2.1 and 7.0 Hz, 1H), 1.55-1.80 (m, 3H), 1.33-1.46 (m, 1H), 1.20-1.33 (m, 1H), 1.09 (s, 3H), 1.08 (s, 3H), 0.70-1.13 (m, 3H), 0.95 (d, J=7.0 Hz, 3H), 0.86 (d, J=7.0 Hz, 3H), 0.74 (d, J=6.5 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=140.0 (d, J PCCC =5.6 Hz), 132.9 (d, J PC =119 Hz), 132.4 (d, J PCCC =9.4 Hz, 2C), 132.1 (d, J PCCCC =2.2 Hz), 128.0 (d, J PCC =12.2 Hz, 2C), 112.7, 78.0 (d, J PC =108 Hz), 77.3 (d, J POC =8.3 Hz), 48.8 (d, J POCC =5.0 Hz), 43.1, 41.3 (d, J POCC =3.8 Hz), 33.9, 31.4, 25.3, 24.4 (d, J PCCC =5.0 Hz), 23.7 (d, J PCCC =6.7 Hz), 22.6, 21.9, 21.2, 15.5; HRMS (EI+) m/z calcd for C 22 H 36 O 3 P ([M+H] + ) 379.2402. found 379.2405; [α] D =−15.46°
(R p )-Menthyl cinnamyl(hydroxymethyl)phosphinate 15
In a round bottom flask was introduced 1 (234 mg, 1 mmol, 1 equiv), Pd(OAc) 2 (4.5 mg, 0.02 mmol, 2.0 mol %), xantphos (12.7 mg, 0.022 mmol, 2.2 mol %), a mixture of DMF and 1,2-dimethoxyethane (4.5 mL:0.5 mL), DIPEA (0.23 mL, 1.3 mmol, 1.3 equiv) and cinnamyl acetate (0.17 mL, 1 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in EtOAc and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 3:7 to 2:8) to afford the product as a white solid (55 mg, 16%, de=97%).
To a solution of cinnamylphosphinic acid (9.11 g, 50 mmol, 1 equiv) in toluene (100 mL) was added L-menthol (7.81 g, 50 mmol, 1 equiv). The reaction mixture was then stirred at reflux for 24 h under N 2 and in a flask equipped with a Dean-stark trap. After cooling down the reaction to rt, paraformaldehyde (1.5 g, 50 mmol, 1 equiv) was added and the reaction mixture was stirred at reflux for 24 h under N 2 . The solvent was then removed under vacuum and the crude obtained was recrystallized at rt in a mixture ethyl acetate/diethyl ether (30 mL:150 mL) to afford the product as a white solid (5.6 g, 32%, de>99%). Mp=145-146° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=48.8 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.19-7.39 (m, 5H), 6.55 (dd, J=4.7 and 15.8 Hz, 1H), 6.12-6.27 (m, 1H), 4.20-4.34 (m, 1H), 3.87 (s, 2H), 3.64 (s, 1H), 2.85 (dd, J=7.6 and 17.6 Hz, 2H), 2.06-2.22 (m, 2H), 1.60-1.71 (m, 2H), 1.28-1.54 (m, 2H), 1.15 (q, J=11.7 Hz, 1H), 0.74-1.07 (m, 2H), 0.91 (d, J=6.4 Hz, 3H), 0.86 (d, J=6.8 Hz, 3H), 0.77 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=136.8 (d, J PCCCC =3.3 Hz), 135.0 (d, J PCC =12.2 Hz), 128.5 (2C), 127.5, 126.2 (d, J PCCCCC =1.7 Hz, 2C), 118.4 (d, J PCCC =10.5 Hz), 76.7 (d, J POC =8.3 Hz), 59.5 (d, J PC =106 Hz), 48.6 (d, J POCC =5.6 Hz), 43.5, 34.0, 31.6 (d, J PC =87.3 Hz), 31.5, 25.5, 22.7, 22.1, 21.0, 15.5; HRMS (EI+) m/z calcd for C 20 H 31 O 3 P ([M] + ) 350.2011. found 350.2012; [α] D =−51.60°
(R p )-Menthyl cinnamyl-H-phosphinate 16
To a solution of N-chlorosuccinimide (200 mg, 1.5 mmol, 3 equiv) in dichloromethane (20 mL) at −78° C. and under N 2 was added dropwise a solution of dimethyl sulfide (0.11 mL, 1.5 mmol, 3 equiv) in dichloromethane (3 mL). After 10 minutes at −78° C., a solution of 15 (175 mg, 0.5 mmol, 1 equiv) in dichloromethane (3 mL) was added over 20 minutes. After 1 h at −78° C., triethylamine (0.35 mL, 2.5 mmol, 5 equiv) was added over 15 minutes and the reaction was stirred for 30 minutes at −78° C. After warming up to rt, water was added and the two layers were separated. The aqueous layer was then washed with dichloromethane (×2). The combined organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 9:1 to 7:3) to afford the product as a colorless oil (132 mg, 82%, de>99%). 31 P NMR (121.47 MHz, CDCl 3 ): □=30.9 (dm, J=539 Hz); 1 H NMR (300 MHz, CDCl 3 ): □=7.20-7.41 (m, 5H), 7.17 (d, J=539 Hz, 1H), 6.56 (dd, J=5.9 and 15.8 Hz, 1H), 6.05-6.20 (m, 1H), 4.37-4.63 (m, 1H), 2.80 (dd, J=7.6 and 18.5 Hz, 2H), 2.06-2.24 (m, 2H), 1.62-1.73 (m, 2H), 1.34-1.55 (m, 2H), 1.15 (q, J=11.4 Hz, 1H), 0.75-1.12 (m, 2H), 0.92 (d, J=6.5 Hz, 3H), 0.91 (d, J=7.0 Hz, 3H), 0.82 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=136.8 (d, J PCCCC =3.3 Hz), 135.8 (d, J PCC =14.4 Hz), 128.6 (d, J=1.1 Hz, 2C), 127.8, 126.2 (d, J PCCCCC =2.3 Hz, 2C), 117.0 (d, J PCCC =10.0 Hz), 77.3 (d, J POC =7.8 Hz), 48.4 (d, J POCC =6.1 Hz), 41.8, 34.3 (d, J PC =91.8 Hz), 34.0, 31.4, 25.7, 23.1, 21.9, 20.8, 15.8; HRMS (EI+) m/z calcd for C 19 H 29 O 2 P ([M] + ) 320.1905. found 320.1907; [α] D =−89.75°
(R p )-Menthyl(acetylmethyl)-H-phosphinate 17
To a solution of 1 (234 mg, 1 mmol, 1 equiv) in dichloromethane (3 mL) at 0° C. under N 2 was added triethylamine (0.17 mL, 1.2 mmol, 1.2 equiv) and acetic anhydride (0.10 mL, 1.1 mmol, 1.1 equiv).
The ice-bath was removed and the reaction mixture was stirred for 16 h at rt. The solvent was removed under vacuum and the residue obtained was solubilized in ethyl acetate. The organic layer was washed with NaHCO 3 and brine, dried over MgSO 4 , filtered and concentrated under vacuum to afford the product as a white solid (272 mg, 98%, de=95%). 31 P NMR (121.47 MHz, CDCl 3 ): □=26.8 (dm, J=567 Hz); 1 H NMR (300 MHz, CDCl 3 ): □=7.32 (d, J=567 Hz, 1H), 4.28-4.37 (m, 2H), 4.09-4.24 (m, 1H), 2.18-2.27 (m, 1H), 2.14 (s, 3H), 1.96-2.12 (m, 1H), 1.62-1.74 (m, 2H), 1.36-1.54 (m, 2H), 1.28 (q, J=11.4 Hz, 1H), 0.76-1.11 (m, 2H), 0.93 (d, J=7.0 Hz, 6H), 0.80 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=170.0 (d, J PCOC =6.0 Hz), 79.6 (d, J POC =7.8 Hz), 60.0 (d, J PC =113 Hz), 48.3 (d, J POCC =6.1 Hz), 43.2, 33.6, 31.4, 25.4, 22.7, 21.7, 20.7, 20.1, 15.6
(R p )-Menthyl(acetylmethyl)octylphosphinate 18
In a round bottom flask was introduced 17 (280 mg, 1 mmol, 1 equiv) 1-octene (0.39 mL, 2.5 mmol, 2.5 equiv) and Mn(OAc) 2 (9 mg, 0.05 mmol, 5 mol %). The reaction mixture was stirred for 16 h at 100° C. under air. Ethyl acetate and an aqueous solution of Na 2 S 2 O 4 at 0.5M were added and the two layers were separated. The organic layer was washed with brine, dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 8:2 to 7:3) to afford the product as white solid (218 mg, 57%, de=88%). Mp=57-59° C.; [α] D =−34.59°
Recycling of the Left Over of the Mixture of (Rp) and (Sp) of 1
(S p )-Menthyl(hydroxymethyl)phenylphosphinate 5
In a round bottom flask was introduced 1 (11.7 g, 50 mmol, 1 equiv, mixture of the two diastereoisomers 50:50), Pd(OAc) 2 (225 mg, 1 mmol, 2.0 mol %), xantphos (637 mg, 1.1 mmol, 2.2 mol %), a mixture of DMF and 1,2-dimethoxyethane (225 mL:25 mL), DIPEA (11.3 mL, 65 mmol, 1.3 equiv) and bromobenzene (5.26 mL, 50 mmol, 1 equiv). The reaction mixture was stirred under a flow of N 2 for 10 minutes and then heated at 115° C. for 24 hours before cooling to rt. The solvent was then removed under vacuum and the resulting residue was dissolved in EtOAc and washed with a saturated aqueous solution of NaHCO 3 and brine. The organic layer was dried over MgSO 4 , filtered and concentrated under vacuum. The crude obtained was purified by column chromatography (hexane/ethyl acetate 5:5 to 3:7) to give a mixture of the two diastereoisomers (1:1). The residue was recrystallized using diethyl ether (100 mL) at rt to afford the product as a white solid (3.7 g, 24%, de=97%). Mp=103-105° C.; 31 P NMR (121.47 MHz, CDCl 3 ): □=37.4 (s); 1 H NMR (300 MHz, CDCl 3 ): □=7.80-7.91 (m, 2H), 7.45-7.62 (m, 3H), 4.09-4.21 (m, 1H), 4.02-4.08 (m, 2H), 2.77-2.87 (m, 1H), 2.29-2.39 (m, 1H), 1.90-2.05 (m, 1H), 1.58-1.69 (m, 3H), 1.22-1.50 (m, 2H), 0.93 (d, J=6.2 Hz, 3H), 0.85 (d, J=7.0 Hz, 3H), 0.76-1.02 (m, 2H), 0.47 (d, J=7.0 Hz, 3H); 13 C NMR (75.46 MHz, CDCl 3 ): □□=132.3 (d, J PCCCC =2.7 Hz), 131.8 (d, J PCCC =9.9 Hz, 2C), 129.4 (d, J PC =124 Hz), 128.4 (d, J PCC =12.1 Hz, 2C), 77.4 (d, J POC =8.3 Hz), 60.4 (d, J PC =115 Hz), 48.6 (d, J POCC =6.0 Hz), 43.6, 34.0, 31.5, 25.4, 22.6, 22.0, 21.0, 15.2; HRMS (EI+) m/z calcd for C 17 H 27 O 3 P ([M+H] + ) 311.1776. found 311.1773; [α] D =−44.58°
The process of the invention for the synthesis of asymmetric non-racemic P-chiral compounds is simple and inexpensive as compared to the known prior art processes. For example, with respect to the Mislow/Han process, the advantages are obvious:
In summary, an invention has been provided that offers several advantages. The present invention easily handles the synthesis of either (R P )- and (S P )-PhP(O)(OMen)H without tedious crystallization at inconvenient temperatures, does not use PhPCl2, does not use (+)-menthol, and can be easily applied to numerous other cases (different from a phenyl substituent). Applicants have prepared two versatile and inexpensive P-chiral building blocks 2 and 3. These are obtained in multigram quantities through simple and practical crystallization conditions, not relying on any chlorophosphine intermediate. The synthetic flexibility is illustrated with the preparation of both (R P )-1 and (S P )-1 from (−)-menthol. The presence of the hydroxymethyl group not only eases the crystallization process, but also offers the possibility to maintain the methylene carbon in other P-chiral derivatives, if desired. Compound 2 represents a novel chiral version of hypophosphorous esters, from which virtually any organophosphorus compound can be synthesized. The presently disclosed methodology represents a leap forward toward the general synthesis of P-chiral compounds.
While the invention has been shown in several of its forms, it is not thus limited but is susceptible to various changes and modifications without departing from the spirit thereof.
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Shown is the preparation and subsequent elaboration of P-chiral compounds that can be used as a building block for many P-chiral ligands used, for example, in asymmetric catalytic reactions. Specifically, a synthesis is shown for RP(O)(OR*)CH 2 OH, with R=H, Ph, aryl, alkyl, and R*=menthol (and other chiral alcohol-derived moieties), especially HP(O)(OMen)CH 2 OH (Men=L-menthol). This versatile building block is easily synthesized via reaction of inexpensive starting materials, H 3 PO 2 , menthol as the chiral auxiliary, and paraformaldehyde.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention generally relates to a current programming apparatus, a matrix type display apparatus, a current programming method, and a drive method of a matrix type display apparatus, and more particularly to ones suitably used for an active matrix type display apparatus using current based driven display elements.
[0003] 2. Description of Related Art
[0004] In an active matrix type display apparatus using electroluminescent elements, a current writing type circuit writing a drive current of a light emitting device into the drive circuit of each pixel to make the drive circuit store the drive current has been used. In the present specification, such an operation of writing a drive current into each pixel of a matrix type display apparatus to make the drive circuit store the drive current is called as current programming, and the circuit for the current programming is called a current programming circuit.
[0005] In FIG. 18 of United States Patent Published Application No. 2002/0195964, a current programming circuit holding a current flowing in a data line as a gate-source voltage of a transistor is disclosed. Moreover, in the document, it is mentioned that gradation displays of black and low luminance levels can be improved by flowing the current into the direction of cancelling a writing current at the time of writing data into the current programming circuit.
[0006] When a conventional current writing type pixel circuit is used, there is a case where an operation of writing an image data current cannot be stably performed in each pixel circuit. The details of the case are described in the following, but the cause of the case is the dispersion of the threshold value of the drive transistor of each pixel.
SUMMARY OF THE INVENTION
[0007] It is an object of the present invention to provide a current programming apparatus, an active matrix type display apparatus, and a current programming method of these apparatus, all making it possible to perform the writing operation of the image data current mentioned above stably.
[0008] A current programming apparatus of the present invention is a current programming apparatus including:
[0009] a current source;
[0010] a plurality of first circuits commonly connected with a data line, each receiving supply of a data current through the data line;
[0011] a second circuit having a terminal connected to the current source; and
[0012] a switch electrically connecting or breaking the terminal of the second circuit with or from the data line, wherein
[0013] the current source generates a predetermined current and supplies the generated current to the second circuit through the terminal while the switch is off, whereby a value of the predetermined current is written in the second circuit; and
[0014] the current source generates a current based on data, and the second circuit generates a current based on the written value of the predetermined current, and a difference current between the current generated by the current source and the current generated by the second circuit is supplied to one of the first circuits through the data line while the switch is on, whereby a value of the difference current is written in the first circuit as a value of the data currents.
[0015] A matrix type display apparatus of the present invention is a matrix type display apparatus including:
[0016] a current source;
[0017] a plurality of display elements arranged in a matrix to be current based driven;
[0018] a plurality of pixel circuits each provided to each of the display elements, the pixel circuits commonly connected in column directions with data lines to receive supply of data currents through the data lines;
[0019] predetermined current setting circuits having a terminal connected to the current source; and
[0020] switches each electrically connecting or breaking the terminal with or from each of the data lines, wherein
[0021] the current source generates predetermined currents to supply the generated currents to the predetermined current setting circuits through the terminal while the switches are off, whereby a value of the predetermined currents are written in the predetermined current setting circuits; and
[0022] the current source generates a current based on data, and one of the predetermined current setting circuits generates a current based on the written values of the written predetermined currents, and difference currents of the currents generated by the current source and the currents generated by the predetermined current setting circuits are provided to the pixel circuits, whereby values of the difference currents are written into the pixel circuits as values of the currents based on the data.
[0023] A current programming method of the present invention is a current programming method including:
[0024] a first step of supplying a data current to each of a plurality of first circuits connected to a data line commonly through the data line to write a value of the data current into the first circuits; and
[0025] a second step of supplying a predetermined current to a second circuit to write a value of the predetermined current into the second circuit, wherein
[0026] the second step includes a step of breaking the second circuit from the data line electrically and a step of making a current source generate a predetermined current to supply the generated current to the second circuit, and
[0027] the first step includes a step of connecting the second circuit with the data line electrically, a step of making the current source generate a current based on data, a step of making the second circuit generate a current based on the value of the predetermined current written at the second step, and a step of supplying a difference current of the current generated by the current source and the current generated by the second circuit to one of the first circuits through the data line.
[0028] A drive apparatus for driving electro-optic elements of the present invention includes:
[0029] a matrix circuit unit ( 1 ) in which circuits ( 110 , 120 ) for generating drive currents to be supplied to the electro-optic elements (EL) are arranged in a matrix;
[0030] a current source ( 4 ) for supplying a writing current (Idata 1 ) to each of the circuits through one of a plurality of data lines;
[0031] a current setting circuit ( 130 ) for flowing a compensation current (Iz) in a direction of cancelling the writing current in each of the data lines, the current setting circuit provided to each of the data lines; and
[0032] switches connecting or breaking the current setting circuits with or from the data lines corresponding to the current setting circuits electrically, wherein
[0033] currents for generating the compensation currents (currents for setting the compensation currents) are supplied from the current source to the current setting circuits in a state in which the current setting circuits and the data lines corresponding to the current setting circuits are electrically broken.
[0034] Moreover, an active matrix display apparatus of the present invention includes:
[0035] a pixel circuit unit ( 1 ) in which electro-optic elements (EL) luminance of which changes according to flowing currents and pixel circuits ( 110 , 120 ) for generating drive currents to be supplied to the electro-optic elements are arranged in a matrix;
[0036] a current source for supplying a writing current (Idata 1 ) to each of the pixel circuits through a plurality of data lines;
[0037] a current setting circuit ( 130 ) provided to each of said data lines for flowing a compensation current in each data line into a direction of cancelling the writing current; and
[0038] a switch (M 5 ) connecting or breaking the current setting circuit with or from a data line corresponding to the current setting circuit electrically, wherein
[0039] a current for generating the compensation current (a current for setting the compensation current) is supplied from the current source to the current source setting circuit in a state in which the current setting circuit and the data line corresponding to the current setting circuit is broken by the switch.
[0040] It is preferable that the current source setting circuit includes a holding capacitor (C 1 ) holding a voltage obtained by converting the current supplied from the current source, and a transistor (M 1 ) for supplying a current according to the voltage held by the holding capacitor to the data line as the compensation current.
[0041] In the present invention, a current (Idata 2 ) having a magnitude obtained by subtracting the compensation current (Iz) from the writing current (Idata 1 ) supplied from the current source is supplied to the pixel circuits.
[0042] According to the present invention, the influences of the parasitic capacitance of a data line can be suppressed, and the writing operation of current can be stabilized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 is a diagram showing an example of the configuration of pixel circuits and a zero current setting circuit according to a first embodiment of the present invention;
[0044] FIG. 2 is a timing chart for illustrating the operation of the pixel circuits and the zero current setting circuit according to the first embodiment of the present invention;
[0045] FIG. 3 is a configuration diagram showing the configuration of an active matrix field emission display apparatus according to the present invention;
[0046] FIG. 4 is a diagram showing the configurations of pixel circuits and a zero current setting circuit of a comparison example; and
[0047] FIG. 5 is a diagram showing an example of the configuration of pixel circuits and a zero current setting circuit according to a second embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0048] In the following, the preferred embodiments of the present invention are described in detail with reference to the attached drawings.
First Embodiment
[0049] FIG. 3 is a configuration diagram showing the configuration of an active matrix field emission display apparatus according to the present invention.
[0050] In FIG. 3 , a reference numeral 1 denotes a pixel circuit unit composed of pixel circuits arranged in a matrix. In the pixel circuit unit 1 , electroluminescent elements and circuits driving the electroluminescent elements are arranged in a matrix, and the pixel circuit unit 1 includes scanning signal lines connecting them in row directions and data lines connecting them in column directions.
[0051] A reference numeral 2 denotes data line switches performing the separation and the connection of the data lines. A reference numeral 3 denotes a zero current setting circuit provided to each pixel circuit column into which a current is written based on a zero setting current (a reference current). A reference numeral 4 denotes column current control circuits supplying line-sequential data line current signals Idata and zero setting currents to the data lines connected with pixel circuit groups arranged in the column directions. A reference numeral 5 denotes a column scanning circuit connected to the column current control circuits 4 for supplying the line-sequential data line current signals Idata to the data lines.
[0052] The column current control circuits 4 are variable current sources. The column current control circuits 4 generate currents based on data, and supply to the generated currents to the plurality of pixel circuits in the column directions, which are connected to the column current control circuits 4 with the data lines. The column current control circuits further generate zero setting currents independent of data, and supply the generated zero setting currents to the zero current setting circuits 3 .
[0053] The column scanning circuit 5 samples three image signals of R, G and B input into the column current control circuits 4 to each column.
[0054] A reference numeral 6 denotes a row scanning circuit connected to the pixel circuits arranged in the row directions, and sequentially outputs line scanning signals P 1 m and P 2 m to each line (a letter m denotes an integer of (1-M) on the supposition that there are M row scanning signal lines). Because each pixel circuit includes two row selection signal lines in the examples of the pixel circuits shown in the following embodiments, it is supposed that two row scanning signals also exist here. However, there can be cases where each pixel circuit includes one, three or the like of row selection lines in addition to the case of two row selection lines.
[0055] FIG. 1 shows a current programming circuit according to a first embodiment of the present invention. The current programming circuit 100 of the present embodiment includes a first row pixel circuit 110 , a second row pixel circuit 120 (although pixel circuits are continuously arranged in a third row, a fourth row and so forth after the second row pixel circuit 120 , the illustration of them is omitted in FIG. 1 ), and a zero current setting circuit 130 . Although only a part of the current programming circuit 100 connected to one data line is shown in FIG. 1 , it is needless to stay that the matrix display apparatus of FIG. 3 includes a plurality of data lines and the same current programming circuit is provided to each data line.
[0056] FIG. 2 is a timing chart for illustrating the operation of the circuit of FIG. 1 . The ordinate axes of FIG. 2 indicate the voltage values of each signal, and the abscissa axes of FIG. 2 indicate times. The signal input into each of signal lines L, P 1 z , P 2 z , . . . of FIG. 1 is denoted by the same marks as those in FIG. 1 .
[0057] In the present specification, a data line 150 indicates only a part to which the pixel circuits 110 , 120 , . . . are commonly connected, and the data line 150 is distinguished from wiring 160 on a current source side from a switch M 5 .
[0058] A reference mark Idata 1 in FIG. 2 denotes a current flowing through the wiring 160 connected to the column current control circuits 4 , not shown in FIG. 1 , on the left side from a supply port of a current Iz generated by the zero current setting circuit 130 . The reference mark Iz denotes the output current of the zero current setting circuit 130 , and a reference mark Idata 2 denotes a current flowing through a part nearest to the switch M 5 of the data line.
[0059] FIG. 4 is a diagram showing the configuration of a current programming circuit as a comparison example.
[0060] Although the configurations of the pixel circuits 110 and 120 and the zero current setting circuit 130 of the comparison example shown in FIG. 4 are the same as those shown in FIG. 1 , the configuration of the comparison example does not include the data line switch M 5 between the zero current setting circuit 130 and the first row pixel circuit 110 . The configuration of the comparison example differs from that shown in FIG. 1 in that the data line 150 portion, to which each of the pixel circuits 110 , 120 , . . . are connected, is continuous to the wiring 160 portion of the zero current setting circuit 130 .
[0061] First, for making it easy to understand, the configuration and the operation of the comparison example, which is not provided with the data line switch M 5 , is described using FIGS. 2 and 4 .
[0062] Now, the operation of the first row pixel circuit connected to a certain data line is considered. When the row scanning signal P 11 becomes a high level in FIG. 2 , an nMOS transistor M 7 used as a switch for a first program (row selection) is turned on, and a pMOS transistor M 9 as a switch for light emission selection turns off. Moreover, when the row scanning signal P 21 becomes the high level, an nMOS transistor M 6 used as a switch for a second program turns on.
[0063] As a result, the image data current Idata 2 flowing through the data line is led to the gate and the drain of a pMOS transistor M 8 used as a drive transistor, and charges a capacity C 2 connected between the gate and the source.
[0064] The voltage of the capacity C 2 connected to the gate of a pMOS transistor M 8 used as a switch for drive is set as a gate-source voltage sufficient for the current driving the electroluminescent element (field luminescent element) EL based on the image data current flowing through the data line to flow through the pMOS transistor M 8 . Next, when the row scanning signal P 21 becomes a low level, the nMOS transistor M 6 used as the switch for the second program turns off, and the voltage of the capacity C 2 is held. The period until now is a first row current setting period (drive current programming period).
[0065] After that, when the row scanning signal P 11 becomes the low level, the nMOS transistor M 7 used as the switch for the first program (row selection) turns off, and the pMOS transistor M 9 used as the switch for the light emission selection turns on. The supply of a drive current to the electroluminescent element EL is controlled by the gate potential of the transistor M 8 for drive, and the current flowing through the electroluminescent element EL is controlled. A period during which the electroluminescent element EL is emitting light (is not emitting light in case of a black display) is a light emitting period. Moreover, when the first row current setting period ends, a second row current setting period begins, and a drive current is sequentially written in the current setting period of each row based on an image data signal.
[0066] By the way, although it is preferable that the current of a line-sequential data line current signal is zero in the minimum luminance (black) display, it is actually difficult to make the current zero owing to the circuit configuration. Even if the image data input into one of the column current control circuits 4 of FIG. 3 is made to a black display signal, that is even if the signal voltage is made to the black display voltage level, the output current of the column current control circuit 4 does not become zero completely, and a little current (called as a zero current) flows through the connected wiring 160 . If the current of the line-sequential data line current signal does not become zero, it is impossible to make the drive current of the electroluminescent element EL zero, and the setting of the black display cannot be performed sufficiently. Moreover, because the zero current is different at each data line owing to the dispersion of the column current control circuits 4 , it is difficult to perform the subtraction of the zero current uniformly.
[0067] The inventors of the present application have paid attention to the problem previously, and proposed a method of providing the zero current setting circuits for performing the setting of the black display correctly (Japanese Patent Application Laid-Open No. 2004-312015). This patent application proposed a current programming circuit 100 including a zero setting circuit 130 as shown in FIG. 4 . A zero current is programmed in the zero current setting circuit 130 in a predetermined period (the period is called as a zero current setting period) in a vertical blanking period. In a current programming period of the pixel circuits 110 , 120 , etc., a current is supplied from the zero current setting circuit into the data line in the direction of cancelling the current from column current circuits.
[0068] During the zero current setting period, the image data inputted into one of the column current control circuits 4 of FIG. 3 is made to a black display signal. That is, the signal voltage is made to be the black display voltage level.
[0069] As stated above, the output current of the column current control circuit 4 does not completely become zero, but a zero current flows through the connected wiring 160 . Here, the control signals P 1 z and P 2 z are made to be the high level to turn nMOS transistors M 3 and M 2 on, respectively, the zero current flow into the zero current setting circuit 130 and the voltage across a capacity C 1 connected to the gate of a pMOS transistor M 1 is set as a level correlated to the zero current. When the control signals P 1 z and P 2 z become the low level, the voltage of the capacity C 1 is held.
[0070] In the scanning period, a current Iz which is determined by the voltage across the capacity C 1 flows through the pMOS transistors M 1 and M 4 . The current flows into the data line, where a data current Idata 1 has been supplied from column current circuit. Since the current Iz on the data line cancels a part of the data current Idata 1 , current Idata 2 to be supplied to pixel circuits satisfies the formula of Idata 2 =Idata 1 −Iz.
[0071] Consequently, as the zero current is canceled, it becomes possible to set the current to flow in the pixel circuits completely zero at the time of a black display. Thus, by providing the zero current setting circuits, it becomes possible to set the true black displays.
[0072] However, the inventors of the present application have found that, even if the setting of the current is tried to be performed by the zero current setting circuits, it is difficult to stably perform the zero current setting owing to the influences of parasitic capacitance Cx of the data lines. Hereafter, the problem is described.
[0073] In FIG. 1 , the parasitic capacitance Cx of a data line is shown. The capacity Cx results from wiring capacity, the capacity between the gate and the source of the transistor of the pixel circuits connected to a data line, and the like. Because the zero setting current is a minute current, it is not always easy to write a current based on the zero setting current during a limited vertical blanking period even if the current is tried to be set with the zero current setting circuit when the influences of the parasitic capacitance of the data line are exerted.
[0074] For example, it is supposed that pixel circuits from the first to the nth rows are connected to a certain data line, and that the voltage across the capacity C 2 of the nth pixel circuit is set to be high for setting the nth pixel circuit to be high luminance. Then, the potential of the data line, or the voltage across the parasitic capacitance Cx, becomes low. In the zero current setting period in the next frame, it becomes difficult to fully raise the potential of the capacity C 1 of the zero current setting circuit. This is because the zero current setting is the minute current writing operation and the zero current setting period is finite.
[0075] Furthermore, the potential of the data line is highin the case where the nth pixel has been black display and the potential of the data line is lowin the case where the nth pixel has been high luminance. A difference is caused between the potentials of the data line in these two cases, which makes performing the zero current setting unstable.
[0076] In order to solve the problem, as shown in FIG. 1 , the inventors of the present application have devised to provide the switch M 5 of an nMOS transistor between the data line 150 and the current output terminal of the zero current setting circuit 130 , and to turn the switch M 5 on and off with the control signal on the signal line L. Then, the inventors have devised to turn off the switch M 5 during the zero current setting period for separating the data line and the pixel circuits 110 , 120 , . . . from the zero current setting circuit 130 . Thereby, the zero current is separated from the parasitic capacity of the data line during the zero current setting period to make it possible to write the zero current into the zero current setting circuit correctly. Moreover, because the zero current is not influenced by the parasitic capacitance, the writing of the zero setting current can be performed more quickly.
[0077] Although the capacity C 1 may be individually formed as a capacity element, the capacity C 1 also may not be formed as an element, but the parasitic capacitance formed between the gate and the source (the capacity of the overlapping of the gate electrode and the source region, or the like) may be used as capacity C 1 .
Second Embodiment
[0078] FIG. 5 is a diagram showing an example of the configuration of the current programming circuit according to a second embodiment of the present invention. In the present embodiment, the configuration of the zero current setting circuit 130 is more simplified by omitting the nMOS transistor M 3 and the pMOS transistor M 4 , and by connecting the PMOS transistor M 1 to the data line directly. In such a configuration, also the effect similar to that of the first embodiment also can be acquired.
[0079] Although the active matrix type display apparatus using the current based driven display elements is picked up to be described as an example of using the current programming apparatus according to the present invention above, the current programming apparatus according to the present invention can be applied to a use, as long as the use is that using a current setting circuit holding a current to be flown into a data line as the gate-source voltage of a transistor. The use of the current programming apparatus according to the present invention is not limited to the active matrix type display apparatus using the current based driven display elements such as electroluminescent elements and electron emitting elements, but the current programming apparatus according to the present invention is used as a circuit for current programming such as an analog memory. In case of using the current programming apparatus as the analog memory, the current programming apparatus adopts a configuration in which the electroluminescent element EL is removed from each of the pixel circuits, and analog value is taken out from the circuit as a current value. Moreover, the application of the present invention is not restricted to the matrix-like display apparatus, but the present application can be applied also to a line-like display apparatus.
[0080] The present invention is used for an active matrix type display apparatus of a current based driven type light emitting devices such as the electroluminescent elements (EL elements) and other electro-optic elements, and also used for an analog memory.
[0081] This application claims priority from Japanese Patent Application No. 2004-342129 filed Nov. 26, 2004, which is hereby incorporated by reference herein.
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A current programming apparatus includes a current source; a plurality of first circuits to which data currents are supplied through a data line, the first circuits commonly connected with the data line; a second circuit having a terminal connected to the current source; a switch connecting or breaking the second circuit with or from the data line, wherein the current source generates a predetermined current to supply the generated current to the second circuit through the terminal while the switch is off, whereby the value of the predetermined current is written in the second circuit, and wherein the current source generates a current based on data, and the second circuit generates a current based on the written value of the predetermined current, and a difference current between the current generated by the current source and the current generated by second circuit is supplied to the first circuits through the data line while the switch is on, whereby the value of the current is written in the first circuits as the value of the data current. The influence of parasitic capacitance of the data line can be suppressed to stabilize the writing operation of the current.
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BACKGROUND OF THE INVENTION
The present invention relates to the magnetic resonance arts. It finds particular application in conjunction with gradient coils for a magnetic resonance imaging apparatus and will be described with particular reference thereto. However, it is to be appreciated that the present invention will also find application in conjunction with localized magnetic resonance spectroscopy systems and other applications which utilize gradient magnetic fields.
In magnetic resonance imaging, a spatially uniform and temporally constant magnetic field is created through an examination region in which a subject to be examined is disposed. A series of radio frequency pulses and magnetic field gradients are applied to the examination region. Gradient fields are conventionally applied as a series of gradient pulses with pre-selected profiles. The radio frequency pulses excite magnetic resonance and the gradient field pulses phase and frequency encode the induced resonance. In this manner, phase and frequency encoded magnetic resonance signals are generated.
Many MRI techniques are highly sensitive to magnetic field homogeneity. However, the geometric shape and/or magnetic susceptibility of a subject being scanned, built-in main magnet tolerances, environmental and/or site effects, and the like contribute to the main magnetic field's inhomogeneity and/or non-uniformity. In turn, this leads to imaging problems.
Methods for controlling the homogeneity of the main magnetic field include both passive and active shimming techniques. The passive technique includes arranging shim steel on the inside diameter of the superconductive coil assembly to minimize static magnetic field inhomogeneities based upon NMR field plot measurements. The active shimming technique generally employs multiple orthogonal shim coils and/or gradient coil offsets. An electrical current is applied to the shim coils and/or gradient coil offsets in order to cancel inhomogeneities in the main magnetic fields.
Gradient magnetic field pulses are typically applied to select and encode the magnetic resonance with spatial position. In some embodiments, the magnetic field gradients are applied to select a slice or slab to be imaged. Ideally, the phase or frequency encoding uniquely identifies spatial location. In bore-type magnets, linear magnetic field gradients are commonly produced by cylindrical gradient field coils wound on and around a cylindrical former. Discrete coils are wound in a bunched or distributed fashion on a similar or larger diameter cylindrical tube, commonly 30-65 centimeters in diameter or larger.
Historically, gradient coil designs were developed in a “forward approach,” whereby a set of initial coil positions were defined and the fields, energy, and inductance calculated. If these quantities were not within the particular design criteria, the coil positions were shifted (statistically or otherwise) and the results re-evaluated. This iterative procedure continued until a suitable design was obtained.
Recently, gradient coils are designed using the “inverse approach,” whereby gradient fields are forced to match predetermined values at specified spatial locations inside the imaging volume. Then, a continuous current density is generated which is capable of producing such fields. This approach is adequate for designing non-shielded or actively shielded gradient coil sets.
Conventional shielded gradient coil sets have been designed based on the assumption that no correction to the magnitude of the higher order gradient magnetic field terms was to be made. Therefore, conventional gradient coil designs force field contributions from terms of higher spatial order to be negligible within the imaging volume. This is usually accomplished by setting specific moment coefficients to be zero. Although such designs enhance the uniformity of the gradient magnetic field with a subsequent improvement in the distortion characteristics of the final image, they are characterized by high inductance and resistance values, which result in a significant reduction in the gradient coil's peak magnetic field, rise time, slew rate, increase in heating characteristics, and reduction in duty cycles.
Conversely, design requirements call for fast switching, high duty cycles, and high peak gradient coils force the introduction of higher order, non-zero terms in the gradient magnetic field. These higher order terms distort image quality by introducing spatial misregistration of spins. Passive distortion correction algorithms have been implemented for the correction of such image distortions. In particular, two distortion correction methods have been employed.
One method includes the use of specially designed RF pulses with a field intensity variance to account for the distortion characteristics of the gradient magnetic field. The pulses are applied prior to pulsing the gradient magnetic field during the MR sequence. One disadvantage of this technique is that it is limited to a two-dimensional MR sequence with limited oblique capabilities. In addition, a signal intensity correction algorithm is necessary during the postprocessing of the MR image.
A second prior art method of gradient distortion correction employs a postprocessing correction algorithm that predicts the image distortions (pixel or voxel displacements) generated by the higher order terms of the gradient magnetic field and attempts to invert this action. However this technique suffers from several disadvantages. First, this technique is ineffective in eliminating aliasing when the gradient coil's rollover point is inside the field of view. Second, a signal intensity correction algorithm must be applied to the undistorted image. Also, the technique is ineffective for gradient field non-uniformities exceeding 35% of the gradient field's ideal value over any imaging volume.
Therefore, a need exists for a gradient coil set with correctable higher order terms. The present invention contemplates a new and improved gradient coil set which overcomes the above-referenced problems and others.
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention, a magnetic resonance apparatus includes a main magnet which generates a main magnetic field through and surrounding an examination region, where the main magnetic field contains inhomogeneities. A gradient coil assembly generates gradient magnetic fields across the examination region, where the gradient magnetic fields include higher order harmonics. A multi-axis shim set is disposed adjacent the gradient coil assembly. The multi-axis shim set cancels inhomogeneities in the main magnetic field and compensates for distortions caused by the higher order harmonics of the gradient magnetic field. An RF transmitter and coil assembly excites magnetic resonance dipoles in and adjacent the examination region. An RF coil and receiver assembly receive and demodulate magnetic resonance signals from the resonating dipoles. A reconstruction processor reconstructs the demodulated magnetic resonance signals into an image representation.
In accordance with another aspect of the present invention, a method of magnetic resonance imaging includes generating a temporally constant main magnetic field through an examination region, where the main magnetic field contains inhomogeneities. Resonance is induced in selected dipoles in the examination region such that the dipoles generate magnetic resonance signals. A gradient magnetic field, having higher order harmonics which cause image distortions, is generated across the examination region to encode the magnetic resonance signals along at least one axis. Correction currents are applied to shim coils to (i) minimize the inhomogeneities in the main magnetic field and (ii) compensate for the higher order harmonics in the gradient magnetic field. The encoded magnetic resonance signals are received, demodulated, and reconstructed into an image representation free from distortions caused by the higher order harmonics of the gradient magnetic field.
In accordance with another aspect of the present invention, a temporally constant main magnetic field having inhomogeneities is generated in an examination region. Radio frequency pulses excite and manipulate resonance of selected dipoles in a subject disposed in the examination region. Gradient pulses are applied to at least one gradient coil assembly to generate gradient magnetic fields for encoding the excited resonance, where the gradient magnetic fields have inhomogeneities caused by higher order harmonics. Received and demodulated resonance signals are reconstructed into an image representation. A method of real-time correction of the main and gradient magnetic field inhomogeneities includes applying DC correction currents to a multi-axis shim set and superimposing AC correction current pulses on the DC correction currents.
One advantage of the present invention is that it eliminates aliasing effects for magnetic resonance sequences with large fields of view.
Another advantage of the present invention resides in real-time correction of distortions caused by higher orders of the gradient magnetic field.
Another advantage of the present invention is that it eliminates the need for a distortion correction algorithm.
Another advantage of the present invention is that it provides for gradient coil designs of a prescribed dimension which cover a prescribed imaging volume with reduced inductance and increased efficiency.
Another advantage of the present invention is that it reduces post-processing time for a magnetic resonance image.
Yet another advantage of the present invention resides in the elimination of artifacts from distortion characteristics of the magnetic field gradient.
Another advantage of the present invention is that it reduces overall time for a magnetic resonance study.
Still another advantage of the present invention is that increases the effective imaging volume.
Still further advantages and benefits of the present invention will become apparent to those of ordinary skill in the art upon reading and understanding the following detailed description of the preferred embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may take form in various components and arrangements of components, and in various steps and arrangements of steps. The drawings are only for purposes of illustrating preferred embodiments and are not to be construed as limiting the invention.
FIG. 1 is a diagrammatic illustration of a magnetic resonance imaging system in accordance with the present invention;
FIG. 2 is a diagrammatic illustration of a cross-section of the magnetic bore in accordance with the present invention;
FIG. 3 is a flow chart for designing a shielded gradient coil assembly having non-zero higher order terms of the gradient magnetic field in accordance with the present invention;
FIG. 4 is a diagrammatic illustration of one quadrant of an exemplary primary x-gradient coil in accordance with the present invention;
FIG. 5 is a diagrammatic illustration of one quadrant of an exemplary shielding x-gradient coil in accordance with the present invention;
FIG. 6 is a distortion grid for a transverse slice through the z-0.0 plane for an exemplary gradient coil set with no rollover point in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIG. 1, a main magnetic field control 10 controls superconducting or resistive magnets 12 such that a substantially uniform, temporally constant magnetic field is created along a z-axis through an examination region 14 . Although a bore-type magnet is illustrated in FIG. 1, it is to be appreciated that the present invention is equally applicable to open magnetic systems with vertically directed fields, or any other magnetic resonance imaging configuration. A couch (not illustrated) suspends a subject to be examined within the examination region 14 .
Ideally, the main magnetic field is uniform throughout the examination region 14 or imaging volume. However, in practical application, non-uniformities and/or inhomogeneities are present in the main magnetic field that are deleterious to the reconstructed images. In order to correct these inhomogeneities, a shim coil power supply 25 supplies electric current to a shim coil set 23 , which comprises a plurality of dedicated shim or correction coils. Preferably, the active shims 23 take form in 12-18 layers of coils which surround the bore. Alternately, the main magnetic field may be shimmed to correct for inhomogeneities by applying DC gradient offsets to gradient coils 22 via the gradient amplifiers 20 .
A magnetic resonance echo means applies a series of radio frequency (RF) and magnetic field gradient pulses to invert or excite magnetic spins, induce magnetic resonance, refocus magnetic resonance, manipulate magnetic resonance, spatially and otherwise encode the magnetic resonance, to saturate spins, and the like to generate magnetic resonance imaging and spectroscopy sequences. More specifically, gradient pulse amplifiers 20 apply current pulses to a gradient coil assembly 22 to create magnetic field gradients along x, y, and z axes of the examination region 14 with zero or minimal fringe fields outside of the bore. As will be described more fully below, higher harmonics of the gradient magnetic fields may cause image distortions. Such distortions are corrected in a real-time fashion by using the shim coil set.
A radio frequency transmitter 24 transmits radio frequency pulses or pulse packets to a whole-body RF coil 26 to transmit RF pulses into the examination region 14 . A typical radio frequency pulse is composed of a packet of immediately contiguous pulse segments of short duration which, taken together with each other and any applied gradients, achieve a selected magnetic resonance manipulation. The RF pulses are used to saturate, excite resonance, invert magnetization, refocus resonance, or manipulate resonance in selected portions of the examination region. For whole-body applications, the resonance signals are commonly picked up by the whole-body RF coil 26 , but may be picked up by other specialized RF coils.
For generating images of limited regions of the subject, local coils are commonly placed contiguous to the selected region. For example, an insertable head coil 30 is inserted surrounding a selected brain region at the isocenter of the bore. The insertable head coil preferably includes local gradient coils 32 which receive current pulses from the gradient amplifiers 20 to create magnetic field gradients along x, y, and z-axes in the examination region within the head coil. A local quadrature radio frequency coil 34 is used to excite magnetic resonance and receive magnetic resonance signals emanating from the patient's head. Alternatively, a receive only local radio frequency coil can be used for quadrature reception of resonance signals introduced by body coil RF transmissions. An RF screen 36 screens the RF signals from the RF head coil from inducing any currents in the gradient coils and the surrounding structures. The resultant radio frequency signals are picked up in quadrature by the whole-body RF coil 26 , the local RF coil 34 , or other specialized RF coils and demodulated by a receiver 38 , preferably a digital receiver.
A sequence control processor 40 controls the gradient pulse amplifiers 20 and the transmitter 24 to generate any of a plurality of multiple echo sequences such as echo planar imaging, echo volume imaging, gradient and spin echo imaging, fast spin echo imaging, and the like. In addition, the sequence control processor 40 controls the shim coil power supply 25 to generate a predetermined shim sequence. More particularly, the predetermined shim sequence is tailored to correct both inhomogeneities in the main magnetic field and image distortions caused by higher order harmonics of the gradient magnetic fields. For the selected echo sequence, the receiver 38 receives a plurality of data lines in rapid succession following each RF excitation pulse. An analog-to-digital converter 42 converts each data line to a digital format. The analog-to-digital converter 42 is disposed between the radio frequency receiving coil and the receiver 38 for digital receivers and is disposed downstream (as illustrated) from the receiver for analog receivers.
Ultimately, the radio frequency signals received are demodulated and reconstructed into an image representation by a reconstruction processor 50 which applies a two-dimensional Fourier transform or other appropriate reconstruction algorithm. The image is then stored in an image memory 52 . A human-readable display 54 , such as a video monitor, provides a human-readable display of the resultant image. The image may represent a planar slice through the patient, an array of parallel planar slices, a three-dimensional volume, or the like.
FIG. 2 illustrates a cross-sectional view of the bore of the magnetic resonance apparatus. In one embodiment, the shim coil assembly 23 is disposed between the main magnet 12 and the gradient coil assembly 22 , as shown. The gradient coil assembly 22 includes a dielectric former 60 having an inner radius a and an outer radius b. The gradient coil assembly includes a primary gradient coil set 22 a and a secondary or shielding coil set 22 b. The shielding coils 22 b are designed to cooperate with the primary gradient coil set 22 a to generate a magnetic field which has a substantially zero magnetic flux density outside an area defined by the outer radius of the former.
The primary and secondary gradient coil sets are each made up of primary and secondary x, y and z-gradient coils that are mounted on the former 60 . In one embodiment, the primary x, y, and z-gradient coils are mounted on the inner surface of radius a of the former, while the secondary x, y, and z-gradient shielding coils are mounted on the outer surface of radius b of the former. The primary and secondary x, y, and z-gradient coils are constructed of a conductive material, such as foil or wire, of patterns determined by the below-referenced design procedure. In one embodiment, the coils are laminated to the cylindrical outer and/or inner surfaces of the former. Alternately, the x, y, and z-gradient coils are wound into grooves in the former and potted in an epoxy. The coil windings are preferably manufactured from a relatively thin conductive sheet, such as copper. The sheet is preferably cut before lamination to the former by water jet cutting, laser cutting, etching, or the like, and then bonded to a thin insulating substrate, minimizing radial thickness.
Prior art gradient coil sets are typically designed based on the assumption that no correction is made to the magnitude of the higher order gradient magnetic field terms. In contrast, the present gradient coil assembly is designed to generate higher order, e.g. third order, fifth order, and beyond, non-zero gradient magnetic filed components. Such non-zero components aid in desired performance characteristics, such as fast switching, high duty cycles, and high peak gradients.
Invariably, the higher order harmonics of the gradient magnetic field cause image distortion by introducing spatial misregistration of spins. As is described more fully below, gradient distortion coefficients, which are caused by the non-zero higher order harmonics, are calculated. With the gradient distortion coefficients known, AC current pulses are superimposed on the shim coils concurrently with the gradient pulses on the gradient coils in order to compensate for distortions. In other words, DC currents are applied to the shim coils in order to correct inhomogeneities in the main magnetic field and AC current pulses are superimposed on the shim coils to correct for the distortions caused by the higher orders of the gradient magnetic field.
In addition, prior art gradient coils sets typically are designed such that their gradient magnetic field profile has an inherent rollover point along, but near the edge of its respective axis. At the rollover point, the first derivative of the gradient magnetic field is zero. After passing the rollover point, where the first derivative is zero, the gradient field takes on non-unique values, i.e., assumes identical values to the gradient field on both sides of the rollover point. This leads to aliasing. When portions of the subject are disposed between the rollover point and the bore, areas of the subject that are located beyond the rollover point will alias back into the image, which causes ghosting of the image. Signals from two planes near the edge that are subject to the same gradient field strength are indistinguishable and are combined. In this manner, a ghost of the material beyond the rollover point is folded back on the material inside the rollover point.
In contrast, the present gradient coil assembly has a flux density that possesses no such rollover point within the physical volume bounded by the inner former. By designing the x, y, and z-gradient coils such that the first derivative of the gradient magnetic field in and adjacent to the examination region is non-zero, i.e., there is no rollover point, the above-discussed aliasing problems are minimized. Because there is no rollover point on the graph of gradient magnetic field versus position, all data values are unique.
The theoretical development, the design procedure and the numerical results for an exemplary shielded gradient coil having non-zero higher order terms with no rollover point of the gradient magnetic field along its perspective axis and inside the physical boundaries defined by the inner surface of the gradient tube is now discussed. While the present discussion focusses on shielded gradient coils sets, it is to be appreciated that the present invention is applicable to non-shielded gradient coil sets as well. Specifically, the theoretical development, the design, and the results of a gradient coil where the z component of the magnetic field varies linearly along the transverse direction (x, y-gradient coil), as well as, the axial gradient coil (z-gradient coil) will be presented. The x-gradient coil will be presented in its entirety as a representative for the transverse coils.
The flow chart for designing such a gradient coil structure is shown in FIG. 3 . Initially, a geometric configurations of the primary gradient coil step 100 sets the primary coil configuration and a secondary shielding coil configuration step 102 sets the secondary coil configuration. Namely, radius and length for each coil set are chosen. Next, an energy, and optionally inductance, minimization step 104 optimizes the primary gradient coil set. As a result of the minimization process 104 , a first continuous current distribution generation step 106 generates the current distribution for the primary gradient coil set. The first continuous current distribution is confined to the geometric boundaries defined in step 100 . The first current distribution is selected such that it generates a magnetic gradient field across the examination region having non-zero higher order terms. In addition, the first derivative of the gradient magnetic field in and around the examination region is non-zero. Following this step, a second continuous current distribution selection step 108 generates the current distribution for the secondary, shielding coil set such that the second continuous current distribution is confined to the geometric boundaries defined in step 102 . The second continuous current distribution generates a magnetic field which, when combined with the magnetic field from the first current distribution, generates a substantially zero fringe magnetic field outside the secondary coil.
Further, in a current discretization step 110 , the continuous current distribution of the primary gradient coil set and the secondary, shielding coil set are discretized to generate the number of turns which is required for each coil within each coil set. Optionally, a verifying step 112 applies the Biot-Savart law to the discrete current pattern to verify its validity. Gradient distortion coefficients are calculated 114 for the x, y, and z gradient coils using a spherical decomposition algorithm. Preferably, the orders are normalized to the first derivative of the magnetic field. Once the gradient distortion coefficients are known, shim coil correction current pulses are calculated 116 , which will compensate for the gradient distortions.
The theoretical development of the energy optimization algorithm step 104 is discussed for both the transverse and the axial gradient coil. The development is done for a self-shielded gradient coil structure because the algorithm for optimizing a non-shielded gradient coil structure is identical to the algorithm for the self-shielded gradient coil structure. For the actively shielded gradient coil design, the total length of the primary coil is denoted as L a . The length of the shielding coil is assumed to be infinite. The radius of the primary coil is denoted as a, while the radius of the shielding coil is denoted as b.
Initially, in the design of the finite, shielded, transverse x-gradient coil, the gradient magnetic field must be antisymmetric in the x direction around the geometric center of this coil, while it is symmetric along the y and z directions. In order to generate such a field, the analytical expression of the current for the primary coil is written as:
{right arrow over (J)} a ( {right arrow over (r)} )=[ j φ a (φ, z ) â φ +j z a ( φ, z ) â z ]δ( ρ−a ) (1)
where δ(ρ−a) is the restriction that the current is confined on the cylindrical surface with radius a. The restriction to inner coil length, the confinement of the current density on the cylindrical surface, the azimuthal and axial symmetries for the j φ a and j z a and the demand that the current density obeys the continuity equation provide the Fourier series expansion for both components around the geometric center of the coil as follows: j φ a ( φ , z ) = cos ( φ ) ∑ n = 1 ∞ j φ n a cos ( k n z ) for z ≤ L a 2 ( 2 ) j z a ( φ , z ) = sin ( φ ) ∑ n = 1 ∞ - j φ n a k n a sin ( k n z ) for z ≤ L a 2 ( 3 )
In this case j φn a are the Fourier coefficients, L a represents the total length of the inner coil, and k n =(2nπ)/L a because the current can not flow off the ends of the cylinder. Furthermore, both current components are zero for ¦z¦>L a /2.
In order to minimize the fringe field of the primary coil in the area which is outside both the primary and the shielding coils, the Fourier transform of the current for the shielding coil must satisfy the following relationship: j φ b ( ± 1 , k ) = - aI 1 ′ ( ka ) bI 1 ′ ( kb ) j φ a ( ± 1 , k )
with
j φ a ( ± 1 , k ) = L a 4 ∑ n = 1 ∞ j φ n a ψ n ( k ) ( 4 ) ψ n ( k ) = [ sin ( k - k n ) L a 2 ( k - k n ) L a 2 + sin ( k + k n ) L a 2 ( k + k n ) L a 2 ] ( 5 )
In this case, the expression for the z component of the gradient magnetic field in the area inside both coils can be written as: B z = - μ 0 aL a 4 π cos ( φ ) ∑ n = 1 ∞ j φ n a ∫ 0 + ∞ kk cos ( kz ) ψ n ( k ) l 1 ( k ρ ) K 1 ′ ( ka ) [ 1 - l 1 ′ ( ka ) K 1 ′ ( kb ) l 1 ′ ( kb ) K 1 ′ ( ka ) ] ( 6 )
where I m ′, K m ′ represent the derivatives with respect to the argument of the modified Bessel functions of the first and the second kind. Furthermore the expression for the stored magnetic energy can also be written as: W = - μ 0 a 2 L a 2 16 ∑ n = 1 ∞ ∑ n ′ = 1 ∞ j φ n a j φ n ′ a ∫ 0 + ∞ k ψ n ′ ( k ) l 1 ′ ( ka ) K 1 ′ ( ka ) [ 1 - l 1 ′ ( ka ) K 1 ′ ( kb ) l 1 ′ ( kb ) K 1 ′ ( ka ) ] ( 7 )
Alternatively, W may be replaced by an arbitrary quadratic function with respect to current which will lead to different properties in the final design. For the higher order derivatives for the gradient magnetic field, considering only odd terms due to the symmetry conditions, the expressions for the odd derivative terms as derived from equation (6) are: B z 2 n + 1 ρ = ρ 0 = ∂ 2 n + 1 B z ∂ ρ 2 n + 1 ρ = ρ 0 = - μ 0 aL a 4 π cos ( φ ) ∑ n = 1 ∞ j φ n a ∫ 0 + ∞ kk cos ( kz ) ψ n ( k ) ∂ 2 n + 1 l 1 ( k ρ 0 ) ∂ ρ 2 n + 1 ρ = ρ 0
K 1 ′ ( ka ) [ 1 - l 1 ′ ( ka ) K 1 ′ ( kb ) l 1 ′ ( kb ) K 1 ′ ( ka ) ] for n = 0 , 1 , 2 , 3 , … , N ( 8 )
As a next step, the functional E is constructed in terms of W and B z (2n+1) for the derivative constraints, and the alternative F functional in terms of W and B z for the field constraints as: E ( j φ n a ) = W - ∑ j = 1 N λ j ( B z ( r → j ) 2 n + 1 - B zSC ( r → j ) 2 n + 1 ) z = z 0 , ρ = ρ 0 derivative constraints F ( j φ n a ) = W - ∑ j = 1 N λ j ( B z ( r → j ) - B zSC ( r → j ) field constraints
where λ j are the Lagrange multipliers and B zsc 2n+1 , B zsc represent the constraint values of the derivative or field constraints for the z component of the magnetic field at the specified N points. Minimizing E or F, a quadratic function of the current, with respect to the current coefficients j φn a , produces a matrix equation which j φn′ a must satisfy: ∑ n ′ 1 ∞ j φ n ′ a aL a π 2 ∫ 0 ∞ k ψ n ( k ) ψ n ′ ( k ) l 1 ( ka ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] = ∑ j1 N λ j cos ( φ j ) ∫ 0 ∞ kk cos ( kz j ) ψ n ( k ) l 1 ( k ρ j ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] field constraints ( 9 ) ∑ n ′ 1 ∞ j φ n ′ a aL a π 2 ∫ 0 ∞ k ψ n ( k ) ψ n ′ ( k ) l 1 ( ka ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] = ∑ j1 N λ j cos ( φ j ) ∫ 0 ∞ kk cos ( kz j ) ψ n ( k ) ∂ 2 n 1 l 1 ( k ρ 0 ) ∂ ρ 2 n 1 ρ ρ 0 K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] derivative constraints ( 10 )
where the evaluation of the Lagrange multipliers may be done via the constraint equations for field and derivative constraints.
By truncating the previous infinite summations at M terms and using compact notation, the previous expressions (9) and (10) are modified as: ∑ n ′ = 1 M j φ n ′ a C n ′ , n = ∑ j = 1 N λ j D jn ( 11 )
or in matrix form:
J a C=λDJ a =λDC −1 (12)
but
B z =J a D t B z =λDC −1 D t (13)
which leads to
λ=B z [DC −1 D t ] −1 J a =B z [DC −1 D t ] −1 DC −1 (14)
Inverting the previous matrix equation leads to a solution for j φn a , and hence for the current density. When the continuous current distribution for both the primary and shield coils is evaluated, the stream function technique is used to discretize the current density for both primary and shield coils. This yields an absolute integer number of turns for both coils for a given common current value per loop. Following the discretization, the magnetic gradient field and the eddy currents inside the desired imaging volume are calculated.
For the design of an exemplary shielded G x gradient coil, the radius of the cylinder for the primary coil is equal to 0.338393 m and its total length is restricted to 1.132 m. In addition, the radius of the secondary coil is equal to 0.435324 m. The constraints are shown in Table 1 for the design of this exemplary gradient coil. As shown in Table 1, the first constraint point defines a gradient strength for the first primary and single shield coil to be 26.0 mT/m. The second constraint point specifies a +2.0\% linearity of the gradient field along the gradient (x) axis and up to the distance of 28.5 cm for the isocenter of the gradient field, while the third constraint point specifies a −22% uniformity of the gradient field inside the 45 cm imaging volume.
TABLE 1
Constraint set used for the design of an
exemplary G x gradient coil.
N
ρ i (m)
φ i (rad)
Z i (m)
B zsc (T)
1
0.001
0.0
0.000
0.000026
2
0.285
0.0
0.000
0.007558193
3
0.001
0.0
0.225
0.00002028
For the exemplary G y shielded gradient coil, the radius of the primary coil is a=0.334018 m with a length of 1.136 m, while the radius of the secondary coil is b=0.431014 m. As shown in Table 2, the first constraint point defines a gradient strength to be 26.0 mT/m. The second constraint point specifies a 2% linearity of the field gradient along the gradient (y) axis and up to the distance of 32 cm for the isocenter of the gradient field, while the third constraint point specifies a −21% uniformity of the gradient field inside the 45 cm imaging volume.
TABLE 2
Constraint set used for the design of an
exemplary G y gradient coil.
N
ρ i (m)
φ i (rad)
Z i (m)
B zsc (T)
1
0.001
0.0
0.000
0.000026
2
0.3205
0.0
0.000
0.007558193
3
0.001
0.0
0.225
0.00002058
With the presence of these constraints in Table 1 and Table 2 and the application of the inverse approach methodology, the values for the Fourier coefficients for the current density of the shielded gradient coils are generated. By applying the stream function technique to the continuous current densities for both transverse shielded coils G y , G x , the discrete current patterns for these coils were generated. Specifically, for the G x gradient coil, the stream function technique generates 21 discrete loops on the primary coil, as shown in FIG. 3, and 10 loops on the single shield as shown in FIG. 4 . The common current per loop is 382.74 Amps. In this embodiment, the eddy current from the discrete coil configuration is 0.295% over a 50 cm DSV. By discretizing the current density for the G y gradient coil, the current density for the primary coil is approximated by 21 loops with a common current of 371.36 Amps, while the shielding coil is approximated by 10 loops carrying the same current per loop. For the G y gradient coil, the eddy currents are only 0.257%. Employing the Biot-Savart law to the discrete current densities for both the G y , G x shielded gradient coils, the gradient magnetic field for both these coil structure is evaluated along the perspective gradient axis and at z=0.0 m plane. It is to be appreciated that inside the physical region defined by the inner surface of the gradient coil no rollover is present, as shown in FIG. 6 . Table 3 and Table 4 illustrate the magnetic properties for the G y , G x shielded gradient coils.
TABLE 3
Magnetic properties for the
exemplary G x shielded gradient coil.
Property
A COIL
B COIL
COMBINED
Middle Cu Radius
338.393 mm
435.3244 mm
650 mm/880 mm
envelope
Electrical Length
1132 mm
1539 mm
Inductance +
598 μH
Cable
Discrete Turns
21
10
Resistance + Cable
0.167Ω
Linearity at
+5.06%
+13%
+4.75%
50 cmDSV
Rollover in ρ
Greater
Greater than
Greater
(cm)
than Body
Body coil
than
coil
Radius
Body coil
radius
Radius
Gradient Strength
@400A
44.53 mT/m
−17.3 mT/m
27.2 mT/m
Slew Rate Linear
@650V
66 T/m/sec
@1200V
129 T/m/s
Slew Rate Sine
@600V
73 T/m/sec
@1200V
136 T/m/sec
Residual Eddy
<0.3%
Current @50 cm DSV
Net Thrust Force
44 lbs
(lbs) @400 A
TABLE 4
Magnetic properties for the
exemplary G y shielded gradient coil.
Property
A COIL
B COIL
COMBINED
Middle Cu Radius
334.0175 mm
431.014 mm
660 mm/880 mm
Envelope
Electrical Length
1132 mm
1535 mm
Inductance +
595 μH
Cable
Discrete Turns
21
10
Resistance + Cable
0.166Ω
Linearity at
+3.6%
+13%
+2.5%
50 cmDSV
Rollover in ρ
Greater
Greater
Greater than
(cm)
than
than
Body coil
Body coil
Body coil
Radius
Radius
Radius
Rollover in z
34.2 cm
(cm)
Gradient Strength
45.74 mT/m
−17.74 mT/m
28 mT/m
@400A
Slew Rate Linear
@650V
69 T/m/sec
@1200V
133 T/m/sec
Slew Rate Sine
@650V
76 T/m/sec
@1200V
141 T/m/sec
Residual Eddy
<0.3%
Current
@50 cm DSV
NET THRUST
48 lbs
FORCE (LBS)
@400A
Initially, for the design of the finite, shielded, axial G z gradient coil, the gradient magnetic field must be antisymmetric in the z direction around the geometric center of this coil, while being symmetric along the x and y directions. There is no azimuthal dependence on the current density. To generate such a field, the analytical expression of the current for the primary coil is written as:
{right arrow over (J)} a ( {right arrow over (r)} )= j φ a ( z )â φ δ( ρ−a ) (15)
where δI(ρ−a) is the restriction that the current is confined on the cylindrical surface with radius a. The restriction to inner coil length, the confinement of the current density on the cylindrical surface, the azimuthal and axial symmetries for the j φ a , and the demand that the current density obeys the continuity equation yield the Fourier series expansion for both components around the geometric center of the coil as follows: j φ a ( z ) = ∑ n = 1 ∞ j φ n a sin ( k n z ) for z ≤ L a 2 ( 16 )
where j φn a are the Fourier coefficients, L a represents the total length of the inner coil, and, because the current can not flow off the ends of the cylinder, k n =(2nπ)/L a . Furthermore, both current components are zero for ¦z¦>L a /2.
In order to minimize the fringe field of the primary coil in the area which is outside both the primary and the shielding coil, the Fourier transform of the current for the shielding coil satisfies the following relationship: j φ b ( k ) = - aI 1 ( ka ) bI 1 ( kb ) j φ a ( k )
with ( 17 ) j φ a ( k ) = iL a 2 ∑ n = 1 ∞ j φ n a ψ n ( k ) ψ n ( k ) = [ - sin ( k - k n ) L a 2 ( k - k n ) L a 2 + sin ( k + k n ) L a 2 ( k + k n ) L a 2 ] ( 18 )
In this case, the expression for the z component of the magnetic field in the area inside both coils is written as: B z = - μ 0 aL a 2 π ∑ n = 1 ∞ j φ n a ∫ 0 + ∞ kk sin ( kz ) ψ n ( k ) l 0 ( k ρ ) K 1 ( ka ) [ 1 - ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] ( 19 )
where I m ′ and K m ′ represent the derivatives with respect to the argument of the modified Bessel functions of the first and the second kind. In addition, the higher order derivatives for the z component of the magnetic field along the z direction are given as: B z 2 n + 1 z = z 0 = ∂ 2 n + 1 B z ∂ z 2 n + 1 z = z 0 = - μ 0 aL a 2 π ∑ n = 1 ∞ j φ n a ∫ 0 + ∞ kk ( - 1 ) n + 2 k 2 n + 1 cos ( kz 0 ) ψ n ( k ) l 0 ( k ρ ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] ( 20 )
Furthermore the expression for the stored magnetic energy can also be written as: W = μ 0 a 2 L a 2 4 ∑ n = 1 ∞ ∑ n ′ = 1 ∞ j φ n a j φ n ′ a ∫ 0 + ∞ k ψ n ( k ) ψ n ′ ( k ) l 1 ( ka ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] ( 21 )
As a next step, the functional E is constructed in terms of W and B z (2n+ 1) for the derivative constraints, and the alternative F functional is constructed in terms of W and B z for the field constraints as: E ( j φ n a ) = W - ∑ j = 1 N λ j ( B z ( r → j ) 2 n + 1 - B zSC ( r → j ) 2 n + 1 ) z = z 0 , ρ = ρ 0 derivative constraints F ( j φ n a ) = W - ∑ j = 1 N λ j ( B z ( r → j ) - B zSC ( r → j ) field constraints
where λ j are the Lagrange multipliers and B zsc 2n+1 and B zsc represent the constraint values of the derivative or field constraints for the z component of the magnetic field at the specified N points. Minimizing E or F, a quadratic function of the current, with respect to the current coefficients j φn a , reveals a matrix equation in which j φn′ a must satisfy: ∑ n ′ = 1 ∞ j φ n ′ a ( aL a π ) ∫ 0 + ∞ k ψ n ( k ) ψ n ′ ( k ) l 1 ( ka ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] = - ∑ j = 1 N λ j ∫ 0 + ∞ kk sin ( kz j ) ψ n ( k ) l 0 ( k ρ j ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] field constraints ( 22 ) ∑ n ′ = 1 ∞ j φ n ′ a ( aL a π ) ∫ 0 + ∞ k ψ n ( k ) ψ n ′ ( k ) l 1 ( ka ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] = - ∑ j = 1 N λ j ∫ 0 + ∞ kk ( - 1 ) n + 2 k 2 n + 1 cos ( kz 0 ) ψ n ( k ) l 0 ( k ρ j ) K 1 ( ka ) [ 1 - l 1 ( ka ) K 1 ( kb ) l 1 ( kb ) K 1 ( ka ) ] derivative constraints ( 23
where the evaluation of the Lagrange multipliers is done via the constraint equation. After truncating the previous infinite summations at M terms and using compact notation, the previous expressions (22) and (23) are modified as: ∑ n ′ = 1 M j φ n ′ a C n ′ , n = ∑ j = 1 N λ j D jn ( 24 )
or in matrix form:
J a C=λDJ a =λDC −1 (25)
but
B z =J a D t B z =λDC −1 D t (26)
which leads to
λ=B z [DC −1 D t ] −1 J a =B z [DC −1 D t ] −1 DC −1 (27)
Inverting the previous matrix equation, yields a solution for j φn a , and hence for the current density. The center of mass technique is used to discretize the current density for both primary and shield coils in such a way that an absolute integer number of turns for both coils is provided for a given common current value per loop. Following the discretization, the magnetic gradient field and the eddy currents inside the desired imaging volume are calculated.
Similar design procedures were followed for the axial gradient coil. In this embodiment, the radius of the cylinder for the first primary coil is equal to a=0.348145 m and its total length is restricted to 1.050 m. In addition, the radius of the secondary coil is equal to b=0.425929 m. The constraints are shown in Table 5 for the design of this exemplary gradient coil. As shown in Table 5, the first constraint point defines a gradient strength for the first primary and common shield coil to be 28.0 mT/m. The second constraint point specifies a−5.0% linearity of the gradient field along the gradient (z) axis and up to the distance of 22.5 cm for the isocenter of the gradient field, while the rest of the constraint points specify the uniformity of the gradient field inside the 45 cm imaging volume.
TABLE 5
Constraint set used for the design for the G z
gradient coil.
N
ρ i (m)
φ i (rad)
Z i (m)
B zsc (T)
1
0.0000
0.0
0.001
0.000028
2
0.0000
0.0
0.000
0.00600000
3
0.1125
0.0
0.001
0.0000279
4
0.2250
0.0
0.001
0.0000279
With the presence of these constraints in Table 5 and the application of the inverse approach methodology , the values for the Fourier coefficients for the current density shielded G z coil are generated. Applying the center of mass technique to the continuous current densities for both coils, the discrete current patterns for these coils are generated. Specifically, for the first primary and the shield configuration, the center of mass technique generates 60 discrete loops on the primary coil. The common current per loop is 376.067 Amps. In this case, the eddy current from the discrete coil configuration is 0.19% over a 50 cm DSV. Using elliptic integrals of the first and second kind, the gradient magnetic field for the shielded G z gradient coil is evaluated. Table 6 illustrates the magnetic properties of the shielded G z gradient coil.
TABLE 6
Magnetic properties for the exemplary
G z shielded gradient coil.
Primary
Property
Coil
Shield Coil
COMBINED
Middle Cu Radius
348.145 mm
425.929 mm
650 mm/880 mm
Electrical Length
1050 mm
1362 mm
Inductance +
575 μH
Cable
Discrete Turns
54
34
Resistance + Cable
0.174Ω
Linearity at
−11.0%
−15%
−7.1%
50 cmDSV
Rollover in ρ
Greater
Greater
Greater
(cm)
than
than
than
Body coil
Body coil
Body coil
Radius
Radius
Radius
Rollover in z
37.0 cm
39.8 cm
35.6 cm
(cm)
Gradient Strength
58.94 mT/m
−29.08
29.86 mT/m
@400A
mT/m
Slew Rate Linear
@650V
75 T/m/sec
@1200V
146 T/m/sec
Slew Rate Sine
@650V
83 T/m/sec
@1200V
155 T/m/sec
Residual Eddy
<0.25%
Current @50 cm DSV
NET THRUST FORCE
−0.0212 lbs
(LBS) @400A
Employing the spherical decomposition algorithm inside a 50 cm DSV, the normalized higher order harmonics for the x, y, and z gradient coils are given in Table 7. The orders are normalized to the first derivative of the magnetic field.
TABLE 7
Higher order harmonics for the x, y,
and z gradient coils normalized to the first
derivative of the magnetic field.
X Gradient
Y Gradient
Z Gradient
Order
Coil
Coil
coil
1
X1 = 1
Y1 = 1
Z1 = 1
3
X3 = −0.01746
Y3 = −0.012643
Z3 = −0.01386
5
X5 = −0.02596
Y5 = −0.021837
Z5 = −0.044789
7
X7 = −0.00418
Y7 = −0.013692
Z7 = −0.019567
9
X9 = +0.00420
Y9 = +0.009330
Z9 = +0.018849
11
X11 = −0.00120
Y11 = −0.002767
Z11 = −0.008617
13
X13 = −0.00022
Y13 = +0.000552
Z13 = +0.003052
Table 8 illustrates the uncorrected and corrected pixel position when all orders of gradient field inhomogeneities are present and when the 3rd and 5th orders are corrected for the X gradient coil on a 25 cm DSV. Furthermore, table 8 indicates the percentage change for correcting these higher orders. The outcome from the 3rd and 5th order corrected for the gradient field is considered as the basis for the percentage calculation. In addition, table 9 illustrates the uncorrected and corrected pixel position when all orders are present and when the 3rd and 5th orders are corrected for the Y gradient coil on a 25 cm DSV. Furthermore, table 9 indicates the percentage change for correcting these higher orders. The outcome from the 3rd and 5th order corrected for the gradient field is considered as the basis for the percentage calculation. Table 10 illustrates the uncorrected and corrected pixel position when all orders are present and when the 3rd and 5th orders are corrected for the Z gradient coil on a 25 cm DSV. Furthermore, table 10 indicates the percentage change for correcting these higher orders. All columns represent pixel displacement in cm.
TABLE 8
Uncorrected and corrected pixel
positions for an exemplary x gradient coil.
3rd and
3rd order
5th Orders
IDEAL
ALL ORDERS
Corrected
Corrected
% Change
0
0
0
0
0%
0.5000
0.5000
0.5000
0.5000
0%
2.0000
2.0003
2.0003
2.0000
0.0%
5.0000
5.0049
5.0052
5.0000
0.1%
5.5000
5.5064
5.5070
5.5000
0.12%
6.0000
6.0081
6.0091
6.0000
0.13%
6.5000
6.5101
6.5115
6.5000
0.16%
7.0000
7.0123
7.0144
7.0000
0.18%
7.5000
7.5148
7.5177
7.5001
0.2%
8.0000
8.0175
8.0215
8.0001
0.22%
8.5000
8.5203
8.5257
8.5001
0.24%
9.0000
9.0234
9.0306
9.0002
0.26%
9.5000
9.5266
9.5359
9.5003
0.28%
10.0000
10.0299
10.0419
10.0004
0.30%
10.5000
10.5333
10.5485
10.5006
0.33%
11.0000
11.0366
11.0558
11.0009
0.36%
11.5000
11.5399
11.5637
11.5012
0.33%
12.0000
12.0431
12.0724
12.0017
0.35%
12.5000
12.5462
12.5819
12.5023
0.35%
TABLE 9
Uncorrected and corrected pixel
positions for an exemplary y gradient
coil.
3rd and 5th
3rd order
Order
IDEAL
ALL ORDERS
Corrected
Corrected
% Change
0
0
0
0
0%
0.5000
0.5000
0.5000
0.5000
0%
2.0000
2.0005
2.0005
2.0000
0.03%
5.0000
5.0035
5.0038
5.0000
0.07%
5.5000
5.5045
5.5050
5.5000
0.08%
6.0000
6.0058
6.0066
6.0000
0.10%
6.5000
6.5072
6.5083
6.5001
0.11%
7.0000
7.0088
7.0104
7.0001
0.13%
7.5000
7.5105
7.5128
7.5002
0.14%
8.0000
8.0124
8.0155
8.0003
0.16%
8.5000
8.5144
8.5186
8.5004
0.17%
9.0000
9.0166
9.0221
9.0006
0.18%
9.5000
9.5189
9.5260
9.5010
0.19%
10.0000
10.0212
10.0303
10.0012
0.20%
10.5000
10.5237
10.5351
10.5014
0.21%
11.0000
11.0263
11.0404
11.0028
0.21%
11.5000
11.5289
11.5461
11.5038
0.22%
12.0000
12.0316
12.0524
12.0052
0.22%
12.5000
12.5343
12.5593
12.5071
0.22%
TABLE 10
Uncorrected and corrected
pixel positions for an exemplary z
gradient coil.
3rd and 5th
3rd order
Order
IDEAL
ALL ORDERS
Corrected
Corrected
% Change
0
0.0
0
0
0%
0.5000
0.5000
0.5000
0.5000
0%
2.0000
1.9998
1.9998
2.0000
0.01%
5.0000
4.9969
4.9972
5.0000
0.02%
5.5000
5.4957
5.4963
5.5000
0.08%
6.0000
5.9943
5.9952
6.0000
0.10%
6.5000
6.4925
6.4939
6.5000
0.12%
7.0000
6.9904
6.9924
7.0000
0.14%
7.5000
7.4878
7.4906
7.5000
0.16%
8.0000
7.9847
7.9886
7.9998
0.19%
8.5000
8.4811
8.4864
8.4998
0.22%
9.0000
8.9767
8.9838
8.9997
0.26%
9.5000
9.4716
9.4810
9.4995
0.30%
10.0000
9.9657
9.9778
9.9993
0.34%
10.5000
10.4588
10.4743
10.4990
0.38%
11.0000
10.9507
10.9705
10.9987
0.44%
11.5000
11.4415
11.4663
11.4983
0.49%
12.0000
11.9309
11.9617
11.9977
0.56%
12.5000
12.4187
12.4567
12.4970
0.63%
It should be appreciated that the specified current patterns can be changed to produce either better linearity at the price of coil efficiency, and/or greater efficiency at the price of linearity. Further, the dimensions (radius and/or length) of the cylindrical gradient coils can be changed to be increased or decreased according to the preferred application. In addition, the lengths of the primary coils and/or the secondary coils can be similar or different.
The various correction coils of the shim set may be shielded or not. In addition, the order of the field inhomogeneities that are correctable by the active shim set in unlimited. The multi-axis shim set may be incorporated with alternative gradient coil geometries, such as elliptical, planar, flared, and the like. The proposed shim set and gradient coil design for the primary and shielding coils may be bunched or thumbprint designs or any combination of the two. In addition each active shim set may be used to compensate for eddy currents due to gradient pulsing. It is to be appreciated that one shim set may be used to corrected gradient magnetic field inhomogeneities for both a whole-body gradient coil and an insertable head gradient coil set or an generation of gradient coil mounted or inserted into the same magnet/active shim set.
The invention has been described with reference to the preferred embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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A magnetic resonance apparatus includes a main magnet ( 12 ) which generates a main magnetic field through and surrounding an examination region ( 14 ). The main magnetic field contains inhomogeneities which affect image quality. A gradient coil assembly ( 22 ) generates gradient magnetic fields across the examination region, which contain higher order harmonics causing inhomogeneities in the gradient magnetic field. A multi-axis shim set ( 23 ) is selectively excited in order to cancel both the main magnetic and gradient magnetic field inhomogeneities. More particularly, DC currents are applied by a shim coil power supply ( 25 ) to cancel the main magnetic field inhomogeneities. AC current pulses are superimposed on the DC currents by the shim coil power supply ( 25 ) in order to correct the gradient magnetic field inhomogeneities. The existence of correctable higher order gradient magnetic field harmonics provides for fast switching, high duty cycles, and high peak gradients, without adding distortions to the resulting magnetic resonance images.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of International Application PCT/FI97/00387 filed Jun. 18, 1997.
FIELD OF THE INVENTION
The present invention relates to a method for drying and/or cooling a web, in which the web is passed over the circumference of a blow drum or equivalent blow device and dried by means of a pressurized drying gas that is blown out of openings formed in the mantle of the blow drum into a gap between an outer face of the blow drum and the web. A support zone is formed by the pressurized gas between the outer face of the blow drum and the web. Gas moistened with water evaporated from the web is passed out of the support zone into the interior of the blow drum through other openings formed in the mantle of the blow drum into a set of exhaust ducts placed at least partially inside the blow drum.
The present invention also relates to a device for drying and/or cooling a web including a blow drum or equivalent blow device. The web to be dried is guided over the circumference of the blow drum. In the interior of the blow drum, a system of gas ducts has been formed and communicates with blow openings formed into the mantle of the blow drum. A support zone is formed by pressurized gas between the outer face of the blow drum and the web to be dried. Exhaust openings are formed in the mantle of the blow drum for removal of the moistened gas out of the support zone.
BACKGROUND OF THE INVENTION
The highest web speeds in paper machines are currently of an order of about 25 meters per second, but before long, a speed range of from about 25 m/s to about 40 m/s is likely to be taken into use. Even with the highest running speeds that are employed now, and with the ever higher running speeds in the future, the dryer section has become and will likely remain a bottle-neck for the runnability of a paper machine.
In the prior art, in multi-cylinder dryers of paper machines, twin-wire draw and/or single-wire draw is/are employed. In twin-wire draw, the groups of drying cylinders comprise two wires which press the web, one from above and the other one from below, against heated faces of drying cylinders. Between the rows of cylinders, which are usually horizontal rows, the web has free and unsupported draws which are susceptible to fluttering which may result in web breaks. In single-wire draw, each group of drying cylinders comprises only one drying wire on whose support the web runs through the entire group so that, on the drying cylinders, the drying wire presses the web against the heated cylinder faces, and on the reversing cylinders situated between the drying cylinders, the web remains at the side of the outside curve. Thus, in single-wire draw, the drying cylinders are placed outside the wire loop, and the reversing cylinders are placed inside the wire loop. In prior art "normal" groups with single-wire draw, the heated drying cylinders are placed in the upper row, and the reversing cylinders are placed in the lower row, these rows generally being horizontal and parallel to one another. So-called "inverted" groups with single-wire draw are also known, in which the heated drying cylinders are placed in the lower row and the reversing suction cylinders or rolls in the upper row, the substantial objective of such inverted groups being to dry the web from the side opposite in relation to the side of the web dried in a normal group with single-wire draw.
In the area of the dryer section of a paper machine, various problems have occurred, for which the present invention suggests novel efficient solutions. These problems include the large length of the dryer section which increases the costs of the dryer section and the machine hall. It is not desirable to enlarge the diameter of drying cylinders in order to increase the capacity because the drying cylinder is basically a pressure vessel and large rotating masses create problems. Problems have also been caused by the difference in speed between the paper web and the wires, which has resulted in wear of the wires and, at the worst, even in paper breaks in the dryer section. Problems also have occurred in the controllability of the web draw and in the runnability of the web. The cross-direction shrinkage which deteriorates the quality of the paper or board, has also been a problem, especially when the cross-direction shrinkage is uneven.
With respect to the prior art related to the present invention, reference is made, for example, to the following publications.
Swedish Patent No. 463,568 (corresponding to International Publication No. 90/14467) describes a method for drying paper in a paper machine by means of which cross-direction shrinkage of the paper web is influenced and favorably prevented in a paper machine comprising at least one heated drying cylinder and at least one drying wire. In the paper machine, the paper web is passed over the drying cylinder in direct contact with its cylinder face at the same time as the drying wire is passed from outside onto the paper web, wherein the longitudinal edges of the paper web are drawn or sucked into contact with one or more cylinders while the web is carried around these cylinders. Thus, in the construction described in this patent, suction is used in connection with the drying cylinder, and the web to be dried is in a direct contact with the face of the drying cylinder. Also, the paper web is supported by the cylinder face over its entire width while the paper web is running over the drying cylinders.
European Patent No. 0 238 470 describes a device in the dryer section of a paper machine, preferably in the dryer section of a cylinder dryer, which device permits control of shrinkage and/or stretch of the paper web in the cross direction of the web in relation to the running direction of the dryer section. The device includes belts, most commonly two belts, which extend or run through the whole dryer section or a part of it and which belts are arranged in the lateral area of the paper web so that they distribute the force that is directed perpendicularly to the running direction of the web and mainly acts in the lateral areas of the paper web. The belt and/or the paper web is coated with an adhesive layer from the side of the web/belt that is placed towards the paper web/belt, in which case, the belt and the paper web act upon each other. In the arrangement described in EP '470, the paper web is attached by its edges to a separate support belt, which support belt is aligned with a groove arranged on the circumference of the cylinder.
Swedish Patent No. 468,217 describes a carrying device for passing the stock web through the dryer section of a paper machine. In the device, carrying belts are arranged on both sides of the stock web in its edge areas in the longitudinal direction, which carrying belts are passed onto rolls, operated by guide members, and grasp corresponding grooves arranged on the rolls, so that shrinkage in the cross direction is prevented. The guide members of each dryer belt comprise a number of individual guides that are placed in pairs above and below the carrier belt and the stock web. In an arrangement in accordance with SE '217, paper is attached from its edges by means of two mechanical chains, and this arrangement is meant for very slow running speeds only.
Finnish Patent Application No. 895928 (corresponding to U.S. Pat. No. 5,135,614) describes a suction roll in which the paper web adheres to the face of the suction roll over its whole width, and an intensified hold is arranged in the lateral areas of the suction roll. The suction roll comprises a perforated roll mantle and a suction space inside the roll mantle which can be subjected to a vacuum. A suction flow thus enters through the perforations in the roll into the roll interior and the paper web is pressed towards the outer face of the roll mantle. The suction space is divided at least into three vacuum spaces in the direction of width of the roll, while the suction space comprises at least two partition walls inside the roll. By means of the partition walls, the suction roll is divided into different vacuum zones such that it is possible to provide the outer vacuum spaces with a higher vacuum than the vacuum space in the mid area of the roll, whereby the vacuum profile is arranged to be growing towards the edges of the roll across the width of the roll and the percentage of shrinkage in the lateral areas of the paper web is reduced, which has a favorable effect on the evenness of the shrinkage.
Finnish Patent No. 84088 (corresponding to U.S. Pat. No. 5,397,438) describes a method in the transfer of a paper web for reducing and equalizing the cross-direction shrinkage of the paper web in the dryer section of a paper machine. The drying wire is provided, in its lateral areas, with an adhesive substance for the time of the process, in which connection, by means of adhesion means, an adhesion force is produced in the drying stage between the lateral areas of the wire and the paper, whereby cross-direction shrinkage of the paper web is prevented. The adhesive substance is removed when it is no longer needed.
U.S. Pat. No. 4,980,979 describes a suction roll whose function is to provide at least one end of the roll with a higher vacuum level than the rest of the roll in order to make threading of the web easier and which suction roll thus has a function corresponding to that described in Finnish Patent Application No. 895928.
With further respect to the prior art, reference is made to Finnish Patents Nos. 64,335 and 82,019 (corresponding to U.S. Pat. No. 5,199,623) which describe arrangements in which a support wire is not used, but the web is carried by an airborne nozzle blowing.
With respect to additional prior art closely related to the present invention, reference is made to the current assignee's Finnish Patent Application No. 943040 (corresponding to U.S. Pat. No. 5,575,084) which describes a method and device for drying and cooling a paper web or equivalent. In the method, for drying and cooling the paper web or equivalent, the web is passed over the circumference of a revolving roll or equivalent on support of a support wire or equivalent on the face of the support wire or equivalent that is placed facing the roll, and the web is dried and/or cooled by means of a gas. It has been considered one novelty of this method that drying and/or cooling gas is blown through openings formed in the mantle of the roll into the space between the outer face of the roll and the web supported by the support wire or equivalent, whereby a support zone formed by pressurized gas is formed between the outer face of the roll and the web. Moistened or humidified gas is passed out of the support zone into the interior of the roll through exhaust openings formed in the mantle of the roll, and more specifically into a system of ducts placed inside the roll.
OBJECTS AND SUMMARY OF THE INVENTION
An object of the present invention is further development of the above web drying and/or cooling constructions.
Another object of the present invention is to provide a web drying and/or cooling arrangement and method in which problems connected with the cross-direction shrinkage of the paper web are taken into consideration in the drying of the paper web.
A further object of the invention is development of the web drying and/or cooling constructions and methods described above so that the diameter of the drying drum does not impose limitations, but can be freely selected, as well as so that the geometry of the dryer group formed by means of the drying drums can be selected freely without deterioration of the efficiency.
Another object of the invention is further development of the above web drying and/or cooling constructions and methods so that the drying can be arranged only on the part of the drying drum that is covered by the material to be dried as well as so that it is possible to use a so-called geometry of inverted group.
A further object of the invention is further development of the above web drying and/or cooling constructions and methods so that the proportion of revolving masses in the dryer group is minimized.
An additional object of the invention is to develop the prior art web drying and/or cooling constructions and methods so that the construction is simple and easy to build and, additionally, so that the drying of the paper web can be made as uniform as possible.
In view of achieving the objects stated above and others, in the method in accordance with the invention, the web to be dried is supported in the lateral areas by means of a revolving edge support placed at each end of the blow drum and which is separate from the blow drum, and a support zone is sealed in the running direction of the web by means of the circumferential faces and/or friction faces of the edge supports.
The device in accordance with the invention comprises revolving edge supports arranged in connection with the ends of the blow drum, apart from the blow drum. The revolving edge supports are arranged to support and guide the web to be dried. The blow drum is arranged stationarily in its position by means of support constructions.
Thus, by means of the arrangement in accordance with the invention, a contact-free mode of drying supported by the edges is provided, in which mode of drying the material web runs supported by an air cushion. In such an arrangement, it is possible to use high temperatures and the geometry of the dryer group can be selected freely, because the efficiency is not lowered. The height of the air cushion is selected suitable for the edge supports by means of the ratio of blow air to exhaust air, and the support of the edges can be made more effective by subjecting the circumferential and/or friction faces of the edge supports to a vacuum. Thus, suction is used in the effective section only.
In the arrangement in accordance with the invention, only the edges of the web and/or the support band are supported, and the support zone, i.e., air cushion, is formed between the stationary nozzle face of the drum and the web. In this arrangement, air circulation can be arranged either through the nip opening or through the ends. In the arrangement in accordance with the invention, only the edge supports revolve, sealing the support zone at the same time, and they are mounted in bearings outside the blow area and isolated from the blow area, in which case, it is possible to use blow air having a high temperature.
Very good possibilities for control of cross-direction shrinkage which takes place during drying of the paper web or a corresponding web-like material are achieved by means of an arrangement in accordance with the invention, because the outer circumferences of the equipment can easily be arranged to increase the hold at the edge and, additionally, if required, cooling can be arranged in them, and the mid-part and the ends of the drying drum can be isolated from each other. The edges are supported by means of a vacuum, in which case, a direct blowing or an airborne nozzle blow can be applied onto the face of the web material to be dried, and the pressure of the supporting air cushion can be selected by means of the pressure ratio of the blow air to the exhaust air into/out of the blow drum. If necessary, the blow openings in the blow drum can be provided with suitable nozzles, in which case, a suitable distance is achieved between the blow drum and the web material to be dried. Additionally, the coverage angle on the drying drum can be selected as desired in accordance with the rest of the geometry of the group.
It is possible to use the device in accordance with the invention either as provided with a support band or without a band.
In one exemplifying embodiment of the invention, it is possible to divide the blow drum into blocks or sections in the longitudinal direction of the web, in which case, the temperature of the blow air can be regulated in the zones in the longitudinal direction of the web. Additionally, the stationary blow drum can be divided into blocks, in which case, it is possible to regulate the profile, the speed and the temperature of the blowings.
Additionally, in the arrangement in accordance with the invention, the type of the nozzles can be selected in accordance with the grade of the paper or board and thus, the thickness and strength factors of paper or board can be taken into account, such as, for example, dry solids content, porosity, etc. The blow face of the drum can be divided into different temperature areas by using division of the drum into zones in the longitudinal direction and in the cross direction of the web, in which case, it is also possible to regulate the web profile both in the longitudinal direction and in the cross direction. In an arrangement in accordance with the invention, the edge supports operate as sealing faces for the air cushion, and the mid-area of the drum may be isolated from the lateral areas. In this manner, for example, mounting in bearings and corresponding arrangements can be carried out in ordinary conditions, and the temperature and moisture circumstances otherwise influential in the drying, need not be taken into account when choosing the arrangements. The edge supports can be provided with cooling if necessary. In view of energy consumption, direct gas heating is the most advantageous application for the heating of the drying drum in accordance with the invention. Naturally, other alternatives occurring to a person skilled in the art are also within the scope of the invention.
In the arrangement in accordance with the invention, a difference in pressure may be brought about over the web-like material, and the thickness of the support zone, i.e., air cushion, is selected in compliance with the distance of the circumference of the edge supports, i.e., the equivalent diameter. Since, by means of the edge support, an additional support has been created in the lateral areas of the web to be dried, the rest of the web to be dried can be equalized easily while drying and, thus, cross-direction shrinkage of the web can be controlled and especially any tensions that may follow from such shrinkage are eliminated. In the arrangement in accordance with the invention, roughening of the circumference of the edge supports, formation of grooves or other friction enhancing element can be used as additional support, if required, and this can be enhanced further by subjecting the friction faces to a vacuum.
In the arrangement in accordance with the invention, the web can also be spread by arranging the circular edge support faces to open in the direction of progress of the web. The spreading effect is based on the fact that the web can be stretched also in the cross direction in the dry solids content area in which it is stretched (drawn) in the longitudinal direction. The opening angle of the edge supports can be made adjustable such that the extent of the stretch can be regulated by means of the opening angle. When a support wire is used in connection with the web, the edges of the support wire are arranged penetrable to air so that the vacuum effect produced by the arrangement is not transferred to the wire. At a higher dry solids content, the opening angle of the edge supports can be used to maintain the existing web width, for example, to eliminate the shrinkage of the web in free gaps. By means of spreading of the web, it is possible to affect the uniformity of quality in the product in respect of factors of strength, to improve the runnability, and/or to increase the production.
The invention will be described in detail with reference to some preferred embodiments of the invention illustrated in the figures in the accompanying drawings. However, the invention is not confined to the illustrated embodiments alone.
BRIEF DESCRIPTION OF THE DRAWINGS
Additional objects of the invention will be apparent from the following description of the preferred embodiment thereof taken in conjunction with the accompanying non-limiting drawings, in which:
FIGS. 1A, 1B, 1C, 1D, 1E and 1F are schematic illustrations of an exemplifying embodiment of the invention, in which FIG. 1A is a schematic sectional view in the longitudinal direction of the drum, FIGS. 1B and 1C are schematic sectional views in the cross direction of the drum taken along the lines 1B--1B, 1C--1C, respectively, of FIG. 1A, FIG. 1D is a schematic view taken in the direction of arrows 1A in FIG. 1A, FIG. 1E is a schematic three-dimensional illustration of the drum in accordance with the invention, and FIG. 1F is a schematic illustration of an exemplifying embodiment of the nozzle arrangement of the blow drum;
FIGS. 2A and 2B are schematic illustrations of a second exemplifying embodiment of the invention;
FIG. 3 schematically shows a mode of sealing the nip between the drum and the guide roll;
FIG. 4 schematically shows an embodiment in which the guide rolls in contact with the drum are displaceable;
FIGS. 5A and 5B schematically show an embodiment of a friction face provided on the circumference of the edge support;
FIGS. 5C, 5D, 5E, 5F, 5G and 5H show different modes of arrangement of the edge support of the web and/or support band;
FIG. 5I schematically shows the edge supports that open in the direction of progress of the web;
FIG. 6 schematically shows a sector suction arrangement arranged in connection with the edge support of the blow drum in accordance with the invention;
FIGS. 7A and 7B schematically show examples of regulation arrangements for use with the invention for regulation of the temperature and the blow pressure in connection with the cross-direction profile of the drum and/or with the zone division of the drum in the longitudinal direction;
FIG. 7C schematically shows an arrangement in which a blow drum in accordance with the invention is divided into evaporation zones in the longitudinal direction of the web;
FIG. 7D schematically shows an arrangement connected with the hold of the edge when the web to be dried is passed from a drum onto a roll or from a drum onto a drum; and
FIGS. 8A, 8B, 8C and 8D schematically show certain basic embodiments of dryer groups that can be provided by means of an arrangement in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the accompanying drawings wherein like reference numerals refer to the same or similar elements, the blow device in accordance with the invention shown in FIGS. 1A-1E is designated 10 and is this embodiment, is in the form of a drum 10 having a mantle 12 provided with intake or blow holes 44 and exhaust holes 46. Holes 44 and 46 are also referred to as openings herein. Drying gas P in , which is typically heated air, is passed into the drum 10 and blown through the holes 44 at the surface of the web-like material W to be dried, for example a paper web. In this exemplifying embodiment of the invention, the web W is supported by a support band or wire 15 so that a positive pressure is formed between the outer face of the drum 10 and the web W. By means of a suitable blow pressure, the web W is separated from the face of the drum 10. The separation of the web W from the face of the drum 10 permits the flow of the drying gas from the intake holes 44 to a support zone or air cushion 11 and from the air cushion 11 into the exhaust holes 46, and the drying process proper is thus able to take place via these gas flows. More particularly, with a suitable blow pressure, which pressure depends on the force that the support band 15 applies to the web W, i.e., on the tension of the wire, a support zone consisting of pressurized gas, the so-called air cushion 11, is formed between the outer face of the drum 10 and the web W supported by the wire 15, which air cushion 11 carries and dries the web. The blown gas/air is dry and heated and, thus, able to increase its humidity or bind humidity. The blow speed of the drying gas is from about 20 meters per second to about 150 meters per second, preferably from about 40 meters per second to about 120 meters per second, and the temperature of the drying gas during drying is from about 30° C. to about 450° C., preferably from about 70° C. to about 350° C.
The humid gas resulting from the drying of the web W is removed from the support zone 11 through the exhaust holes 46 arranged between the blow holes 44. Additionally, it is possible to use direct-blow nozzles that blow perpendicularly toward the web or, for example, a pressure nozzle technique as shown in FIG. 1F, in which case, the blowing takes place through slot nozzles and the exhaust passages are between the slots. The rest of the face of the drum 10 aside from the gas flow holes 44,46 can be smooth or grooved. The grooves can be placed in the longitudinal or cross direction to the mantle of the drum 10 or in between these, i.e., along a diagonal. The grooves can also be radial in relation to the inflow holes 44 and exhaust holes 46. The drying gas P in is passed through the intake duct 13 and through the holes 44 in the mantle 12 face of the drum 10 into the space between the outer face of the drum 10 and the web W, into which zone, the air cushion 11 is thus formed. The exhaust hoes 46 are arranged between the intake holes 44 and through the exhaust holes, the gas that has bound the humidity from the web W is removed through one or more exhaust ducts 14 arranged at least partially in the interior of the drum 10. The web W is passed while supported by the wire 15 over an alignment roll 61 onto the face of the drying drum 10 and away from the drum 10 over another alignment roll 61.
In FIG. 1A, the rotating edge support is denoted by reference numeral 22, and the outer circumference of the edge support forms, together with the support band 15, sealing faces for the support zone, i.e., for the air cushion 11. The edge supports 22, which are separate from the drum 10 and isolated therefrom by isolation members 21, revolve around an axle 27 thus drawing the support band 15 around the arcuate circumference of the drum 10. The blow drum 10 is mounted stationary by means of support structures 23. Additionally, the intake and exhaust ducts 13,14 can function as support members for the drum 10. The air-intake and exhaust-air arrangements can also be placed so that the ducts 13,14 pass through the ends of the drum 10.
FIG. 1B is a schematic sectional view taken along the line 1B--1B in FIG. 1A, in which sectional view the alignment or guide rolls 61 are shown. By means of guide rolls 61, the web W to be dried and the support band 15 are passed around the drum 10 and away from the drum 10. As shown in FIG. 1B, the intake air flow P in is passed in the intake duct 13 into the interior of the drum 10, and from the interior of the drum 10 through the blow holes 44 to the area of the support zone or air cushion 11. Exhaust air is removed through the exhaust holes 46.
In FIG. 1C, in the sectional view taken along the line 1C--1C in FIG. 1A, the exhaust air duct 14 of the blow drum 10 is shown, through which the exhaust air coming from the holes 46 is passed out of the drum 10 interior as an exhaust air flow P out .
FIG. 1D is an end view seen in the direction of arrows 1A in FIG. 1A, in which the edge supports 22 of the drum 10 and the axle 27 of the supports are shown. Axle 27 is arranged to revolve on a bearing 27L mounted on the support constructions 23. The diameter of the drum is indicated by a dashed line.
As shown in FIG. 1E, the edge supports 22 of the blow drum 10 revolve around the axle 27. At the same time the edge supports 22 seal the air system. A groove 22U for the threading ropes is arranged in connection with the edge support 22 at one end for threading of the web. Suction PA is applied through the axles 27 to enhance the hold of the web produced by the edge supports 22. Isolation members 21 may be arranged in connection with the edge support 22. The area between the edge supports 22 of the blow drum 10, in which area, the air cushion 11 is formed, has a positive pressure of about from 0 Pa to about 5000 Pa. In FIG. 1E, the support constructions of the drum 10 are denoted generally by reference numeral 23, and the air intake duct 13 and the exhaust air duct 14 are shown. A groove 17 or equivalent can be arranged in the drum 10 to permit passage of any paper lumps, i.e., clods, that may be carried along by the web to be dried.
FIG. 1F shows an arrangement for the nozzle arrangement of the blow drum 10 in which a nozzle face 18 formed on the face of the drum 10 is curved so that it passes air from the intake openings 44 to the support zone. On the other hand, the faces passing to the exhaust openings or holes 46 are constructed to guide the exhaust air flow P out into the duct 46 and further into the exhaust duct 14 (see, e.g., FIG. 1E).
In the exemplifying embodiment of the invention shown in FIGS. 2A and 2B, the blow device 10 is formed so that several guide rolls or wheels 71 are arranged in connection with the mantle 12 of the drum 10 so that they form edge supports 22 that have the shape of an arc of a circle. A support band 15x runs around each set of guide rolls or wheels 71 and around additional guide rolls or wheels 71' which enable the support band 15x to form a closed loop around the guide rolls or wheels 71. The web W to be dried is passed via the guide rolls 61 over the arc of a circle formed by the guide rolls or wheels 71. Air is blown to the air support zone or cushion 11 through the blow holes 44 formed in the mantle 12, which air support zone is formed between the support bands 15x and the wire 15, so that the air serves to dry the paper web W or equivalent. The edges of the wire 15 are supported by the support bands 15x which are placed on the revolving guide and axle parts 72,73.
FIG. 3 shows a safety gap E arranged between the blow device 10 and the guide rolls 61, and it schematically shows a method of sealing the nip N between the drum 10 and the guide roll 61, into which nip the web W is passed supported by the wire. A blow device 25 is placed in the nip area, by means of which a sealing blow P 25 is blown in a direction opposite to the running direction of the support fabric and the web W to thereby seal the nip.
FIG. 4 schematically shows an embodiment in which the guide rolls 61 of the edge support 22 are each displaceable by means of a spring 62 connected with an arm 63.
FIGS. 5A and 5B schematically show an embodiment in which suction is applied to the area of the edge supports 22. The hold of the web W is arranged by means of grooves 59 on the edge supports. The reference I refers to one suction sector, and reference arrow PA refers to the vacuum/suction produced. FIGS. 5A and 5B show an embodiment of the friction face on the circumference of the edge support 22. The grooves 59 can be subjected to a vacuum through the passage and the form of a parallelogram in the grooving eliminates any discontinuity in the friction face.
FIG. 5C shows an embodiment of the blow drum 10 with a support band 15, in which embodiment, the grip of the web W on the edge support 22 can be adjusted by the tightness of the support band 15 (tightness force 22M).
In the embodiment shown in FIG. 5D, the grip of the web W on the edge support 22 is made more effective by means of a vacuum via ducts 53. Cooling of the edge of the support band 15 can be carried out by cooling the edge supports 22, for example, by means of air. Through the duct 54, for example, outside air is passed into the duct 54 made inside the edge support 22 so that the edge of the support band 15 can be cooled. The cooling medium may be other than air, for example liquid or some other gas.
In the embodiment shown in FIGS. 5E and 5F, edges of the support band 15 or the web W are supported on the circumference of the edge supports 22 by means of separate loop bands 57 running over the band 15 so that the band 15 is between the loop bands 57 and the blow device 10. The tension of the support bands 15 is adjusted by means of displaceable guide rolls or wheels 56.
FIGS. 5G and 5H show the support of the edges of the support band 15 or the web W against the circumference of the edge supports 22 by means of the blow boxes 58. By means of blow boxes 58, a backup support effect is created, whose hold effect consists of the blow pressure multiplied by the desired surface area.
FIG. 5I schematically shows the edge supports 22 that open in the direction of progress S of the web W, viewed from above. At a suitable dry solids content of the web W, it is possible to install the edge supports 22 opening in the direction of progress S of the web W, in which case the web W can be stretched in the cross direction. The ratio of the spreading per side to the opening angle is tan α=x/2/D wherein α is the opening angle and D is the diameter of the edge support 22, in which connection the distance that the web runs during spreading is x=π·D/2. A number of such units made out of edge supports 22 can be arranged one after the other, in which connection passing of the web W from one unit to the other takes place, for example, by means of a turning roll. The opening angle α of the edge support 22 is preferably adjustable, for example by adjusting the turning angle of the shaft 27 in the direction of the arrow S 2 and by moving the frame construction 23 in the direction indicated by the arrow S 1 . When a support wire is used, its edges must be penetrable to air, so that the vacuum effect does not pass to the wire.
FIG. 6 schematically shows the sector-suction area SI of the edge supports 22, in which sector-suction area the suction effect may be arranged in the desired sector area SI on the circumference of the edge supports 22. In such a case, the web W to be dried is passed from the guide roll 61 over the sector SI and further away from the guide roll 61. The sector area SI may be any desired length, i.e., so that it comprises a certain number of circumferential sectors, and the guide rolls 61 may be shifted to the desired location.
FIG. 7A is a schematic illustration of an exemplifying embodiment including separate temperature regulation of the cross-direction profile and/or longitudinal segment division. The blow device 10 is partitioned into discrete cross-direction or axial sections, each extending over a portion of the longitudinal axis of the blow device. The segments on the stationary drum 10 are each provided with their own heat sources 67, into which heat sources the air is passed by means of a common blower 68.
FIG. 7B is a schematic illustration of an exemplifying embodiment including separate temperature and blow pressure regulation in the cross-direction profile and/or longitudinal segment division of the blow drum 10. The blow device 10 is partitioned into discrete cross-direction or axial sections, each extending over a portion of the longitudinal axis of the blow device. In this embodiment, each air intake pipe 13 is provided with a heat source 67 of its own and with a blower 68 of its own. Each section may also have a dedicated exhaust duct 14. Each heat source and blower can be set to have the desired temperature and blow pressure parameters.
FIG. 7C shows division of the blow drum 10 into two segments 101,102 in the longitudinal direction of the web. In other words, the blow drum 10 is partitioned into a plurality of discrete sections in a longitudinal, running direction of the web W. In this manner, different drying values can be used in the longitudinal direction of the web W by adjusting the drying values of the segments 101,102 as desired.
As shown in FIG. 7D, support bands 85 are used in the grip of the edge of the web W on a run from a drum 10 to a roll 80 or from a drum 10 to a drum 10. The band 85 is placed at each edge of the drum 10, the bands are pervious to air and robust that they hold the shrinkage force of the web W. The contact grip of the section supported by the band 85 is created by a separate vacuum device 86 which, when sealed against the band 85 and sucking through it, attaches the web W to the band 85.
FIG. 8A schematically shows a typical dryer group R with or without a wire provided with blow drums 10 in accordance with the invention, which dryer group comprises large blow drums 10 and small drums 11 between them. All blow drums 10,11 comprise suction sectors SI having an adjustable length of web contact. Between the drums 10,11 there are reversing rolls 61 whose edge zones are subjected to a vacuum.
As shown in FIG. 8B, the dryer group R is composed of blow drums 10, in which dryer group, the web W to be dried runs over the blow drums 10 on the suction zones SI, guided by the reversing rolls 61. Thus, the group R shown in FIG. 8B mainly corresponds to the preceding one but the geometry is different. One-sided drying is eliminated by means of a so-called inverted group R A which is also composed of blow drums 10 A in accordance with the invention, between which there are rolls or suction rolls 61 A . The draw with no wire meets the requirements imposed on an inverted group. In the group gap R-R A , the web W is passed from the reversing roll 61 of the preceding group R straight onto the reversing roll 61 A of the following group R A
FIG. 8C schematically shows a dryer group R with or without a wire provided with blow drums 10 in accordance with the invention, in which group the web W to be dried runs supported from its edges by edge supports and guided by the drum and the rolls or by suction rolls 61 and so that both faces of the web W are altematingly turned toward the face of the drying drum 10.
FIG. 8D shows an embodiment corresponding to the preceding one but without rolls. The web W runs directly from the drum 10 to the drum 10.
The examples provided above are not meant to be exclusive. Many other variations of the present invention would be obvious to those skilled in the art, and are contemplated to be within the scope of the appended claims. Thus, the invention has been described above only with reference to some of its advantageous embodiments. However, the invention is not intended to be narrowly confined to the disclosed embodiments. Numerous variations and modifications are possible within the scope of the inventive idea defined in the following claims.
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Method for one of drying and cooling a web in which a web is passed over an arcuate circumference of a blow device, a gas is directed from an interior of the blow device at the web through first openings formed in a mantle of the device to form a support zone between the mantle and the web, and moistened exhaust gas is drawn from the support zone into the interior of the blow device through second openings formed in the mantle. A revolving edge support is arranged at each end of the blow device to support the web during the passage of the web over the circumference of the blow device, the edge supports being separate from the blow device, and the edge supports include one of interior circumferential and friction surfaces to seal the support zone. A device for one of drying and cooling a web includes an elongate blow device having a circumference over which the web is guided to run, intake and exhaust ducts arranged in an interior of the blow device and a mantle including first openings in flow communication with the intake duct and second openings in flow communication with the exhaust duct. The device also includes a revolving edge support arranged at each end of the blow device for supporting and guiding the web during running of the web over the circumference of the blow device, the edge supports being separate from the blow device, and support constructions for supporting the blow device in a stationary position.
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RELATED APPLICATION
This patent application claims priority upon commonly owned U.S. provisional patent application Ser. No. 60/397,922 filed Jul. 22, 2002 entitled “Proactive Prevention of SMTP Mass Mailing Worms”, which provisional patent application is hereby incorporated by reference in its entirety into the present patent application.
TECHNICAL FIELD
This invention pertains to the field of preventing malicious attacks to computers, and, in particular, preventing e-mail propagation of malicious computer code.
BACKGROUND ART
As used herein, “malicious computer code” is any code that enters a computer without an authorized user's knowledge and/or without an authorized user's consent. Malicious computer code that propagates from one computer to another over a network, e.g., via e-mail, is often referred to as a “worm”. Most worms that spread from one computer to another are spread via e-mail over the Internet. The most common way to send e-mail over the Internet is using the SMTP (Simple Mail Transfer Protocol). SMTP is part of TCP/IP (Transfer Control Protocol/Internet Protocol). SMTP was originally designed to send only that e-mail that consists solely of text and that is encoded using the ASCII character set, which is limited. It soon became apparent that computer users wished to send other than straight ASCII characters as e-mail, and so encoding schemes such as UUencode and MIME were developed. These encoding schemes are capable of encoding any type of file, including a binary graphics file, into ASCII so that it can be sent as an e-mail attachment.
FIG. 1 illustrates a common system by which a client computer 1 can send e-mail to a recipient computer 5 over an open network 4 such as the Internet. In FIG. 1 , it is assumed that there are a plurality N of client computers 1 located within an enterprise 3 . Enterprise 3 may be a company, a university, a government agency, etc. Computers 1 are coupled to each other and to an e-mail server computer 2 over a Local Area Network (LAN) 6 . E-mail server 2 collects and formats e-mails sent from computers 1 and sends them to the designated recipients 5 using the SMTP protocol. It is assumed that there are a plurality J of recipient computers.
FIG. 2 illustrates a similar network in which client computers 1 are not associated with the same enterprise 3 , but rather may be more geographically dispersed and are subscribers to an Internet Service Provider (ISP). In this case, computers 1 communicate with the ISP's e-mail server 2 via the Public Switched Telephone Network (PSTN) 6 . In other respects, the functioning of the networks illustrated in FIGS. 1 and 2 are the same.
DISCLOSURE OF INVENTION
Computer-implemented methods, systems, and computer-readable media for detecting the presence of malicious computer code in an e-mail sent from a client computer ( 1 ) to an e-mail server ( 2 ). An embodiment of the inventive method comprises the steps of: interposing ( 41 ) an e-mail proxy server ( 31 ) between the client computer ( 1 ) and the e-mail server ( 2 ); allowing ( 42 ) the proxy server ( 31 ) to intercept e-mails sent from the client computer ( 1 ) to the e-mail server ( 2 ); enabling ( 43 ) the proxy server ( 31 ) to determine when a file ( 30 ) is attempting to send itself ( 30 ) as part of an e-mail; and declaring ( 44 ) a suspicion of malicious computer code when the proxy server ( 31 ) determines that a file ( 30 ) is attempting to send itself ( 30 ) as part of an e-mail.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other more detailed and specific objects and features of the present invention are more fully disclosed in the following specification, reference being had to the accompanying drawings, in which:
FIG. 1 is a system level diagram of a conventional network for sending e-mail from within an enterprise 3 .
FIG. 2 is a system level diagram of a conventional network for sending e-mail via an Internet Service Provider (ISP) computer 2 .
FIG. 3 is a block diagram illustrating an embodiment of the present invention.
FIG. 4 is a flow diagram illustrating an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Nefarious persons sending malicious computer code via e-mails have resorted to many tricks to spread their malicious messages. A typical e-mail may look something like this:
IP x.y.z.1:25 (SMTP) HELLO someone RCPT to: edGXYZ.com FROM: XYZGx17as.com SUBJECT: HELLO DATA MIME-encoded attachments
One of the tricks employed by authors of malicious code is to falsify the “FROM” field so that the recipient of the e-mail will be lulled into thinking that the e-mail was sent from a known, reputable source.
Sometimes the malicious code will be encrypted, making it difficult for a conventional anti-virus scanner to analyze it.
Modern worms such as Klez self-activate simply by the user clicking open the e-mail message itself: the user doesn't even have to click on the e-mail attachment containing the worm. Klez has operated through the popular e-mail software known as Microsoft Outlook. Klez contains its own SMTP client embedded in the worm; it does not rely on Outlook.
The present invention thwarts the propagation of malicious computer code being sent in an email from a client computer 1 to an e-mail server 2 , by means of interposing (step 41 of FIG. 4 ) an e-mail proxy server 31 (hereinafter referred to as “proxy”) between the client computer 1 and the e-mail server 2 . The client computer 1 thinks that the proxy 31 is the real e-mail server 2 . The proxy 31 may be associated with the client computer 1 , e.g., it may reside within computer 1 .
FIG. 3 illustrates the basic architecture of proxy 31 . Redirector 36 intercepts e-mail messages, and tricks client file 30 into thinking that redirector 36 is e-mail server 2 . Scan manager 32 is coupled to re-director 36 , and contains intelligence for examining the contents of e-mails. Decomposer 33 is coupled to scan manager 32 ; and unpacks (e.g., unzips) objects and sends the decomposed objects back to scan manager 32 one by one. Decomposer 33 is invoked when the e-mail being analyzed by scan manager 32 contains many objects, e.g., an e-mail body and several e-mail attachments that are zipped or otherwise combined. In that case, decomposer 33 unzips the objects and presents them to scan manager 32 one by one for further analysis. API 34 such as Norton Antivirus Application Programming Interface (NAVAPI) 34 is coupled to scan manager 32 , and presents scan manager 32 with ready access to conventional antivirus software. Extensions 35 such as Norton Antivirus Extensions (NAVEX) 35 are coupled to NAVAPI 34 and contain all of the scanning engines, virus signatures, and virus names used in conventional antivirus scanning. Modules 31 - 36 may be implemented in hardware, software, and/or firmware, or any combination thereof.
In the embodiment where e-mail server 2 adheres to the SMTP protocol, proxy 31 adheres to the SMTP protocol as well. Generally speaking, proxy 31 adheres to the same protocol adhered to by e-mail server 2 .
At step 42 of FIG. 4 , proxy 31 is enabled to intercept e-mail sent from the client computer 1 to the e-mail server 2 . The enabling may be accomplished by the user of computer 1 clicking on a “e-mail scanning” feature on antivirus software (such as Norton Antivirus manufactured by Symantec Corporation of Cupertino, Calif.) that has been installed on the user's computer 1 . Such an enabling may, for example, serve to activate proxy 31 every time a client file 30 within client computer 1 attempts to access the computer's port 25 , which is the conventional port used in personal computers for sending e-mail over the Internet.
At step 43 , scan manager 32 determines whether file 30 is attempting to send itself, either as part of the e-mail body or as an e-mail attachment. The determination that is made in step 43 can vary based upon the type of file 30 . The name of the file 30 is ascertained by redirector 36 and given to scan manager 32 . In the WIN32 API of Microsoft Corporation, scan manager 32 determines whether file 30 is a file in the PE (portable executable) format. The PE header identifies file 30 as a PE file. Section headers determine the type of the section, e.g., code sections, data sections, resource sections, etc. For a PE file in the WIN 32 API, scan manager 32 examines the entire code section or code sections. Scan manager 32 performs a compare between two versions of file 30 : the version that has been intercepted and that now resides within proxy 31 versus the version that resides in client computer 1 . In one embodiment, scan manager 32 declares a suspicion of malicious code in step 44 when the two versions are nearly identical. If the two versions are not nearly identical, scan manager 32 declares in step 45 that no malicious code is present in file 30 . “Nearly identical” is defined throughout this patent application to mean that no more than one byte out of a preselected threshold number of bytes varies between the two versions. In one embodiment, the preselected threshold number of bytes is 512. Other preselected threshold numbers can be selected based on the application. The reason for not insisting upon perfect matching between the two versions of the file is that the malicious code occasionally modifies a byte of the file.
Once a suspicion of malicious code is declared in step 44 , one or more optional steps 46 , 47 , and 48 can be invoked. Steps 46 and 48 serve to reduce the number of unwanted false positives (declaring a file 30 to be contaminated when it isn't).
In optional step 46 , the user of computer 1 is given a set of choices when a suspicion of malicious code has been declared in step 44 . These choices may be presented to the user via a dialog box which pops up on the user's monitor. Such a dialog box may look like the following:
Malicious Worm Alert
Filename: readme.exe
Norton AntiVirus has detected a malicious worm on your computer that is trying to e-mail itself to other computers. If this Malicious Worm Alert appeared when you were not sending an e-mail message, the worm is trying to spread itself by e-mail, and you should select the “Quarantine this worm (Recommended)” option from the following drop down list. You can get more information about the worm from the Symantec Security Response virus encyclopedia.
Select one of the following actions:
Stop this worm from e-mailing itself. This stops the worm from e-mailing itself at this time, but does not quarantine the worm. This action leaves the worm on your computer, where it can possibly be activated again. Select this option only if you are sure you want to leave the worm on your computer. Quarantine this worm (Recommended). This permanently stops the worm by putting it in the Norton AntiVirus Quarantine. While in Quarantine, the worm will not be able to spread itself. This is the safest action. Allow this application to send e-mail attachments. This sends the e-mail containing a potential worm. Such a worm could infect the recipient's computer. Select this option only if you are sure the e-mail is not infected with a worm. Always allow this application to send e-mail attachments. In the future, Norton AntiVirus will not check this file for worms. This is the riskiest action, because such a worm could e-mail itself from your computer without your knowledge.
Note that the file name of the suspicious file 30 is given to the user, along with four choices. If the second choice is selected (quarantining the worm), file 30 is encrypted and sent to the headquarters of the antivirus company (in this case, Symantec) for analysis.
It is expected that the user would rarely select choices three or four (allowing the application to send e-mail attachments). Such a choice might be selected when the user is attempting to e-mail the entire e-mail software program to a recipient 5 .
In optional step 47 , an alert is sent to every client computer 1 associated with the enterprise 3 . The alert serves to warn other users of possible problems.
In optional step 48 , scan manager 32 checks to see whether a digital signature has been affixed to file 30 , and, if so, verifies the digital signature with a trusted source in a conventional manner. If the digital signature is present and is verified by the trusted third party, scan manager 32 then rescinds the declaration of suspected malicious code found in step 44 , and deems the file 30 to be clean after all.
The above description is included to illustrate the operation of the preferred embodiments and is not meant to limit the scope of the invention. The scope of the invention is to be limited only by the following claims. From the above discussion, many variations will be apparent to one skilled in the art that would yet be encompassed by the spirit and scope of the present invention.
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Computer-implemented methods, systems, and computer-readable media for detecting the presence of malicious computer code in an e-mail sent from a client computer ( 1 ) to an e-mail server ( 2 ). An embodiment of the inventive method comprises the steps of: interposing ( 41 ) an e-mail proxy server ( 31 ) between the client computer ( 1 ) and the e-mail server ( 2 ); allowing ( 42 ) the proxy server ( 31 ) to intercept e-mails sent from the client computer ( 1 ) to the e-mail server ( 2 ); enabling ( 43 ) the proxy server ( 31 ) to determine when a file ( 30 ) is attempting to send itself ( 30 ) as part of an e-mail; and declaring ( 44 ) a suspicion of malicious computer code when the proxy server ( 31 ) determines that a file ( 30 ) is attempting to send itself ( 30 ) as part of an e-mail.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a machine for liquid treatment of fabrics in rope form forming a closed loop of the type that uses a reduced ratio of the treatment bath.
2. Description of the Prior Art
Machines of this type are already known comprising an impregnation device for the rope fabric with a treatment bath, a movable mechanical conveyor device with adjustable speed and being provided with a perforated supporting surface for the fabric, said surface being located above the level of the treatment bath which is contained in a lower vat, means for transferring the fabric from the impregnation device to the mechanical conveyor, and placing the fabric thereon so that pleats are formed, and a reel for guiding the fabric from the outlet of the mechanical conveyor to the inlet of said impregnation device.
In the German patent document Nos. 2,439,747 and 2,531,528 are described machines of this type wherein the rope mechanical conveyor is a linear conveyor having a conveyor rectilinear section and between the outlet and the inlet of this conveyor, the fabric is guided by a horizontally extending pipe having a length almost equal to that of the mechanical conveyor. Inside said pipe, the fabric is impregnated by the treatment liquid and at the same time the fabric is advanced through the inside of the pipe by the action of the liquid itself which is pressure-fed into the pipe through an annular nozzle, i.e. the fabric advance along said pipe is made by the transportation system called "jet".
Jasper & Co. GmbH's German Pat. No. 2,620,387 discloses a machine wherein the rope of fabric mechanical conveyor is provided with a perforated circular platform rotatively fitted above a fixed vat containing the treatment bath. In this machine, the fabric rope advance is also performed by the "jet" system i.e. by the action of the treatment liquid pressure in the impregnation device and also comprises an impregnation and guide pipe of the fabric rope which is circularly curved or wound above the circular conveyor and also comprises a reel for guiding the fabric from the conveyor to the dragging and impregnation device but said reel has not been designed to carry out the fabric advance.
All these machines have the disadvantage that with the fabric driving "jet" system used, the pressure injected liquid exerts a strong dragging action against the fabric which can then be damaged, particularly when short staple woven fabrics are dealt with. Also in these known machines it is very difficult to coordinate the speed transferred to the fabric by the liquid action with the speed at which the fabric is carried by means of the mechanical conveyor, so that it is easy for pilings or stresses to be produced in the fabric before or after its passage through the impregnation device.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a machine for liquid treatment of fabrics in rope form making a closed loop of the type hereinbefore disclosed, i.e. of the type using a reduced ratio of a treatment bath wherein the fabric is impregnated by the treatment liquid and then transported making pleats while keeping the fabric from any contact with the treatment bath, and coming back again to be successively subjected to impregnation.
Another object of the invention is to provide a machine of said type whereby any possible danger of fabric damage when running through the several areas of the machine is avoided.
Still another object of the invention is to provide a machine of said type wherein the fabric travelling motion is obtained by mechanical means with exclusion of any hydraulic dragging action against the fabric.
With this purpose, the machine of the invention comprises a draw winch as a sole means for achieving the continuous motion of the ring of the fabric rope alongside the machine and which drives the fabric through a fabric impregnation device together with a treatment liquid, this liquid being poured without any pressure on the moving fabric so that the fabric is free from any dragging action, an inclined curved profile channel taking up the fabric rope together with the impregnation liquid and the rope being arranged to make pleats the rope is then released to a mechanical conveyor device of a known type, which allows the liquid to be separated from the rope and fall into a lower vat and carries the pleated fabric rope up to a point where the fabric is removed from the conveyor by said draw winch.
According to a preferred embodiment of the invention, said draw winch has a variable geometry which enables it to change the ideal interface with the fabric rope from a straight transverse profiled surface to a surface where the transverse profile is V-shaped, so that this surface can thus be adapted according to the kind of fibres making up the fabric to avoid any slippage between the fabric and the draw winch.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects, features and advantages of our invention will be described in detail in the following description with reference to the annexed drawings, wherein:
FIG. 1 is an elevational schematic view of the whole of the essential parts of the machine of the invention;
FIG. 2 is a perspective view of the draw winch which is a portion of the machine of the invention;
FIG. 3 is a plan view showing the shape of the rods in the draw winch;
FIG. 4 is a partly cross-sectional view showing a rod of FIG. 3 fitted on the winch and showing the two end positions and the center position said rod can be made to adopt;
FIG. 5 is an elevational view of the draw winch seen from the right-hand side of FIG. 2 with rods at the center position;
FIG. 6 is a similar view to that of FIG. 5 with rods alternatively shown at their opposed end positions;
FIG. 7 is a perspective schematic view showing the loop arrangement for the machine of the invention; and
FIG. 8 is a view similar to FIG. 7 in different perspective.
DETAILED DESCRIPTION
The machine according to the invention comprises a draw winch generally indicated by 1 provided with operating means which make it rotate in the direction of the arrow A1 in the FIG. 1. On this winch 1 passes a fabric piece in rope form 2 with its end sewn making a closed ring which is continuously moved by said winch 1.
Under this winch 1 from the outlet side of the fabric rope 2, there is an impregnating device provided with a reservoir 3 having an inlet conduit 4 by means of which a fabric treatment liquid, for instance a dyebath, reaches the reservoir 3, this reservoir having a spill edge 5 preferably with a circular shape which surrounds the fabric rope 2 in the position where it goes from the draw winch 1, so that said treatment liquid by simple gravity i.e. without being subjected to any pressure is in contact with the downwardly moving fabric rope 2 and falls down together with it.
Under said reservoir 3 the impregnating device further comprises a channel having a bottom 6 and two sidewalls 7 which bottom 6 is longitudinally curved and extends from an upper end essentially tangent to a vertical plane up to a lower end essentially tangent to a plane substantially horizontal.
The spill edge 5 of the reservoir 3 is downwardly extended to a guide 8 leading the fabric rope 2 together with the accompanying treatment liquid against the upper portion of the bottom 6 of said channel, so that the fabric the form of pleats 9 inside said channel and becomes impregnated with this treatment liquid.
Channel 6,7 ends up over a mechanical conveyor device which comprises a perforated surface 10 is otherwise made, to enable the treatment liquid to pass through to be collected in a lower vat, not illustrated, and from which vat it is conducted, in a known way, by means of a pump towards the inlet conduit 4 of the reservoir 3. Said conveyor device can be of any known type, for instance, made with several superimposed conveyor belts oppositely driven by a rotating circular platform or otherwise, capable of leading the pleated rope 9 up to a point where the rope is removed from the conveyor by the draw winch 1.
To achieve an uniform treatment of the fabric and avoid irregularities particularly if the machine is used for fabric dyeing, it is necessary to avoid piling of the fabric rope being formed at the inlet or at the outlet of the mechanical conveyor 10 and for this purpose and according to the invention, the operating means of said mechanical conveyor 10 are synchronized with the operating means of the draw winch 1. But it is further essential that any slippages cannot be produced between the fabric rope and the draw winch 1 and it is to be borne in mind that the possibilities of slippages being produced can be originated by the kind of fabric material, for instance, slippage trend is higher in a fabric manufactured with synthetic fibres.
With this purpose in mind the draw winch 1 consists of two plates 11 and 12 fixed on a driven shaft 13 and a plurality of rods 14 transversally arranged between the two plates 11,12.
As shown in FIG. 3, said rods 14 are longer than the clearance between the two plates 11 and 12 and two arms 15 and 16 are joined to both ends of the rods making with the rod 14 opposed and equal angles, giving the rod unit a shape similar to a "Z". At the free ends of these arms 15 and 16 short shafts 17 and 18 parallel to each other are fixed, these shafts being rotatively housed in associated holes in plates 11 and 12 distributed thereon on a locus of points concentric to the axis of the winch shaft 13.
With this arrangement each of the rods 14 of the winch can adopt three main positions and all the intermediate positions between them. In FIG. 4 are shown these three main positions, namely a first extreme position in full lines wherein the arm 15 is located in the plane of the drawing and downwardly directed, the arm 16 is located in the drawing plane and upwardly directed and consequently the rod 14 remains located in the drawing plane inclined upwardly from the lower left-hand portion of the drawing towards the upper right-hand portion; a second extreme position in dashed lines reversed as regards the first position and wherein the rod 14 is also located in the drawing plane and inclined downwardly from the upper left-hand portion towards the lower right-hand portion; and in dot and dash lines the rod in the middle position is shown, with the arms 15 and 16 located in planes perpendicular to the drawing plane and consequently the rod 14 is located in a plane rearwardly inclined with respect to the drawing plane. Rod 14 obviously can be located at any other position between those dispersed above.
Successive rods 14 fitted between the plates 11 and 12 of the winch 1 can be arranged at alternate opposed positions which can be varied from the positions shown in FIG. 5, wherein each of the rods 14 is located in a plane parallel to the winch shaft 13 up to the positions shown in FIG. 6 wherein each of the rods 14 is located in a diametral plane of the draw winch and alternately inclined oppositely so that each two adjacent rods 14 are crosslinked in space. This latter position of the rods 14 makes the fabric rope 2 follow on the winch 1 in a wavy running that ensures dressing of the rope by the winch, and thereby prevents any slippage between them when a slippage-prone fabric is being treated. In the fabrics with less slippage characteristics the position of the rods 14 can be varied up to the extreme position shown in FIG. 5.
Preferably one of the shafts 17 of the two extreme shafts 17 and 18 of all the rods 14 is outwardly projected from its housing in the plate 11 and on each of said projected shafts 17 a toothed chain wheel is fitted. A chain 20 (FIG. 2) engages all these toothed wheels 19; this chain alternately engaging the inner and outer portions, with respect to the shaft 13, of the toothed wheels, for example, at 19', 19", etc. This arrangement enables concurrently shifting all the rods 14 of the draw winch 1 in alternately opposite directions and in equal angles.
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A machine for liquid treatment of fabrics in rope form forming a closed loop, which includes a mechanical draw device for cause the continuous advance movement of rope to a device for merely impregnate the rope with the treatment liquid and for producing a folded configuration to the impregnated rope, and conveying means synchronized with the draw device for carrying the folded rope from the impregnation and folding device to a point at which the rope is drawn up by the mechanical draw device.
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[0001] This application is a continuation of U.S. patent application Ser. No. 13/042,402, filed Mar. 7, 2011, which is currently allowed and is a continuation of U.S. Ser. No. 11/999,398, filed Dec. 5, 2007, now U.S. Pat. No. 7,902,985, both of which herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a radio frequency identification (RFID) systems that use RFID tags to track product inventory, or other mobile items.
BACKGROUND OF THE INVENTION
[0003] Information management systems are being developed to track the location and/or status of a large variety of mobile entities such as products, vehicles, people, animals, etc. A widely used tracking technology uses so-called RFID tags that are placed physically on the items being tracked. Reference herein to “items” being tracked is intended to include the variety of entities just mentioned as well as, more commonly, product inventories.
[0004] RFID tags may be active or passive. Active tags typically have associated power systems and can transmit data over modest distances. Passive systems lack internal power but derive transmitting signal power from an incoming RF signal. However, transmitting distances with passive RFID tags are very limited. To read a large number of RFID tags, spread over a wide physical area, requires either a large number of RFID readers, or a reliable system of moving RFID readers. One proposed solution to this problem is to use active RFID tags on the products. However, active tags are relatively costly. Although they lend more function to a tracking system, and transmit more effectively, passive tags are typically more cost effective where inventories being tracked are large.
[0005] What is needed is an improved system for RFID tracking where the scale of the application exceeds the performance capability of conventional RFID approaches.
STATEMENT OF THE INVENTION
[0006] We have developed a new architecture for RFID systems that is adapted to process large numbers of RFID tags and provide information about a large number of items. The system provides for multiple tag readers. The tag readers are active and have both transmit and receive capability. The system includes a new element called a gateway tag that receives information about individual items from the multiple readers and thus contains data on the entire inventory of items. This allows each of the multiple readers to access data for the entire inventory of items. The gateway tag may interface with an information storage center that also contains data for the entire inventory of items.
BRIEF DESCRIPTION OF THE DRAWING
[0007] The invention may be better understood when considered in conjunction with the drawing in which:
[0008] FIG. 1 is a schematic view of a typical RFID tag system;
[0009] FIG. 2 is a representation of a passive RFID tag;
[0010] FIG. 3 is a representation of an active RFID reader;
[0011] FIG. 4 is a schematic view of the RFID tag system of the invention; and
[0012] FIG. 5 is a representation of a gateway RFID tag according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] FIG. 1 is a schematic representation of a typical RFID system wherein the RFID tag is shown at 11 , the RFID reader at 12 and a central information store at 13 . A wide variety of implementations are used for the function of tracking large numbers of items, many of which use the basic elements shown in FIG. 1 . Typically, the RFID tag 11 is a passive device attached to the item being tracked. The reader 12 is an active RFID device that communicates with large numbers of passive RFID tags, and typically either stores data in the reader, and/or relays data to a central database 13 . The central database keeps data for all items in the system. In many applications, for example, large retail outlets, the RFID readers are mobile devices that are moved around the vicinity of the RFID tags to record the RFID tag data. Mobility in this application is necessary since the transmission distance between the RFID tags and the RFID readers is very limited, for example, tens of meters maximum, and typically less than 10 meters. The RFID readers are typically powered, which extends the range of transmission between the RFID readers and a remotely located receiver. That allows the option of using a RFID reader to simply relay RFID tags to a central database. More typically, the reader reads the passive RFID and stores the information locally. This data may be downloaded to the central store periodically, by placing the reader in a docking device that is connected by wireless or hardwired link to the central database. In the latter case, a wireless link between the RFID reader and a remote receiver may or may not be used.
[0014] A passive RFID tag is shown at 21 in FIG. 2 . RFID tags are miniaturized as much as practical to allow for the essential elements of a semiconductor IC chip 22 , typically a CMOS chip, and an antenna 23 . The IC chip contains a memory, usually a read-only memory encoded with item data. The antenna is a serpentine metal conductor that receives small amounts of power from the RFID reader by inductive coupling. When the IC chip is powered, it transmits item data back to the RFID reader via antenna 23 .
[0015] Passive RFID tag designs are available in many sizes and designs. Common characteristics are a platform, an IC chip, and an antenna. Depending on the application the platform may be glass, ceramic, epoxy, paper, cardboard, or any suitable plastic. An onboard power source is not included in a passive RFID tag. All power for the tag is derived from RF signals in the vicinity of the tag. The tag responds to the reader using RF backscatter, which basically reflects the carrier wave from the reader after encoding data on the carrier wave. Variables in the communication specification include the frequency of the carrier, the bit data rate, the method of encoding and any other parameters that may be needed. ISO 18000 and EPCGlobal are the standards for this interface. The interface may also include an anti-collision protocol that allows more than one tag in the range of the reader to signal concurrently. There are many specific implementations of this, and these form no part of the invention.
[0016] A typical schematic for an RFID reader is shown in FIG. 3 . The reader 31 includes RF transceiver chip 32 , microprocessor chip 33 , and battery 34 . The transceiver chip communicates through an attached antenna as indicated. These components allow the reader to not only receive data from the passive RFID tags, but to store and process the data and transmit the data to another device or station. Since the reader is powered, it can transmit data over significant distances, for example, 100 to 3000 thousand feet.
[0017] A schematic of an RFID tag system according to the invention is shown in FIG. 4 . The RFID tags are shown organized in groups A, B, and C. These groups may represent different departments in a retail outlet, separate floors or buildings in a warehouse complex, separate railroad cars or shipping containers, etc. In the arrangement shown, each group communicates with an associated RFID reader 41 , 42 , and 43 . It should be understood that this arrangement is shown by way of example only. There are many alternative configurations using RFID tags and readers. The RFID readers communicate with gateway RFID tag 45 . The link between the RFID readers and the gateway RFID tag may operate at a frequency different than the frequency used in the link between the RFID readers and the passive RFID tags. The readers collectively provide data to the gateway RFID tag for all of the items in the system. This arrangement allows any reader in the system to access data on any item in the system via the gateway RFID tag. Since the transmission to and from the gateway RFID tag to the RFID readers is powered, that link may be essentially any distance within the facility served by the RFID system. The gateway RFID tag may be a standalone unit, or, as indicated in FIG. 4 , interfaced via network 46 to a central database and memory store 47 . The network may be a wireless network, or a wired network (land line).
[0018] A schematic of the gateway RFID tag 45 in FIG. 4 is shown in FIG. 5 . The gateway RFID tag is an active tag, with battery 54 . It also has a processor 53 , a large memory 56 , and an RF transceiver 52 . The gateway RFID tag interfaces with each of the RFID readers as shown in FIG. 4 , and may interface with a central database via a wireless or wired network. The latter is an optional feature. The system may be designed with a direct interface between the RFID readers and the central database, as described in conjunction with FIG. 1 , and with a parallel link between the RFID readers and the gateway RFID tag. Adding a link between the gateway RFID tag and the central database allows data consistency between the two to be verified. Both of these subsystems typically contain data on all of the items being tracked by the system, i.e. universal system data. However, using an arrangement like that shown in FIG. 4 allows the universal system data stored at the gateway RFID tag to be different (typically less detailed) than the data stored at the central database.
[0019] For the purpose of defining terms used herein, a passive RFID tag means a device containing at least an integrated circuit chip operating at a given frequency and an antenna, but no onboard power source. The antenna operates as a low power RF transceiver. The integrated circuit chip contains a memory. An RFID reader means a device containing at least an integrated circuit chip, an antenna, an RF transmitter, an RF receiver, and a power source. The integrated circuit chip in the RFID reader contains a memory. The RFID reader has an RF transmitter that operates at the same frequency as the RFID tags, and an RF transmitter that may operate at a frequency different from that of the RFID tags. A gateway RFID tag means a device containing at least an integrated circuit chip, an antenna, an RF transmitter, an RF receiver, and a power source. The integrated circuit chip in the gateway RFID reader contains a memory. The gateway RFID reader has an RF transmitter that operates at the same frequency as the RFID readers, and may have a communications link to a remote central database. A remote central database has a microprocessor and a memory store. It may or may not be located on the same physical premises as the gateway RFID tag.
[0020] Transmitting range means the range over which signals transmitted from a transmitting device can be received by a receiving device.
[0021] In summary, an aspect of the invention is that data from an item that is not in the vicinity of an RFID reader, and thus not accessible directly from that reader, can nevertheless be accessed by that reader through the gateway RFID tag. The sequence of operations for accomplishing this involves transmitting an RFID signal between a first RFID reader and a first group of passive RFID tags, receiving at the first RFID reader first data from the first group of passive RFID tags, transmitting said first data from the RFID reader to a gateway RFID tag, receiving and storing the first data at the gateway RFID tag, transmitting an RFID signal between a second RFID reader and a second group of passive RFID tags, receiving at the second RFID reader second data from the second group of passive RFID tags, transmitting said second data from the RFID reader to the gateway RFID tag, receiving and storing the second data at the gateway RFID tag, transmitting to the gateway RFID tag a query from the first RFID reader, receiving the query at the gateway RFID tag, and transmitting second data from the gateway RFID tag to the first RFID reader.
[0022] Various additional modifications of this invention will occur to those skilled in the art. All deviations from the specific teachings of this specification that basically rely on the principles and their equivalents through which the art has been advanced are properly considered within the scope of the invention as described and claimed.
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A system and method are disclosed for transporting deterministic traffic in a gigabit passive optical network. A system that incorporates teachings of the present disclosure may include, for example, an Optical Line Termination (OLT) for exchanging data traffic in a Gigabit Passive Optical Network (GPON) having a controller programmed to generate a timeslot schedule for transport of a desired bandwidth of constant bit rate (CBR) data traffic by selecting one or more timeslots from periodic frame clusters operating according to a GPON Transmission Convergence (GTC) protocol. Additional embodiments are disclosed.
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FIELD OF THE INVENTION
[0001] The present invention relates to a method for catalyzing olefin hydroformylation reaction by using a novel solid heterogeneous catalyst, and belongs to the field of heterogeneous catalytic techniques.
BACKGROUND
[0002] Hydroformylation reaction is the reaction that an aldehyde is produced by a reaction between olefins and syngas (CO+H 2 ), wherein the number of carbon atoms of the aldehyde is one more than that of the olefin. The main reason why the hydroformylation technique is widely used in the chemical industry and becomes one of the most important techniques is that the product thereof, aldehydes, is a very useful chemical intermediate. Aldehydes can be used to synthesize carboxylic acids and corresponding esters, and aliphatic amines, etc. The most important application of aldehydes is that they can be converted to alcohols by hydrogenation. Alcohols per se can be widely used as organic solvents, plasticizers, surfactants, or the like in fine chemical engineering field. The study on hydroformylation reaction, especially on the industrialization thereof, is becoming wider and deeper, as the demands for aldehydes and alcohols increase in the industry of fine chemicals, such as plastics, coatings, rubbers, and detergents, which are closely associated with daily life.
[0003] CN 102617308 A discloses an olefin biphasic hydroformylation method. The complex catalyst used in the method is formed by polyether guandinium mesylate ionic liquids (PGMILs) with room temperature solidifiable characteristics, RhCl 3 .3H 2 O or dicarbonylacetylacetonato rhodium, and triphenylphosphine-3,3′,3″-trisulfonic acid sodium (TPPTS). The reaction is carried out in an autoclave made of stainless steel. The selectivity of high-carbon aldehydes is up to 85˜99%. The molar ratio of normal aldehydes to isomeric aldehydes is from 2.0 to 2.4. However, the reaction uses an ionic liquid, which is expensive and complex to be produced. Rh lost into the product phase is from 0.04% to 0.07%. Although the ionic liquid has advantages such as having a high melting point, having no volatility, and the like, the price thereof is relatively high. In particular, for a high-purity ionic liquid, the purification is complex, and the cost for production is high, which limits the application in industry to certain extent.
[0004] CN 102649715 A discloses a method for preparing aldehydes by olefin hydroformylation. In the method, C 2 -C 8 olefins, CO and hydrogen gas are used as raw materials, and an Rh-containing liquid solution is used as the catalyst. The raw materials and the Rh-containing liquid solution catalyst are fed into a highly efficient reactor, being in contact with each other and reacting, to produce a liquid effluent containing aldehydes. The highly efficient reactor used therein is selected from rotating packed bed reactors. U.S. Pat. No. 4,148,830 discloses a hydroformylation method using a liquid phase recycle process. In this method, the resultant aldehyde condensation product is used as a solvent for catalyst. Once the aldehyde product is recovered from the product stream, the medium containing the catalyst is recycled back to the hydroformylation reaction zone. However, in this method, there are some problems in separation of the reaction products and in recovery of the catalyst dissolved uniformly in the reaction products.
[0005] U.S. Pat. No. 6,229,052 discloses a hydroformylation reaction, wherein Rh/grafted polymer is used as a fixed bed for catalyzing propylene in gas phase. The gas phase catalytic reaction gives results similar to those of the slurry bed, namely not only the conversion and the activity are relatively low, but also a significant decrease of the activity of the catalyst is observed.
[0006] U.S. Pat. No. 4,252,678 discloses the production of a colloidal dispersion containing a transition metal, such as Rh, etc. In this process, the catalyst system is consisted of a transition metal component in form of a colloidal dispersion of 1.0 to 20.0 nm and (styrene/butadiene) functionalized copolymer terminated by a hydroxy group, and is used in the hydroformylation reaction of 1-octene. The catalyst prepared by this method cannot be used in fixed bed reactors and trickle bed reactors, and it is difficult to separate the catalyst from the product.
[0007] CN 102281948 A reports polymer-supported transition metal catalyst complexes and methods for use, and produces soluble polymer-supported rhodium catalysts that have a narrow molecular weight distribution. However, all the processes for production of the catalyst, the catalytic reaction, and separation of the catalyst are complex. In the production of the catalyst, it is required to synthesize a soluble polymer by controlling functional monomers and styrene, etc., and then introduce a ligand, and at last support the Rh catalyst. It is required to add compressed gas during the catalytic reaction. The catalyst is separated from the reaction mixture by means of nanofiltration, and the reaction result is not ideal, either.
[0008] The paper “ Study on the Suzuki Coupling Reaction Catalyzed by Palladium Catalyst supported in Microcapsule Film ” (Kaixiao L I, CMFD, No. 8) reports that a Pd-based catalyst is produced by using a microcapsule material, in which phosphorus ligands are connected in the polystyrene microcapsule film, as the support, and used in Suzuki coupling reaction. However, the microcapsule material is a copolymer material, rather than a monopolymer material. The dispersion state of the transition metal component in this catalyst is not mentioned.
[0009] In the current industrial production of aldehydes from olefin hydroformylation reaction, Rh-based homogenous catalytic technique and cobalt-based homogeneous catalytic technique are mainly used. Although the reaction activity and selectivity of homogeneous catalysts cannot be achieved by those heterogeneous catalysts, many homogeneous catalysts cannot be scaled up, only because it is difficult to separate the catalyst from the product. During the production, the activity of a catalyst decreases slowly, so it is necessary to discharge a part of the catalyst continuously, while complementing an equal amount of catalyst. Since the price of Rh is high, it is necessary to recover Rh from the stream discharged. The process of this treatment is complex, and causes burden in the production.
[0010] Recently, the study of the heterogenization of homogeneous catalysts is of wide interest. The heterogenization techniques of homogeneous catalysts are mainly classified into two categories. One is immobilization of homogeneous catalyst, including immobilization by inorganic supports, immobilization by polymer supports, supported liquid phase catalysts, and supported aqueous phase catalysts. The other is a biphasic catalysis, including liquid/liquid biphasic catalysis, fluorine biphasic system, temperature-controlled phase separation catalysis, supercritical fluid biphasic system, ionic liquid biphasic system and supercritical fluid-ionic liquid biphasic system. Many novel concepts come forth from these catalytic systems. However, in these systems, the loss of active metal is great, or the stability of catalysts is poor, or expansive organic ligands or solvents are used, or the production of the catalyst has a heavy and complicated procedure, complex techniques, and the like, so that all of these systems cannot meet the requirements for industrial production. Concerning heterogeneous catalytic systems, there are only a few reports about improving the catalytic property of a heterogeneous catalyst by adding metal auxiliaries thereto. However, since the catalytic activity of these systems is much lower than those of homogeneous catalytic systems, these systems cannot meet the requirements for industrial production, either.
SUMMARY OF INVENTION
[0011] Directed to the disadvantages in the prior art, the object of the invention is to provide a heterogeneous hydroformylation reaction process, which uses highly active solid heterogeneous catalyst and is easily realized industrially.
[0012] For this purpose, the invention provides a method for olefin hydroformylation reaction, wherein the method uses a solid heterogeneous catalyst consisted of a metal component and an organic ligand polymer with hierarchical porosity, wherein the metal component is one or more of Rh, Ir or Co, the organic ligand polymer is a polymer formed by polymerization of an organic ligand monomer containing P and alkenyl group and optional N, the metal component forms coordinated bonds with the P atom or N in backbone of the organic ligand polymer and exists in a monoatomic dispersion state in the solid heterogeneous catalyst, the method comprises subjecting olefins and a CO/H 2 mixed gas to the olefin hydroformylation reaction in a reactor in the presence of the solid heterogeneous catalyst.
[0013] In a preferred embodiment, the olefin is one or more of C 2 to C 18 olefins, and the molar ratio of the olefin to the CO/H 2 mixed gas is 0.1:1 to 1:1.
[0014] In a preferred embodiment, when the olefin is a C 2 to C 3 gaseous olefin, it is fed in the form of gas directly at a volume space velocity of 100 to 20000 h −1 ; when the olefin is a C 4 to C 18 liquid olefin, it is transported into a reaction system by a high-pressure pump at a mass space velocity of 0.01 to 10 h −1 .
[0015] In a preferred embodiment, the reactor is a fixed bed, a trickle bed, or an autoclave reactor.
[0016] In a preferred embodiment, the olefin hydroformylation reaction is carried out in an intermittent manner or in a continuous manner.
[0017] In a preferred embodiment, the reaction temperature of the olefin hydroformylation reaction is 323 to 573 K, and the reaction pressure is 0.05 to 20.0 MPa.
[0018] In a preferred embodiment, the organic ligand polymer with hierarchical porosity has a specific surface area of 200 to 2000 m 2 /g, a pore volume of 0.5 to 5.0 cm 3 /g, and a pore size distribution of 0.5 to 100.0 nm.
[0019] In a preferred embodiment, when the reactor is a fixed bed or a trickle bed, the olefin hydroformylation reaction is carried out on the solid heterogeneous catalyst continuously, the resultant liquid product continuously flows out of the reactor and is collected by a product-collection tank at a temperature of 255-298 K; when the reactor is an autoclave reactor, the olefin hydroformylation reaction is carried out intermittently, the resultant liquid product is obtained by separation from the solid heterogeneous catalyst through filtration, and the obtained liquid product is further processed by flash evaporation or rectification, so as to obtain aldehyde products having high purity.
[0020] In a preferred embodiment, the metal component accounts for 0.01 to 5.0% based on the total weight of the solid heterogeneous catalyst.
[0021] In a preferred embodiment, the organic ligand polymer is a polymer formed by polymerization of an organic phosphine ligand monomer containing P and vinyl group and optional N.
[0022] The advantageous effects of the invention include, but not limited to the following aspects:
[0023] As compared with the current techniques for hydroformylation reaction, in the invention, the reaction process and device are simple, and thus the reaction can be carried out in common fixed beds, trickle beds, or autoclave reactors, since the novel solid heterogeneous catalyst is used; the separation of the catalyst is simple, and the separation of the catalyst from the product is unnecessary in fixed bed and trickle bed, and in autoclave reactor only simple filtration is required; the catalyst is easy to be recovered and can be recycled; the reaction substrates have broad sources, and are suitable for various olefins of C 2 to C 18 ; the production process of the catalyst is simple, the catalyst has stable hydroformylation properties and a high yield. The invention solves the problems in prior art, such as the loss of the metal component, the loss of the ligand, or the difficulty of recovery and recycle of the catalyst, and thus has a broad prospect in industrial applications.
BRIEF DESCRIPTION OF DRAWINGS
[0024] FIG. 1 is a reaction flow chart of an olefin hydroformylation reaction performed continuously according to the invention.
[0025] Description of Reference Numerals in the FIGURE:
[0026] 1 : pressure gauge; 2 : purification tank; 3 : cut-off valve; 4 : pressure regulator valve; 5 : cut-off valve; 6 : pressure gauge; 7 : purification tank; 8 : cut-off valve; 9 : pressure regulator valve; 10 : mass flowmeter; 11 : cut-off valve; 12 : pump; 13 : pressure gauge; 14 : cut-off valve; 15 : mass flowmeter; 16 : pressure gauge; 17 : one-way check valve; 18 : mixer; 19 : preheater; 20 : reactor (fixed bed or trickle bed); 21 : collection tank; 22 : discharge valve; 23 : back pressure valve; 24 : flowmeter
DETAILED DESCRIPTION OF EMBODIMENTS
[0027] The invention realizes a high activity heterogeneous hydroformylation reaction by using a novel solid heterogeneous catalyst, which is consisted of a metal component and an organic ligand polymer with hierarchical porosity (i.e. with hierarchical porosity comprising macropores, mesopores, and micropores). The organic ligand polymer with the hierarchical porosity acts both of a support and a ligand, so as to ensure that the metal active component as a homogeneous catalyst can exist in the pores of the polymer support stably, and thereby the solid heterogeneous catalyst is formed. The problems in the separation of the catalyst from the product and in recycle of the catalyst can be solved by using this solid heterogeneous catalyst system. The method comprises subjecting olefins 1 and CO/H 2 mixed gas to the olefin hydroformylation reaction in a reactor, such as a fixed bed, a trickle bed, or an autoclave reactor, in the presence of the solid heterogeneous catalyst.
[0028] In one preferred aspect, the invention provides a method for catalyzing hydroformylation reaction using a solid heterogeneous catalyst, the method can include, but not limited to, the following characteristic aspects.
[0029] (1) The solid heterogeneous catalyst used is consisted of a metal component and an organic ligand polymer with hierarchical porosity. Preferably, the metal component is one or more of Rh, Ir or Co, the organic ligand polymer with the hierarchical porosity is a polymer formed by polymerization of an organic ligand monomer containing P and alkenyl group and optional N, for example, by solvothermal polymerization. The organic ligand polymer having the hierarchical porosity is preferably a polymer formed by solvothermal polymerization of an organic phosphine ligand monomer containing P and alkenyl group and optional N. Preferably, the metal component accounts for 0.02 to 5.0% of the total weight of the solid heterogeneous catalyst. Preferably, the organic ligand polymer with hierarchical porosity has a specific surface area of 200 to 2000 m 2 /g, a pore volume of 0.5 to 5.0 cm 3 /g, and a pore size distribution of 0.5 to 100.0 nm.
[0030] (2) The olefin used for the olefin hydroformylation reaction may be one or a mixed olefin of C 2 to C 18 olefins. Preferably, when the olefin is a C 2 to C 3 gaseous olefin, it is fed in the form of gas directly, and when the olefin is a C 4 to C 18 liquid olefin, it is transported into a reaction system by a high-pressure pump.
[0031] (3) The olefin hydroformylation reaction can be carried out in a fixed bed, a trickle bed, or an autoclave reactor. That is to say, the olefin hydroformylation reaction can be carried out intermittently or continuously.
[0032] (4) The conditions of the olefin hydroformylation reaction may be preferably as follows: a reaction temperature of 323 to 573K (i.e. 50 to 300° C.), more preferably 353 to 573K; a reaction pressure of 0.05 to 20.0 MPa, more preferably 0.5 to 10.0 MPa. Preferably, the molar ratio of the olefin to the CO/H 2 mixed gas is 0.1:1 to 1:1, wherein the volume ratio of CO to H 2 in the CO/H 2 mixed gas is generally 1:1. Preferably, when the olefin is fed as a gas, the volume space velocity of the gas olefin is 100 to 20000 h −1 , more preferably 500 to 10000 h −1 ; when the olefin is fed in a liquid form, the mass space velocity of the liquid olefin is 0.01 to 10 h −1 , more preferably 0.1 to 10 h −1 ; the stirring speed of the slurry bed is 200 to 1000 rpm.
[0033] (5) Preferably, when the olefin hydroformylation reaction is carried out in a fixed bed or a trickle bed, the hydroformylation reaction is carried out on the solid catalyst continuously, the resultant liquid product continuously flows out of the reactor and is collected by a product-collection tank at a temperature of 255-298 K; when the olefin hydroformylation reaction is carried out in an autoclave reactor, the olefin hydroformylation reaction is carried out intermittently, the resultant liquid product can be separated from the solid heterogeneous catalyst by simple filtration, for example. More preferably, the obtained liquid products can be further processed by flash evaporation or rectification, or the like, according to the different boiling temperatures thereof, so as to obtain aldehyde products with high purity.
[0034] The invention also provides a flow chart of catalyzing the hydroformylation reaction by the novel heterogeneous catalyst, as shown in FIG. 1 . Syngas from a steel cylinder passes through a pressure gauge 1 for showing the total pressure, flows through a purification tank 2 for purifying the gas, passes through a cut-off valve 3, passes through a pressure regulator 4 for regulating the pressure, passes through a cut-off valve 5, passes through a pressure gauge 16 for showing the pressure prior to the mass flowmeter, and then passes through a check valve 17 for controlling the flow rate of the syngas. A gaseous olefin (e.g. C 2 -C 3 ) from a steel cylinder passes through a pressure gauge 6 for showing the total pressure, flows through a purification tank 7 for purifying the gas, passes through a cut-off valve 8, passes through a pressure regulator 9 for regulating the pressure, passes through a mass flowmeter 10 for controlling the flow rate of the gaseous olefin, passes through a cut-off valve 11; a liquid olefin (e.g. C 4 -C 18 ) passes through a high-pressure metering pump to increase to a desired pressure, passes through a pressure gauge 13 for showing the pressure of the liquid olefin, passes through a cut-off valve 14. The syngas and the gaseous olefin or the liquid olefin are mixed sufficiently in a mixer 18, preheated by a preheater 19, and then enter a reactor 20 charged with the solid heterogeneous catalyst, to perform the hydroformylation reaction. The product is collected in a collection tank 21, and subjected to gas-liquid separation. Thereafter, the reaction pressure is controlled by a back pressure valve 23. The tail gas is metered by a flowmeter 24, and then is exhausted. The liquid product passes through a cut-off valve 22 intermittently, and then is discharged, weighted and analyzed.
[0035] In one preferred aspect, the method for producing the solid heterogeneous catalyst used in the invention is as follows.
[0036] 1) At a temperature of 293 to 473 K and in an inert gas (such as nitrogen or argon) protective atmosphere, an appropriate amount of radical initiator is added to an organic solvent of an organic ligand monomer containing P and alkenyl group and optional N, and stirred for 0.5-100 hours. Here, the organic solvent used may be benzene, toluene, tetrahydrofuran, methanol, ethanol, or trichloromethane. The radical initiator used may be cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile, or azodiisoheptonitrile.
[0037] 2) At a temperature of 293 to 473 K and in a protective atmosphere of inert gas (such as nitrogen or argon), the stirred solution mentioned above is kept standing for 10-100 hours, to carry out the polymerization reaction.
[0038] 3) The solvent is drawn off from the reacted mixture at room temperature under vacuum, so as to obtain an organic ligand polymer with hierarchical porosity.
[0039] 4) The above-mentioned organic ligand polymer with the hierarchical porosity is put into an organic solvent (which may be the same as the above-mentioned organic solvents) containing a metal component, such as one or more of Rh, Ir or Co. It is stirred at a temperature of 293 to 473 K and in a protective atmosphere of inert gas (such as nitrogen or argon) for 0.5-100 hours. After stirring, it is cooled to the room temperature, the solvent is drawn off at room temperature under vacuum, and thereby the desired solid heterogeneous catalyst used in the olefin hydroformylation reaction is obtained.
[0040] In the production of the catalyst of the invention, the organic ligand monomer used can include, but not limited to, one or more of the followings:
[0000]
[0041] In order to explain the production method of the catalyst and the use thereof in the olefin hydroformylation reaction better, examples for the production of some catalyst samples (in which only tri(4-vinylphenyl)phosphine monomer (i.e. the monomer L-2 mentioned above) is used as the exemplary organic ligand monomer for explanation) and use thereof in reaction process are provided below. However, the invention is not limited to the Examples listed. Unless otherwise indicated, the “percent” used in this application is by weight.
[0042] In the following Examples, all raw materials are as follows.
[0043] H 2 /CO mixed gas (containing 50 vol. % H 2 and 50 vol. % CO): Zhonghao Guangming Chemical Industry Research & Design Institute Ltd.
[0044] ethylene: Zhonghao Guangming Chemical Industry Research & Design Institute Ltd., purity≧99.999 vol. %
[0045] propylene: Zhonghao Guangming Chemical Industry Research & Design Institute Ltd., purity≧99.999 vol. %
[0046] 1-octene: Shanghai Chemical Reagent Co., analytical pure
[0047] 1-decene: Shanghai Chemical Reagent Co., analytical pure
[0048] 1-dodecene: Shanghai Chemical Reagent Co., analytical pure
[0049] tri(4-vinylphenyl)phosphine: synthesized by Zhejiang University, chemical pure
[0050] The measurements of the specific surface area and the pore size distribution of samples were performed on an Autosorb-1 adsorption analyzer of Quantachrome Instruments Co. Before test, the samples were pretreated at 373 K for 20 hours. A N 2 adsorption-desorption test was carried out at a liquid nitrogen temperature of 77 K.
Example 1
[0051] 10.0 g tri(4-vinylphenyl)phosphine was dissolved in 100.0 ml tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas. 1.0 g radical initiator azodiisobutyronitrile was added into the above solution, and stirred for 2 hours. The stirred solution was kept standing at 373 K under a protective atmosphere of nitrogen gas for 24 h. Then it was cooled to room temperature, the solvent was drawn off at room temperature (about 298 K) under vacuum, and thereby a P-containing ligand polymer with hierarchical porosity was formed by polymerization from tri(4-vinylphenyl)phosphine via solvothermal method. The technical route for the polymerization of the tri(4-vinylphenyl)phosphine ligand polymer support in this example was shown as follows:
[0000]
[0000] wherein the polymerization degree n was 450-550, a hierarchical porosity comprising macropores, mesopores, and micropores was contained, the BET specific surface area measured was 981 m 2 /g, the pore volume was 1.45 cm 3 /g, and the pore size distribution was 0.5 to 100.0 nm.
[0052] 50.10 mg of dicarbonylacetylacetonato rhodium (I) was dissolved into a three-necked flask charged with 100.0 ml of tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas by stirring 1.0 g of the P-containing ligand polymer having the hierarchical porosity prepared above was added thereto. This mixture was stirred at 298 K under a protective atmosphere of nitrogen gas for 24 hours, then the solvent was drawn off at room temperature under vacuum, and thereby a metal Rh solid heterogeneous catalyst supported by the P-containing ligand polymer itself having the hierarchical porosity was obtained. The solid heterogeneous catalyst supported by the P-containing ligand polymer itself having the hierarchical porosity prepared above was charged into a fixed bed reactor. Ethylene gas as olefin and CO/H 2 mixed gas (in which the volume ratio of H 2 :CO=1:1) in molar ratio of 1:2 were charged thereto. The reaction was started under following conditions: at 393K, under 1.0 MPa, at a volume space velocity of the olefin gas of 1000 h −1 , at a volume space velocity of the CO/H 2 mixed gas of 2000 h −1 . The resultant liquid product propylaldehyde was collected in a cold trap collection tank. The liquid product was analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using ethanol as the internal standard. The tail gas of the reaction was on-line analyzed by an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The results were shown in Table 1.
Example 2
[0053] Concerning the synthesis of the tri(4-vinylphenyl)phosphine ligand polymer support, see Example 1. 0.5 mg of dicarbonylacetylacetonato rhodium (I) was dissolved into a three-necked flask charged with 100.0 ml of tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas by stirring. 1.0 g of the P-containing ligand polymer having the hierarchical porosity prepared above was added thereto. This mixture was stirred at 298 K under a protective atmosphere of nitrogen gas for 24 hours, then the solvent was drawn off at room temperature under vacuum, and thereby a solid heterogeneous catalyst of metal Rh-supported by the P-containing ligand polymer itself having the hierarchical porosity was obtained. The solid heterogeneous catalyst of metal Rh-supported by the P-containing ligand polymer itself having the hierarchical porosity prepared above was added into a fixed bed reactor. Ethylene gas as olefin raw material and CO/H 2 mixed gas (in which the volume ratio of H 2 :CO=1:1) in molar ratio of 1:2 were charged thereto. The reaction was started under the following conditions: at 393K, under 3.0 MPa, at a volume space velocity of the olefin gas of 2000 h −1 , at a volume space velocity of the CO/H 2 mixed gas of 4000 h −1 . The resultant liquid product propylaldehyde was collected in a cold trap collection tank. The liquid product was analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using ethanol as the internal standard. The tail gas of the reaction was on-line analyzed by an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The results were shown in Table 1.
Example 3
[0054] Concerning the synthesis of the tri(4-vinylphenyl)phosphine ligand polymer support, see Example 1. 12.53 mg of dicarbonylacetylacetonato rhodium (I) was dissolved into a three-necked flask charged with 100.0 ml of tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas by stirring. 1.0 g of the P-containing ligand polymer having the hierarchical porosity prepared above was added thereto. This mixture was stirred at 298 K under a protective atmosphere of nitrogen gas for 24 hours, then the solvent was drawn off at room temperature under vacuum, and thereby a solid heterogeneous catalyst of metal Rh supported by the P-containing ligand polymer itself having the hierarchical porosity was obtained. The solid heterogeneous catalyst prepared above was added into a fixed bed reactor. Propylene gas as olefin raw material and CO/H 2 mixed gas (in which the volume ratio of H 2 :CO=1:1) in molar ratio of 1:2 were charged thereto. The reaction was started under the following conditions: at 393K, under 1.0 MPa, at a volume space velocity of the olefin gas of 1000 h −1 , at a volume space velocity of the CO/H 2 mixed gas of 2000 h −1 . The resultant liquid product butylaldehyde was collected in a cold trap collection tank. The liquid product was analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using ethanol as the internal standard. The tail gas of the reaction was on-line analyzed by an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The results were shown in Table 1.
Example 4
[0055] Concerning the synthesis of the tri(4-vinylphenyl)phosphine ligand polymer supporter, see Example 1. 12.53 mg of dicarbonylacetylacetonato rhodium (I) was dissolved into a three-necked flask charged with 100.0 ml of tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas by stirring. 1.0 g of the P-containing ligand polymer having the hierarchical porosity prepared above was added thereto. This mixture was stirred at 298 K under a protective atmosphere of nitrogen gas for 24 hours, then the solvent was drawn off at room temperature under vacuum, and thereby a solid heterogeneous catalyst of metal Rh supported by the P-containing ligand polymer itself having the hierarchical porosity was obtained. 1.2 g of 1-octene and 4.8 g of toluene as a solvent were weighed out and placed in an autoclave reactor, then the solid heterogeneous catalyst of Rh supported by the P-containing ligand polymer itself having the hierarchical porosity prepared above was added into the autoclave reactor. Once the reactor was closed and an airtight test was performed, syngas (in which the volume ratio of H 2 :CO=1:1) was charged, the air in the reactor was replaced 3 times, and then the syngas was continuously fed at 393 K under 1.0 MPa, until the reaction pressure was remained unchanged. When the stirring speed of the autoclave was 1000 rpm, the reaction was started. After 4 hours, the autoclave was opened, and the liquid product was extracted from the autoclave reactor, while the catalyst may be remained in the autoclave for recycle. The liquid product was analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using ethanol as the internal standard. The tail gas of the reaction was on-line analyzed by an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The results were shown in Table 1.
Example 5
[0056] Concerning the synthesis of the tri(4-vinylphenyl)phosphine ligand polymer supporter, see Example 1. 12.53 mg of dicarbonylacetylacetonato rhodium (I) was dissolved into a three-necked flask charged with 100.0 ml of tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas by stirring. 1.0 g of the P-containing ligand polymer having the hierarchical porosity prepared above was added therein. This mixture was stirred at 298 K under a protective atmosphere of nitrogen gas for 24 hours, then the solvent was drawn off at room temperature under vacuum, and thereby a solid heterogeneous catalyst of metal Rh supported by the P-containing ligand polymer itself having the hierarchical porosity was obtained. 1.2 g of 1-decene and 4.8 g of toluene as a solvent were weighed out and placed in an autoclave reactor, then the solid heterogeneous catalyst of metal Rh-supported by the P-containing ligand polymer itself having the hierarchical porosity prepared above was added into the autoclave reactor. Once the reactor was closed and an airtight test was performed, syngas (in which the volume ratio of H 2 :CO=1:1) was charged, the air in the reactor was replaced 3 times, and then the syngas was continuously fed at 393 K under 1.0 MPa, until the reaction pressure was remained unchanged. When the stirring speed of the autoclave was 1000 rpm, the reaction was started. After 4 hours, the autoclave was opened, and the liquid product was separated from the catalyst via filtration from the autoclave reactor, while the catalyst may be remained in the autoclave for recycle. The liquid product was analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using ethanol as the internal standard. The tail gas of the reaction was on-line analyzed by an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The results were shown in Table 1.
Example 6
[0057] Concerning the synthesis of the tri(4-vinylphenyl)phosphine ligand polymer supporter, see Example 1. 12.53 mg of dicarbonylacetylacetonato rhodium (I) was dissolved into a three-necked flask charged with 100.0 ml of tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas by stirring. 1.0 g of the P-containing ligand polymer having the hierarchical porosity prepared above was added thereto. This mixture was stirred at 298 K under a protective atmosphere of nitrogen gas for 24 hours, then the solvent was drawn off at room temperature under vacuum, and thereby a solid heterogeneous catalyst of metal Rh supported by the P-containing ligand polymer itself having the hierarchical porosity was obtained. The solid heterogeneous catalyst of Rh supported by the P-containing ligand polymer itself having the hierarchical porosity prepared above was added into a trickle bed reactor. Syngas (in which the volume ratio of H 2 :CO=1:1) was charged. The reaction was started under the following conditions: at 393K, under 3.0 MPa, at a space velocity of the syngas of 2000 at a mass space velocity of a liquid olefin (LHSV)=0.5 h −1 , wherein 1-dodecene liquid material was pumped into the reactor through a high-pressure metering pump. The liquid product aldehyde was collected in a cold trap collection tank. The liquid product was analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using ethanol as the internal standard. The tail gas of the reaction was on-line analyzed by an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The results were shown in Table 1.
Example 7
[0058] Concerning the synthesis of the tri(4-vinylphenyl)phosphine ligand polymer supporter, see Example 1. 12.53 mg of dicarbonylacetylacetonato rhodium (I) was dissolved into a three-necked flask charged with 100.0 ml of tetrahydrofuran at 298 K under a protective atmosphere of nitrogen gas by stirring. 1.0 g of the P-containing ligand polymer having the hierarchical porosity prepared above was added thereto. This mixture was stirred at 298 K under a protective atmosphere of nitrogen gas for 24 hours, then the solvent was drawn off at room temperature under vacuum, and thereby a solid heterogeneous catalyst of metal Rh supported by the P-containing ligand polymer itself having the hierarchical porosity was obtained. The solid heterogeneous catalyst of Rh supported by the P-containing ligand polymer itself having the hierarchical porosity prepared above was added into a trickle bed reactor. Syngas (in which the volume ratio of H 2 :CO=1:1) was charged. The reaction was started under the following conditions: at 393K, under 3.0 MPa, at a space velocity of the syngas of 2000 h −1 , at a LHSV=0.5 h −1 , wherein 1-octadecene liquid material was pumped into the reactor through a high-pressure metering pump. The liquid product aldehyde was collected in a cold trap collection tank. The liquid product was analyzed by an HP-7890N gas chromatograph equipped with an HP-5 capillary column and an FID detector, using ethanol as the internal standard. The tail gas of the reaction was on-line analyzed by an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The results were shown in Table 1.
[0000]
TABLE 1
the olefin hydroformylation reaction properties on the
novel heterogeneous catalyst
Selectivity, (wt %)
ratio of
normal
Olefin
product to
conversion,
isomeric
product
isomeric
Example
(%)
alkanes
olefins
aldehyde
product (n/i)
Example 1
99.8
0.35
—
99.65
—
Example 2
99.9
0.23
—
99.77
—
Example 3
97.33
1.58
—
98.42
3.06
Example 4
97.78
2.47
16.03
81.49
3.11
Example 5
99.22
0.72
15.76
83.53
3.38
Example 6
89.27
1.77
21.42
76.81
6.29
Example 7
87.39
0.78
25.42
73.8
7.59
[0059] As can be known from the results in Table 1 above, in the method for olefin hydroformylation reaction using novel solid heterogeneous catalyst provided by the invention, the reaction process and device are simple, and thus the reaction can be carried out in normal fixed beds, trickle beds, or autoclave reactors; it is suitable for various olefins of C 2 to C 18 ; the hydroformylation reaction has stable properties with a high yield. The invention solves the problems of the prior art, such as loss of the metal component, loss of the ligand, or the difficulty for recovery and recycle of the catalyst, and thus has a wide prospect in industrial applications.
[0060] The invention has been described in details above, but the invention is not limited to the particular embodiments described herein. Those skilled in the art will understand that other modifications and variations may be made, without departing the scope of the invention. The scope of the invention is defined by the appended claims.
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A method for an olefin hydroformylation reaction comprising subjecting olefins and CO/H2 mixed gas to the olefin hydroformylation reaction in a reactor in the presence of a solid heterogeneous catalyst, which consisting of a metal component and an organic ligand polymer with hierarchical porosity, in which the metal component is one or more of Rh, Ir or Co, the organic ligand polymer is a polymer formed by polymerization of an organic ligand monomer containing P and alkenyl group and optional N, and in the solid heterogeneous catalyst, the metal component forms coordinated bonds with the P atom or N in the backbone of the organic ligand polymer and exists in a monoatomic dispersion state; the reaction technique and device are simple, and the catalyst has a stable hydroformylation property with a high activity and yield.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for operating a roller, and a corresponding roller.
2. Description of the Prior Art
A roller is shown in DE-PS 34 45 890. This known roller is intended for operation with hydraulic oil, i.e., the two longitudinal chambers are filled with hydraulic oil. The longitudinal chamber located on the side of the roller nip has the higher pressure.
SUMMARY OF THE INVENTION
A disadvantage not only of the roller of DE-PS 34 45 890 but also of other deflection equalization rollers, is that at high speeds, they demonstrate a high internal consumption of drive power. Internal consumption of power refers to portions of the drive power which do not go into deformation of the product but instead are used up by the roller itself, i.e. would come about if the roller were rotating without product.
In so-called floating rollers, the power loss due to friction at the longitudinal seals and end cross-seals is comparably slight. The main portion of power loss lies in the losses due to internal fluid friction, which comes about due to the deflection, at the longitudinal seals, of the oil film entrained at the inside circumference of the hollow roller. Particularly at higher speeds, these losses due to fluid friction make up by far the major portion of the power demand.
The present invention is designed in such a way that the internal power losses are reduced.
This task is accomplished, in its method aspects, by the invention as described below according to a preferred embodiment. By using a gaseous pressure medium in the longitudinal chambers, the internal friction which occurs when the pressure medium layer entrained at the inside circumference of the hollow roller is deflected, and the resulting turbulence, are significantly reduced. The gaseous pressure medium, however, sets higher demands with regard to sealing of the longitudinal chambers, which are met by filling the spaces between the longitudinal seals and the end cross-seals with a sealing fluid. In order to make it impossible for the compressed gas to penetrate into these spaces, the pressure of the sealing fluid is higher than the pressure of the compressed gas, i.e., particularly higher than the pressure in the pressure-active longitudinal chamber on the side of the roller nip. Because of this condition, a small portion of the sealing fluid will constantly enter into the longitudinal chambers, going underneath the longitudinal seals and the end cross-seals, on the inside circumference of the hollow roller. If not corrected, this would result in filling the longitudinal chambers with sealing fluid over time. To prevent this from occurring, the penetrating sealing fluid is continuously removed, so that the pure gas filling of the longitudinal chambers is maintained.
The use of compressed gas as a pressure medium is known in deflection-controlled rollers. An example of this type of roller is shown in DE-PS 36 25 801, which shows a rotating hollow roller with a non-rotating cross-beam. The entire space between the cross-beam and the inside circumference of the hollow roller can be filled all around, i.e. without longitudinal seals, with a compressed gas; and zones can be created at individual points, by radial pressure punches, at which the gas pressure does not prevail. In this way, a unilateral force effect comes about. However, since no longitudinal seals are used here, which would seal off longitudinal chambers demonstrating different pressures from one another, the sealing problem does not exist, or does not exist to a comparable degree.
Another example of an air-supported roller is shown in DE-OS 41 03 799, which has a punch-supported deflection-controlled roller as the pressure roller of a film winder. No details of the formation of the air support are described in that patent.
In accordance with an embodiment of the present invention the compressed gas supplied to the pressure-active longitudinal chamber may be tempered, i.e., heated or, particularly, cooled. The latter comes into consideration when the machine is to run at very high speeds. Even a compressed gas heats up, in spite of the lesser internal friction as compared with a hydraulic fluid. This result can shift the desired processing temperature.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawing shows a schematic representation of an exemplary embodiment of the invention.
FIG. 1 shows cross-sections through the roller according to the present invention, specifically, in the right half shows inside the roller (seen in its longitudinal direction), in the left half shows the end region, so that the non-rotating carrier for the end cross-seals which is connected to the cross-beam can be seen;
FIG. 2 shows an enlarged partial view from the right half of FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
The roller 100 includes a fixed cross-beam 1, around which a hollow roller 2 rotates. The cross-beam 1 leaves a space 4 towards the inside circumference 3 of the hollow roller 2, so that the cross-beam can bend within the hollow roller 2 when a stress occurs in the roller nip W, without touching inside circumferences.
The forces caused by the line pressure in the roller nip W are transferred by the hollow roller 2, via a compressed gas in space 4, to the cross-beam 1. Which deflects under the effect of these forces and in this way generates the counter-forces which bring about equilibrium. In the exemplary embodiment shown in FIG. 1, the counter-roller 15 and the roller nip W are located on the top, so that the cross-beam 1 will deflect downwards. For this reason, the cross-beam 1 is slightly flattened on its bottom 1', in order to create room for this deflection, as can be seen in FIG. 1. The compressed gas is located in a semicylindrical longitudinal chamber 7 formed in the space 4. Chamber 7 is compartmentalized by end cross-seals 9 on an end cross-seal carrier 17 connected with the cross-beam 1. End cross seals 9 delimit the space 4 in the axial direction. Longitudinal seals arranged on both sides of the cross-beam 1, of which the longitudinal seal shown in the drawing, on the right side of FIG. 1, is designated as a whole with 5. A corresponding longitudinal seal is found on the left side, in FIG. 1, of the cross-beam, but is not shown in the left side of FIG. 1. In the exemplary embodiment, the two longitudinal seals 5 lie in a connecting plane 6, which is a perpendicular meridian plane to the plane of effect of the roller, i.e., the plane connecting the axes of the roller 100 and the counter-roller 15.
Because of the end dross-seals 9 and the longitudinal seals 5, two longitudinal chambers 7 and 8 are formed in the exemplary embodiment, of which the longitudinal chamber 7 can be filled with compressed gas via the feed line 18, in this exemplary embodiment, while the longitudinal chamber 8 does not have its own compressed gas feed line.
The longitudinal seal 5 and the end cross-seals 9 in each instance include two individual seal elements 20, 20 and 16, 16, respectively. The longitudinal seal 5 is structured to be symmetrical to the connecting plane 6. Close to the connecting plane 6, on both sides of it and at a slight distance from it, longitudinal recesses 23 with a stepped rectangular cross-section are milled into the circumferential surface of the cross-beam 1. The center plane of recess 23 are inclined slightly towards the connecting plane 6 and form an angle of approximately 5° with the latter. In the broader outer part of the longitudinal recesses 23, support strips 24 with an essentially rectangular cross-section are arranged. Support strips 2 are pressed against the flank of the longitudinal recess 23 which faces the connecting plane 6, by non-round wedging pieces 25. Wedging pieces 25 can rotate around cross-wise axes, and are wedged in place in this manner. On the outer corner of the cross-section, located away from the connecting plane 6, the support elements 24 possess a projection with an undercut 10 which is open towards the connecting plane 6. One of the two seal elements forming the longitudinal seals 5, in the form of sealing strips 20, engages undercut 10 with one of its longitudinal edges 11, from the connecting plane 6 side, for each undercut 10. The sealing strips 20 have an approximately L-shaped cross-section, and the longitudinal edge 11 is formed at the free end of the longer shank of the "L." Opposite the other end of the longer shank of the "L," adjacent to the connecting plane 6 is, the shorter shank which projects almost radially towards the inside circumference 3 of the hollow roller 2. The longitudinal edge 12 of sealing strips 20 which makes contact at roller 2 is formed at the free end of the shorter shank of the "L." The shorter shank is beveled, so that the longitudinal edge 12 forms a wiping edge. The sealing strips 20 are arranged symmetrical to the connecting plane 6, and are held in position and in contact with the inside circumference 3 under spring action by two spring strips 13. Spring strips 13 are wedged in under the support strip 24 and project freely, essentially radially outwardly, and rest against the outside of the shorter shank of the "L" with their free edge.
The sealing strips 20, just like the support strip 24, have cross-wise through-bores 14 and 26, respectively, distributed over their length, and open out into an oil drain space formed behind the support strips 24 by the narrower part 27 of the longitudinal recesses 23. The oil drain space extends over the length of the longitudinal seals 5, and is connected, in each instance, with one or more drain channels 28 distributed over the length. Drain channels 28 run in the cross-wise direction, and in turn lead into a longitudinal bore 29 of the cross-beam 1, through which the sealing fluid can be passed outside the cross-beam 1.
The distance between the wiping longitudinal edges 12 of the sealing strips 20 and the connecting plane 6 is about 5 to 20 mm, in a preferred embodiment.
Between the sealing strips 20, a space 30 is formed, into which the radial bores 31 which run between the longitudinal recesses 23 open out. Bores 31 are supplied with sealing fluid from a longitudinal bore 32.
The sealing strips 20 are made of a suitable bronze alloy, and forms an advantageous slip pairing with the steel of the inside circumference 3 of the hollow roller 2.
The end cross-seals 9 are each formed, in corresponding manner, from two sealing strips 16 which are parallel and spaced at a distance from one another. Sealing strips 16 have a rectangular cross-section, engage in rectangular grooves in the end cross-seal carrier 17 in the axial direction, and rest against a ring disk, (not shown), which rotates with the hollow roller 2, to form a seal. A space 30' after fluid which can be filled with sealing fluid is formed between the sealing strips 16.
In the exemplary embodiment, end cross-seals 9 are provided only for the upper longitudinal chamber 7, which is arranged on the side closest to the counter-roller 15 and supplied with compressed gas via the feed line 18. It is also possible, however, to provide end cross-seals for the lower longitudinal chamber 8, for example if the roller 100 is to operate optionally towards either the top or the bottom.
If the roller is supposed to generate a line pressure in the roller nip W between the roller 100 and the counter-roller 15 which acts towards the top, compressed gas under a corresponding pressure is fed to the longitudinal chamber 7 via the feed line 18. The pressure acts against the inside circumference 3 of the hollow roller 2, in its upper half, and produces a line force directed against the roller nip W. On the other hand, the compressed gas "supports" itself against the top of the cross-beam 1, which deflects downwards under these forces. The pneumatic pressure which prevails in the longitudinal chamber 7 acts on the sealing strip 20 shown in FIG. 1 and 2, if at all, in such a way that it is lifted from the inside circumference 3 of the hollow roller 2. Even if compressed gas also reaches the back of the upper sealing strip 20 via the bores 14 in the longer shank of the "L" and thus a certain pressure equalization takes place, a seal exists because of the contact of the spring strip 30 against the bottom of the shorter shank of the "L". Therefore the active surface of the prevailing pressure in the longitudinal chamber 7 will be greater on the top of the upper sealing strip 20 than on the bottom. It should be noted that the spring strips 13, just like the sealing strips 20, extend over the entire length of the longitudinal chambers 7, 8, without interruption.
Therefore, if the upper longitudinal chamber 7 is the "pressure-active" longitudinal chamber, the lower sealing strip 20 in FIG. 1 and 2 is the "active" sealing strip. It is necessary to ensure that the higher the pressure in the longitudinal chamber 7, the tighter this sealing strip is pressed against the inside circumference of the hollow roller 2 with its longitudinal edge 12. For this purpose, a pressure is generated in the space 30 between the sealing strips 20, by the sealing fluid, which pressure increases with the pressure in the longitudinal chamber 7 and is greater, in every case, than the pressure in the longitudinal chamber 7. In the arrangement shown, this pressure of the sealing fluid causes the lower sealing strip 20 to tilt around its longitudinal edge 11 in the undercut 10, in the clockwise direction, thereby pressing the lower sealing strip 20 firmly against the inside circumference of the rotating hollow roller 2, which causes the sealing force to be constantly adjusted to the pressure in the longitudinal chamber 7. The pressure of the sealing fluid in the space 30 also benefits the upper sealing strip 20, which provides a pre-seal in this manner. The sealing fluid in the space results in a much greater sealing effect on the sealing strips 20, because of its much greater viscosity in comparison with the compressed gas, so that the arrangement shown will still function even at higher pressures of the compressed gas in the longitudinal chamber 7, without overly high losses of compressed gas occurring.
Because of the adhesion of the sealing fluid to the inside circumference 3 of the hollow roller 2 which passes by the spaces 30, and is conveyed by the higher pressure of the sealing fluid, a certain proportion of sealing fluid is constantly entrained into the longitudinal chambers, going under the sealing strips 20. This would normally result in the longitudinal chambers 7, 8 filling with oil after a certain period of operation, causing high losses of driver power due to internal friction of the fluid. In order to prevent this, the cross-bores 14 and 26, respectively, are provided in the sealing strips 20 and the support strips 24, respectively, leading into the drain channels 28. As the hollow roller 2 rotates, specifically at the sealing strip 20 against which the inside circumference of the hollow roller 2 makes contact, an accumulation of fluid with a certain internal pressure forms there, because the sealing fluid wiped off the inside circumference collects there. As a result the sealing fluid which has gotten into the longitudinal chambers 7, 8 and has been wiped off the sealing strips 20 is constantly driven out through the drain channels 28, so that the longitudinal chambers 7, 8 cannot fill.
The compressed gas which is brought in via the feed line 18 can be passed into a heat exchanger and tempered there before entering into the feed line. This is particularly appropriate if the roller 100 is operated at high speeds and heating of the compressed gas by its internal friction must be counteracted.
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In a "floating" roller with a fixed cross-beam and a rotating hollow roller, semicylindrical longitudinal chambers are separated and divided off by longitudinal seals and end cross-seals in the space between the crosshead and the hollow roller. At least the longitudinal chamber on the roller nip side can be filled with a compressed gas. The longitudinal seals and the end cross-seals are doubled and are made of closely juxtaposed pairs of sealing strips or. Into the spaces between the sealing strips can be introduced a sealing liquid which seals the longitudinal chambers. Sealing liquid which has penetrated into the longitudinal chambers is continuously removed.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation of U.S. application Ser. No. 09/777,335 filed Feb. 6. 2001 (issued as U.S. Pat. No. 6,652,765); which is a continuation of U.S. patent application Ser. No. 09/259,432 filed Mar. 1, 1999 (issued as U.S. Pat. No. 6,491,723), which is a continuation of U.S. patent application Ser. No. 08/607,903, filed Feb. 27, 1996 (issued as U.S. Pat. No. 5,876,453), which is a continuation-in-part of pending U.S. patent application Ser. No. 08/351,214, filed Nov. 30, 1994, (now abandoned) for “Implant Surface Preparation.”
FIELD OF THE INVENTION
The present invention relates to processes for improving the surfaces of devices to be surgically implanted in living bone, and to implant devices having the improved surfaces.
BACKGROUND OF THE INVENTION
The success of prosthetic devices surgically implanted in living bone depends substantially entirely on achieving and maintaining an enduring bond between the confronting surfaces of the device and the host bone. Surgical procedures for preparing living bone to receive a surgically implanted prosthetic device have been known for twenty years or more, but considerable controversy remains concerning the ideal properties of the surface of the device which confronts the host bone.
It is known through clinical experience extending over several decades that titanium and its dilute alloys have the requisite biocompatability with living bone to be acceptable materials for use in making surgically implantable prosthetic devices, when the site of installation is properly prepared to receive them. There is, however, less certainty about the ideal physical properties of the surfaces of the prosthetic devices which confront the host bone. For example, the endosseous dental implant made of titanium enjoys sufficient predictable success to have become the artificial root most frequently chosen for restoring dentition to edentulous patients, but that success depends in part on the micromorphologic nature of the surface of the implant which comes in contact with the host bone. Because there is no standard for the surface micromorphology of dental implants, the surfaces of commercial implants have a wide range of available textures. It is known that osseointegration of dental implants is dependent, in part, on the attachment and spreading of osteoblast-like cells on the implant surface. It appears that such cells will attach more readily to rough surfaces than to smooth surfaces, but an optimum surface for long-term stability has not yet been defined.
Wilke, H. J. et al. have demonstrated that it is possible to influence the holding power of implants by altering surface structure morphology: “The Influence of Various Titanium Surfaces on the Interface Strength between Implants and Bone”, Advances in Biomaterials , Vol. 9, pp. 309-314, Elsevier Science Publishers BV, Amsterdam, 1990. While showing that increased surface roughness appeared to provide stronger anchoring, these authors comment that it “cannot be inferred exclusively from the roughness of a surface as shown in this experiment. Obviously the shear strength is also dependent on the kind of roughness and local dimensions in the rough surface which can be modified by chemical treatment.”
Buser, D. et al., “Influence of Surface Characteristics on Bone Integration of Titanium Implants”, Journal of Biomedical Materials Research , Vol. 25, pp. 889-902, John Wiley & Sons, Inc., 1991, reports the examination of bone reactions to titanium implants with various surface characteristics to extend the biomechanical results reported by Wilke et al. The authors state that smooth and titanium plasma sprayed (“TPS”) implant surfaces were compared to implant surfaces produced by alternative techniques such as sandblasting, sandblasting combined with acid treatment, and plasma-coating with HA. The evaluation was performed with histomorphometric analyses measuring the extent of the bone-implant interface in cancellous bone. The authors state, “It can be concluded that the extent of bone-implant interface is positively correlated with an increasing roughness of the implant surface.”
Prior processes that have been used in attempts to achieve biocompatible surfaces on surgically implantable prosthetic devices have taken many forms, including acid etching, ion etching, chemical milling, laser etching, and spark erosion, as well as coating, cladding and plating the surface with various materials, for example, bone-compatible apatite materials such as hydroxyapatite or whitlockite or bone-derived materials. Examples of U.S. patents in this area are U.S. Pat. No. 3,855,638 issued to Robert M. Pilliar Dec. 24, 1974 and U.S. Pat. No. 4,818,559 issued to Hama et al. Apr. 04, 1989. A process of ion-beam sputter modification of the surface of biological implants is described by Weigand, A. J. et al. in J. Vac. Soc. Technol ., Vol. 14, No. 1, Jan/Feb 1977, pp. 326-331.
As Buser et al. point out (Ibid p. 890), the percentage of bone-implant contact necessary to create sufficient anchorage to permit successful implant function as a load-bearing device over time remains unclear. Likewise, Wennerberg et al., “Design and Surface Characteristics of 13 Commercially Available Oral Implant Systems”, Int. J. Oral Maxillofacial Implants 1993, 8:622-633, show that the different implants studied varied considerably in surface topography, and comment: “Which of the surface roughness parameters that will best describe and predict the outcome of an implant is not known” (p. 632).
Radio-frequency glow-discharge treatment, also referred to as plasma-cleaning (“PC”) treatment, is discussed in Swart, K. M. et al., “Short-term Plasma-cleaning Treatments Enhance in vitro Osteoblast Attachment to Titanium”, Journal of Oral Implantology , Vol. XVIII, No. 2 (1992), pp. 130-137. These authors comment that gas plasmas may be used to strip away-organic contaminants and thin existing oxides. Their conclusions suggest that short-term PC treatments may produce a relatively contaminant-free, highly wettable surface. U.S. Pat. No. 5,071,351, issued Dec. 10, 1991, and U.S. Pat. No. 5,188,800, issued Feb. 23, 1993, both owned by the assignee of the present application, describe and claim methods and means for PC cleaning of a surgical implant to provide a contact angle of less than 20 degrees.
Copending application Ser. No. 08/149,905, filed Nov. 10, 1993, owned by the assignee of the present application, describes and claims inventions for improving the surfaces of surgically implantable devices which employ, among other features, impacting the surface with particles of the same material as the device to form the surface into a desired pattern of roughness.
SUMMARY OF THE INVENTION
It is a primary object of the present invention to produce an implant surface having a roughness that is substantially uniform over the area of the implant that is intended to bond to the bone in which the implant is placed.
It is a further object of this invention to provide an improved surgically implantable device having on its surface a substantially uniform micromorphology.
It is another object of the invention to provide a process or processes for manufacturing such improved implant devices.
It is an additional object of the invention to provide such improved implant devices which can be manufactured without contaminating the surfaces thereof.
It is a more specific object of the invention to provide an improved etch-solution process that will result in a substantially uniform surface topography on surgically implantable devices.
In accordance with the present invention, the foregoing objectives are realized by removing the native oxide layer from the surface of a titanium implant to provide a surface that can be further treated to produce a substantially uniform surface texture or roughness, and then performing a further, and different, treatment of the resulting surface substantially in the absence of unreacted oxygen. The removal of the native oxide layer may be effected by any desired technique, but is preferably effected by immersing the implant in hydrofluoric acid under conditions which remove the native oxide quickly while maintaining a substantially uniform surface on the implant. The further treatment is different from the treatment used to remove the native oxide layer and produces a desired uniform surface texture, preferably acid etching the surface remaining after removal of the native oxide layer. To enhance the bonding of the implant to the bone in which it is implanted, a bone-growth-enhancing material, such as bone minerals, hydroxyapatite, whitlockite, or bone morphogenic proteins, may be deposited on the treated surface. The implant is preferably maintained in an oxygen-free environment following removal of the native oxide layer, in order to minimize the opportnity for oxide to re-form before the subsequent treatment is performed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic sectional view taken through a body of titanium covered with a layer of native oxide;
FIG. 2 is the same section shown in FIG. 1 after impacting the surface with a grit;
FIG. 3 is the same section shown in FIG. 2 after bulk etching with an acid etch;
FIG. 4 is the same section shown in FIG. 2 after first removing the native oxide and then bulk etching with an acid;
FIGS. 5A and 5B are scanning electron micrographs (“SEMs”) of two titanium dental implants prepared in accordance with the present invention;
FIGS. 6A and 6B are SEMs of the same implants shown in FIGS. 5A and 5B , at a higher magnification level;
FIG. 7 is a graph of the results of an Auger electron spectroscopic analysis of a titanium surface that has been exposed to air;
FIGS. 8A and 8B are SEMs of two titanium dental implants prepared in accordance with the present invention; and
FIGS. 9A and 9B are SEMs of the same implants shown in FIGS. 8A and 8B , at a higher magnification level.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Turning now to the drawings, and referring first to FIG. 1 , a titanium body 10 which has been exposed to air has on its outer surface 12 an irregular layer 14 of an oxide or oxides of titanium which form naturally. This oxide layer 14 is referred to herein as the “native oxide” layer, and typically has a thickness in the range from about 70 to about 150 Angstroms. The native oxide layer that forms naturally on titanium when it is exposed to air is actually a combination of different oxides of titanium, including TiO, TiO 2 , Ti 2 O 3 and Ti 3 O 4 . The concentration of these oxides in the titanium body diminishes with distance from the surface of the body. The oxide concentration may be measured in an Auger spectrometer.
Auger electron spectroscopy (AES) measures the energy of Auger electrons produced when an excited atom relaxes by a radiationless process after ionization by a high energy electron, ion or x-ray beam. The spectra of a quantity of electrons emitted as a function of their energy reveal information about the chemical environment of the tested material. One of the major uses of AES is the depth profiling of materials, to reveal the thickness (depth) of the oxide layer on the surfaces of materials. These Auger electrons lie in an energy level that extends generally between the low energy level of the emission of secondary electrons up to the energy of the impinging electron beam. In this region, small peaks will occur in the spectra at certain energy levels that identify the existence of certain elements in the surface.
As used herein, the term “native oxide layer” refers to the layer which extends from the surface of the material to the depth at which the energy of the peak-to-peak oxygen profile as measured in an Auger electron spectrometer decreases by one-half. For example, in the peak-to-peak oxygen profile reproduced in FIG. 7 , the thickness of the native oxide layer was 130 Angstroms, which is the depth at which the oxygen profile dropped to half its maximum intensity. Thus, removal of a 130-Angstrom layer from the surface of the titanium body would remove the native oxide layer.
FIG. 2 depicts the surface 12 of the titanium body 10 after being grit blasted to achieve initial roughening, as described in more detail below. The oxide layer 14 is still present, but it has a rougher surface than in its original state depicted in FIG. 1 .
FIG. 3 depicts the grit-blasted surface 12 of the titanium body 10 after it has been bulk etched in an etching acid. The etched area 16 where the native oxide layer 14 has been removed by the etching acid exhibits a much finer roughness, but in areas where the oxide layer remains, the initial roughness depicted in FIG. 2 also remains.
FIG. 4 depicts the grit-blasted surface 12 of the titanium body 10 after it has been etched in a first acid to remove the native oxide layer 14 , and then in a second acid to produce the desired topography on the surface 16 produced by the first acid treatment. As described in more detail below, the preferred surface topography has a substantially uniform, fine roughness over the entire surface 16 .
Among the processes previously used to improve the surfaces of dental implants made of titanium is that of etching the surface with an acid, such as a mixture of two parts (by volume) sulfuric acid and one part (by volume) muriatic acid. It has been found that such acid treatments do not etch an oxidized implant surface uniformly or consistently from one region to another.
According to one aspect of the present invention, the native oxide layer is removed from the surface of a titanium implant prior to the final treatment of the surface to achieve the desired topography. After the native oxide layer is removed, a further and different ‘treatment of the surface is carried out in the absence of unreacted oxygen to prevent the oxide layer from re-forming until after the desired surface topography has been achieved. It has been found that this process permits the production of unique surface conditions that are substantially uniform over the implant surface that is so treated.
Removal of the native oxide layer can be effected by immersing the titanium implant in an aqueous solution of hydrofluoric (HF) acid at room temperature to etch the native oxide at a rate of at least about 100 Angstroms per minute. A preferred concentration for the hydrofluoric acid used in this oxide removal step is 15% HF/H 2 O. This concentration produces an etch rate of approximately 200-350 Angstroms per minute at room temperature, without agitation, so that a typical native oxide layer having a thickness in the range from about 70 to about 150 Angstroms can be removed in about one-half minute. Other suitable etching solutions for removing the native oxide layer, and their respective etch rates, are:
50% HF—etch rate˜600 to 750 Angstroms/min.
30% HF—etch rate˜400 to 550 Angstroms/min.
10% HF—etch rate˜100 to 250 Angstroms/min.
A 100% HF was found to be difficult to control, and the etch rate was not determined. The preferred 15% HF solution allows substantially complete removal of the native oxide layer with minimum further consumption of the titanium surface after the implant is removed from the solution.
The native oxide layer may be removed by the use of other acids, or by the use of techniques other than acid etching. For example, the Swart et al. article cited above mentions the use of plasma cleaning to remove thin oxides. Regardless of what technique is used, however, it is important to remove substantially all the native oxide from the implant surface that is intended to interface with the living bone, so that the subsequent treatment of that surface produces a substantially uniform surface texture to promote uniform bonding to the living bone. The native oxide layer is preferably removed from substantially the entire bone-interfacing surface of the implant. In the case of screw-type dental implants, such as implant 10 , illustrated in FIG. 10 , the bone-interfacing surface typically includes the entire implant surface beyond a narrow collar region 14 on the side wall of the implant at the gingival end 12 thereof. This narrow collar region 14 preferably includes the first turn of the threaded portion 16 of the implant. It is preferred not to etch the gingival end 12 itself, as well as the narrow collar region 14 , because these portions of the implant are normally fabricated with precise dimensions to match abutting components which are eventually attached to the gingival end 12 of the implant. Moreover, it is preferred to have a smooth surface on that portion of a dental implant that is not embedded in the bone, to minimize the risk of infection.
The treatment that follows removal of the native oxide layer must be different from the treatment that is used to remove the native oxide layer. A relatively aggressive treatment is normally required to remove the oxide layer, and such an aggressive treatment does not produce the desired uniform surface texture in the resulting oxide-free surface. Thus, after the native oxide layer has been removed, the resulting implant surface is immediately rinsed and neutralized to prevent any further attack on the implant surface. The surface is then subjected to the further, and different, treatment to produce a desired uniform surface texture. For example, the preferred further treatment described below is a relatively mild acid-etching treatment which forms a multitude of fine cone-like structures having relatively uniform, small dimensions. Because of the prior removal of the native oxide layer, even a mild second treatment of the implant surface can produce a substantially uniform effect over substantially the entire bone-interfacing surface of the implant.
Prior to removing the native oxide layer, the oxide-bearing surface may be grit blasted, preferably with grit made of titanium or a dilute titanium alloy. As is taught in the aforementioned copending U.S. patent application Ser. No. 08/149,905, the use of a grit made of titanium avoids contaminating the surface of a titanium implant. Thus, for a dental implant made of commercially pure (“CP”) titanium, the blasting material may be CP B299 SL grade titanium grit. The preferred particle size for this grit is in the range from about 10 to about 60 microns (sifted), and the preferred pressure is in the range from about 50 to about 80 psi.
The surface treatment that follows removal of the native oxide layer from the implant surface may take several forms, singly or in combination. The preferred treatment is a second acid etching step, using an etch solution (“Modified Muriaticetch”) consisting of a mixture of two parts by volume sulfuric acid (96% by weight H 2 SO 4 , 4% by weight water) and one part by volume hydrochloric acid (37% by weight HCI, 63% by weight water) at a temperature substantially above room temperature and substantially below the boiling point of the solution, preferably in the range from about 60° C. to about 80° C. This mixture provides a sulfuric acid/hydrochloric acid ratio of about 6:1. This preferred etch solution is controllable, allowing the use of bulk etch times in the range from about 3 to about 10 minutes. This solution also can be prepared without the risk of violent reactions that may result from mixing more concentrated HCI solutions (e.g., 98%) with sulfuric acid. This second etching treatment is preferably carried out in the absence of unreacted oxygen, and before the implant surface has been allowed to re-oxidize, following removal of the native oxide layer. Of course, the implants may be kept in an inert atmosphere or other inert environment between the two etching steps.
The second etching step produces a surface topography that includes many fine projections having a cone-like aspect in the sub-micron size range. Because of the fine roughness of the surface, and the high degree of uniformity of that roughness over the treated surface, the surface topography produced by this process is well suited for osseointegration with adjacent bone. As illustrated by the working examples described below, the final etched surface consists of a substantially uniform array of irregularities having peak-to-valley heights of less than about 10 microns. Substantial numbers of the irregularities are substantially cone-shaped elements having base-to-peak heights in the range from about 0.3 microns to about 1.5 microns. The bases of these cone-shaped elements are substantially round with diameters in the range from about 0.3 microns to about 1.2 microns, and spaced from each other by about 0.3 microns to about 0.75 microns. The SEMs discussed below, and reproduced in the drawings, illustrate the surface topography in more detail.
The acid-etched surface described above also provides a good site for the application of various materials that can promote bonding of the surface to adjacent bone. Examples of such materials are bone-growth-enhancing materials such as bone minerals, bone morphogenic proteins, hydroxyapatite, whitlockite, and medicaments. These materials are preferably applied to the etched surface in the form of fine particles which become entrapped on and between the small cone-like structures. The bone-growth-enhancing materials are preferably applied in the absence of oxygen, e.g., using an inert atmosphere.
The roughness of the surface to which these materials are applied enhances the adherence of the applied material to the titanium implant. The uniformity of the rough surface enhances the uniformity of the distribution of the applied material, particularly when the material is applied as small discrete particles or as a very thin film.
A preferred natural bone mineral material for application to the etched surface is the mineral that is commercially available under the registered trademark “BIO-OSS”. This material is a natural bone mineral obtained from bovine bone; it is described as chemically comparable to mineralized human bone with a fine, crystalline biological structure, and able to support osseointegration of titanium fixtures.
The invention will be further understood by reference to the following examples, which are intended to be illustrative and not limiting:
EXAMPLE NO. 1
A batch of 30 screw-type cylindrical implants made of CP titanium were grit blasted using particles of CP B299 SL grade titanium grit having particle sizes ranging from 10 to 45 microns, at a pressure of 60 to 80 psi. After grit-blasting, native oxide layer was removed from the implant surfaces by placing 4 implants in 100 ml. of a 15% solution of HF in water at room temperature for 30 seconds. The implants were then removed from the acid, neutralized in a solution of baking soda, and placed in 150 ml. of “Modified Muriaticetch” (described above) at room temperature for 3 minutes. The implants were then removed from the acid, neutralized, rinsed and cleaned. All samples displayed very similar surface topographies and a high level of etch uniformity over the surface, when compared with each other in SEM evaluations. Consistency in the surface features (peaks and valleys) was also observed. The SEMs in FIGS. 5A , 5 B, 6 A and 6 B show the surfaces of two of the implants, Sample A-1 and Sample A-4, at magnifications of 2,000 and 20,000. It will be observed that the surface features over the areas shown are consistent and uniform. The scale shown on the X20,000 photographs is 1 micron=0.564 inch. At this magnification the surfaces appear to be characterized by a two-dimensional array of cones ranging in height (as seen in the SEMs) from about 0.17 inch to about 0.27 inch; the base diameters of these cones varied from about 0.17 inch to about 0.33 inch. Converting these numbers to metric units on the above-mentioned scale (1 micron=0.564 inch) yields:
cone height range (approx.)=0.30 to 0.50 micron
cone base diameter range (approx.)=0.30 to 0.60 micron.
The same degree of uniformity was found in all the samples, and from sample to sample, at magnifications of 2,000 and 20,000, as compared with similar samples subjected to bulk etching without prior removal of the native oxide, as described in EXAMPLE NO. 2 below.
EXAMPLE NO. 2
Four of the implants that had been grit blasted as described in EXAMPLE NO. 1 above were placed in 150 ml. of “Modified Muriaticetch” for 10 minutes. The implants were then removed, neutralized, rinsed and cleaned. SEM photographs taken at magnifications of 2,000 and 20,000 showed that the bulk etch solution failed to remove the native oxide layer after 10 minutes in the etch solution. The failure to remove the native oxide layer (100-150 Angstrom units thick) resulted in a non-uniformly etched surface, as depicted in FIG. 3 . In areas of the implant surfaces where the native oxide was removed, the topography was similar to that observed on the implants in EXAMPLE NO. 1.
EXAMPLE NO. 3
The procedure of this example is currently preferred for producing commercial implants. A batch of screw-type implants made of CP titanium were immersed in a 15% solution of HF in water at room temperature for 60 seconds to remove the native oxide layer from the implant surfaces. A plastic cap was placed over the top of each implant to protect it from the acid. The implants were then removed from the acid and rinsed in a baking soda solution for 30 seconds with gentle agitation. The implants were then placed in a second solution of baking soda for 30 seconds, again with agitation of the solution; and then the implants were rinsed in deionized water. Next the implants were immersed in another solution of two parts by volume sulfuric acid (96% by weight H 2 SO 4 , 4% by weight water) and one part by volume hydrochloric acid (37% by weight HCl, 63% by weight water) at 70° C. for 5 minutes. The implants were then removed from the acid and rinsed and neutralized by repeating the same steps carried out upon removal of the implants from the HF. All samples displayed very similar surface topographies and a high level of etch uniformity over the surface, when compared with each other in SEM evaluations. Consistency in the surface features (peaks and valleys) was also observed. The SEMs in FIGS. 8A , 8 B, 9 A and 9 B show the surfaces of two of the implants, Sample 705MB and Sample 705MC, at magnifications of 2,000 and 20,000. It will be observed that the surface features over the areas shown are consistent and uniform. The scale shown on the X20,000 photographs is 1 micron=0.564 inch. At this magnification the surfaces appear to be characterized by a two-dimensional array of cones ranging in height (as seen in the SEMs) from about 0.17 inch to about 1.128 inch; the base diameters of these cones varied from about 0.17 inch to about 1.128 inch. Converting these numbers to metric units on the above-mentioned scale (1 micron=0.564 inch) yields:
cone height range (approx.)=0.30 to 0.20 microns
cone base diameter range (approx.)=0.30 to 0.20 microns.
The same degree of uniformity was found in all the samples, and from sample to sample, at magnifications of 2,000 and 20,000, as compared with similar samples subjected to bulk etching without prior removal of the native oxide, as described in EXAMPLE NO. 2 above.
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The surface of a device that is surgically implantable in living bone is prepared. The device is made of titanium with a native oxide layer on the surface. The method of preparation comprises the steps of removing the native oxide layer from the surface of the device and performing further treatment of the surface substantially in the absence of unreacted oxygen.
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BACKGROUND
[0001] Filtering contaminates from flowing fluids is a common exercise in systems involved in transportation of fluids. Many such systems employ screens as the filtering mechanism. Screens that expand to substantially fill an annular gap, for example, between concentric tubulars, is another common practice. Some of these systems use swaging equipment to radially expand the screen. Although such equipment serves its purpose it has limitations, including a limited amount of potential expansion, complex and costly equipment and an inability to expand to fill a nonsymmetrical space. Apparatuses and methods that overcome these and other limitations with existing systems are therefore desirable to operators in the field.
BRIEF DESCRIPTION
[0002] Disclosed herein is a screen. The screen includes, a body having a permeable material with energy stored therein configured to change the body from a first volume to a second volume, and a binder in operable communication with the body configured to retain the body in the first volume until the binder is weakened sufficiently for the energy stored within the body to overcome the binder and allow the body to change from the first volume toward the second volume.
[0003] Further disclosed herein is a method of expanding a screen. The method includes, generating energy within a permeable body sufficient to change the body from a first volume to a second volume, binding the permeable body to prevent the generated energy from expanding the permeable body from the first volume to the second volume, weakening the binding to a level sufficient to allow the generated energy to expand the permeable body from the first volume to the second volume, and expanding the body from the first volume toward the second volume.
[0004] Further disclosed herein is a method of conforming a screen to a borehole. The method includes, positioning a screen within a borehole, weakening a binding maintaining the screen at a first volume, expanding the screen toward a second volume with energy stored within the screen, and contacting walls of the borehole with the screen.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
[0006] FIG. 1 depicts a quarter cross sectional view of a screen disclosed herein in an unexpanded configuration; and
[0007] FIG. 2 depicts a quarter cross sectional view of the screen of FIG. 1 in an expanded configuration.
DETAILED DESCRIPTION
[0008] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
[0009] Referring to FIGS. 1 and 2 , an embodiment of a screen disclosed herein is illustrated generally at 10 . The screen 10 includes, a body 14 made of a fluid permeable material 18 with energy stored therein that allows the body 14 to expand from a first volume as illustrated in FIG. 1 to a second volume that is a larger than the first volume. The body 14 , as illustrated in FIG. 2 , has a larger volume than the first volume but is somewhat less than the second volume due to the body 14 contacting walls 22 of a borehole 26 within which the body 14 is positioned. A binder 30 made of a removable material 34 structurally constrains the body 14 at the first volume until the binder 30 is weakened sufficiently to allow the stored energy to be released. During release of the stored energy the body 14 expands toward the second volume.
[0010] The binder 30 , in this embodiment, is a solid that is distributed within the body 14 thereby structurally constraining the body 14 at the first volume. Weakening of the binder 30 can be accomplished in different ways, depending upon the material that the binder 30 is made of. For example, when the binder 30 is made of a dissolvable material exposing the binder 30 to an applicable solvent will allow the binder 30 to dissolve thereby allowing the stored energy to be released and the body 14 to expand toward the second volume. One example of a usable binder material that is soluble in water is the synthetic polymer, polyvinyl alcohol. Dissolution of the binder 30 made of polyvinyl alcohol in water weakens the structural integrity thereof until the energy stored in the body 14 is able to break the binder 30 apart expanding the body 14 in the process. Dissolution of polyvinyl alcohol, like many soluble materials, is accelerated at increased temperatures.
[0011] In an alternate embodiment, the binder 30 could be made of a material having a low melting temperature relative to that of the body 14 . Such an embodiment would allow an operator to release the energy stored in the body 14 by increasing the temperature sufficiently to melt the binder 30 . In still other embodiments, the binder 30 could be made of a material that can be chemically degraded when exposed to a chemical, such as an acid for example. An operator could then expose the binder 30 to an applicable acid to initiate the chemical degradation needed to release the energy within the body 14 .
[0012] Generating energy in the body 14 can be achieved in different ways depending upon the material, chemical and physical characteristics of the body 14 . For example, the body 14 could be made of a material capable of regaining its original shape after being deformed, such as a polymer, that is made into a mat of substantially randomly oriented filaments extruded from one or more spinnerets, for example. The mat could then be compacted to the first volume where it is bound by the binder 30 . An alternate embodiment could employ open celled foam that is deformed through an extrusion process before being bound by the binder 30 .
[0013] Regardless of the material or structure of the body 14 , the body 14 will have fluid filtration characteristics defined by the body 14 . The filtration characteristics, however, may differ depending upon what volume the body 14 is taking. As such, an operator may set the desired filtration characteristics at a volume that the body 14 is expected to have when fully deployed.
[0014] Referring again to FIGS. 1 and 2 , the screen 10 , as illustrated, is employed in a sand screen within the wellbore 26 in an earth formation 38 . The body 14 of the screen 10 is run into the borehole 26 while in the compacted first volume configuration as shown in FIG. 1 . An annular gap 42 between an outer surface 46 of the body 14 and an inner surface 50 defined by the walls 22 of the borehole 26 allow the body 14 to be run without detrimentally scraping the walls 22 . Once the screen 10 is at the desired position within the borehole 26 initiation of degradation of the binder 30 , as discussed above, can begin. Upon sufficient degradation of the binder 30 the body 14 can expand into contact with the walls 22 . The nature of the structure of the body 14 allows it to contact the walls 22 regardless of whether the walls 22 are cylindrical or not and regardless of whether the annular gap 42 is of a consistent size or not. In fact, the walls 22 need not even be symmetrical about the body 14 . Additionally, since the volume of the body 14 , as illustrated in FIG. 2 , is less than the second volume the body 14 will exert a force against the walls 22 . This force will help prevent erosion of the walls 22 that could occur due to fluid flow if a portion of the annular gap 42 were allowed to exist between the walls 22 and the outer surface 46 after the body 14 has expanded.
[0015] In the sand screen application, the screen 10 is positioned on a tubular 54 having perforations 58 therethrough. Fluid, upon being filtered after it flows through the body 14 is able to flow through the perforations 58 and into an inside 62 of the tubular 54 . Once on the inside 62 the fluid can flow longitudinally through the tubular 54 as desired.
[0016] While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
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A screen includes, a body having a permeable material with energy stored therein configured to change the body from a first volume to a second volume, and a binder in operable communication with the body configured to retain the body in the first volume until the binder is weakened sufficiently for the energy stored within the body to overcome the binder and allow the body to change from the first volume toward the second volume.
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The present invention relates to a multifunctional module, units to be used in a multifunctional module, a process for operating a multifunctional module, and use of a multifunctional module.
BACKGROUND
Spinning reactors etc. are unusual in industrial processes even though there are several patents disclosing spinning discs. The spinning disc reactors disclosed by the patents are often complicated and not useful in full scale or pilot scale processes. The technique is utilising the centrifugal force which necessitates very careful design and demand on parts and materials, which also will be more evident when complicated chemical reactions are applied to the technique. Therefore, one problem to be solved by the present invention is how to design a spinning disc reactor module which will fulfil criteria such as mixing immiscible fluids, production of high yields, separation of products etc. Another problem is cleaning of the reactor, and thus accessibility to the interior of the reactor. Yet another problem is how to achieve multifunction to a spinning disc reactor module.
SUMMARY
Accordingly, the present invention provides in on aspect, a solution to the above mentioned technical problems by providing a spinning multifunctional module or a multifunctional module, which comprises one or more units selected from the group consisting of reactor units, filter units, membrane units, reactor-separation units, clarification units, purification units, extraction units, contactor units, and mixer units etc. The spinning multifunctional module has to have at least one unit having a member which rotates around an axis. The units of the multifunctional module can be connected parallel or in series or both to each other. The module can have one or more inlets and one or more outlets, and the module could also comprise a foundation for the units. The foundation could have connections between the units integrated in the foundation, or the connections between the units could be between the units above the foundation. A cover or a hood could cover the foundation and the units leaving the inlets and the outlets to be connected to feeds and end-product collections on the outside of the cover or hood.
The unit operations carried out by the module could be a combination of mixing, blending, reaction, separating, etc. or the module may be a combination of units within the same unit operation, thus the module could for instance separate different fractions of a mixture within a module having different separation units. A module according to the invention could as an alternative carry out one step or several step synthesis, thus be a combination of reactor units and separation units etc. The spinning multifunctional module of the invention comprises units operating under different modes, for instance a reactor unit within the module facilitates contact between reactants that a reaction can take place. A filter unit is a unit wherein a filter is one of the components, a membrane unit is a similar unit. In a filter unit or a membrane unit particles or molecules are separated from the fluids. In a reactor-separator unit reactions take place as well as separation of the product mixture. A clarification unit is a unit wherein a liquid is clarified from particles or sludge, and a purificator unit purifies for instance a fluid. An extractor unit facilitates extraction of for instance substances from one fluid to another or the extraction could be to or from a gas and/or to or from a liquid. A contractor unit could be a packed bed or a fluidised bed. A mixer unit could for instance mix two immiscible fluids to produce for instance an emulsion, or a dispersion, but other types of mixing could also be performed in a mixer unit.
The units of the multifunctional module according to the present invention may have at least one member having a surface, which surface is rotating with the member. The mentioned surface is the surface on which the operation takes place, thus the surface herein is called the operating surface or just surface. The operations could be mixing, reaction, separation etc. The rotating member could be of any type which rotates around an axis, the member could be a disc, such a member is for example a flat or planar disc herein called a T-disc. Another example is a cone-disc, which is a cone with an open end turning upwards, hereinafter called Y-disc. Yet another type of rotating member is a more complicated structure with enhanced surfaces, with two horizontal surfaces separated by a plurality of walls which surround the axis of rotation and which walls divergently extend from one horizontal surface towards the opposite horizontal surface this type of member is hereinafter called a Z-disc. Yet another type of member is the delta disc which has a shape like an upside down turned cone with the small end turning upwards, this type of member is hereinafter called Δ-disc. The rotating member according to the invention could thus be selected from one or more of T-discs, Y-discs, Z-discs, and Δ-discs. The operating surface of the rotating member could be on the outside surfaces of the T-discs, the Y-discs, the Z-discs, or the Δ-discs, or the operating surface could be integrated with the member in the form of one or more channels. The member is rotating around an axis during operation and is operating under centrifugal force, thus creating transportation of products, mixing of products, separation of components, etc., and can be performed in a number of levels and connections within the discs or between discs. The centrifugal force makes heavier components be transported out from the centre of the member to the circumferential edge or only a part of the distance to the edge of the member. The number of revolutions the member is rotating with could be adjusted to optimize the predicted operation. One or more chambers are co-rotating with the rotating member and collecting the materials from the member. The chambers can be surrounding the member's circumferential edge, or the chamber could be below the member's circumferential edge, or the chamber could be over the member's circumferential edge, or the chamber could be at the member's circumferential edge. Within the chamber could a stator be arranged opposite the rotating member. The chambers could be paring chambers having one or more paring devices which could be paring discs, paring tubes or paring passage or combinations thereof. The paring passage could be closed or open, and the paring devices are arranged to the chamber to set a surface of the fluids of the chamber to a certain pre-determined level within the rotating paring chamber. The paring devices could be connected to the paring chambers from below and thus making it possible to lead out fluids by gravitation. The feed of fluids to channels within a disc could also be arranged together with a paring tube, such an arrangement make it possible to feed fluids at different levels within a disc having several layers of channels within the disc. A feed paring tube consists of two tubes one for leading fluids into the channel and one to set the fluid surface to a pre-determined level at an inlet compartment of the disc.
One or more paring discs could be centred on the axis of the rotating member leading out fluids which are close to the centre of the surface or could the paring disc have a radius corresponding to the rotating member, and the paring disc could be a stator which is arranged opposite the rotating member. The paring discs could have any diameter all depending on fraction of the fluids which should be lead out from rotating discs. The fluids could thus be pumped up through the axis of a stator or of a rotating member by the paring discs.
The module of the present invention may also comprise one or more static separators connected to the units having rotating members. The static separators could be connected to the units parallel, or in series, or both, to the units within the module. According to this can the module consist of one or more units having rotating members and one or more static separators. The static separators could be selected from settling tanks, cyclones, coalescer, contractors, filters, membranes, affinity member. One or more high speed separators, or one or more decanter centrifuges, or combinations thereof could be connected to the units parallel, or in series, or both, to the units within the module. Then module could be a combination of the units having rotating members together with any combinations of static separators, high speed separators, and decanter centrifuges.
The present invention relates in another aspect to a reactor unit or a mixer unit. The reactor unit or the mixer unit comprise at least one rotating member having a surface, which surface is rotating with the member, and the member being selected from the group consisting of T-discs, Y-discs, Z-discs, and Δ-discs. The rotating member of the unit rotates around an axis making the unit operate under centrifugal force. The reactor unit or the mixer unit comprises also one or more inlets for fluids above the member at the centre of the disc at the axis or within a radial distance from the centre of the disc, that the fluids are mixed, or reacted or transported, or combinations thereof by radial velocity to the circumferential edge of the member. The unit comprises further one or more chambers for fluids co-rotating with the member. The chambers can be surrounding the member's circumferential edge, or the chambers can be below the member's circumferential edge, or the chambers can be over the member's circumferential edge, or the chambers can be at the member's circumferential edge.
The reactor unit or the mixer unit can comprise one or more inlets for fluids at the centre of the disc at the axis leading fluids into channels within the rotating member. The channels within the discs are going from the centre to the circumference in radial direction leading the incoming fluids to the circumferential edge. The one or more channels may communicate with each other at one or more connection places making two ore more fluids to mix and/or react with each other. The channels may be arranged on several levels in the disc. Channels of different levels can be connected to force two or more fluids to mix and/or to react with each other. Two or more channels at the same level can be connected that two or more fluids could mix and/or react with each other.
The present invention relates in a further aspect to a filter unit or membrane unit comprising at least one member having a surface, which surface is rotating with the member, and the member being selected from the group consisting of T-discs, Y-discs, Z-discs, and Δ-discs. The member is rotating around an axis making the unit operate under centrifugal force, and the member comprises at least two compartments divided by a membrane or a filter or both. One or more inlets for fluids are attached above the disc surface at the centre of the disc at the axis or within the radial distance from the centre, and a part of the fluids are going through the filter or going through the membrane and being transported by radial velocity to the circumferential edge. The filter unit or the membrane unit comprises further one or more chambers for fluids co-rotating with the member. The chambers could be surrounding the member's circumferential edge, or the chambers could be below the member's circumferential edge, or the chambers could be over the member's circumferential edge, or the chambers could be at the member's circumferential edge.
The above mentioned chambers for fluids could be paring chambers having one or more paring discs, paring tubes or paring passage, or combinations thereof, arranged to the surface of the fluids within the one or more paring chambers. The paring passage could be closed or open. The paring discs, tubes or passages can be arranged to lead out the fluids from the chambers, into one or more outlets in radial direction from the member, into one or more outlets below the member, or into one or more outlets above the member, or through the axis up or down, or combinations thereof.
The present invention relates in yet another aspect to a reactor-separator unit comprising at least one member having a surface, which surface is rotating with the member, and the member being selected from the group consisting of T-discs, Y-discs, Z-discs, and Δ-discs. The member of the reactor-separator is rotating around an axis making the unit operate under centrifugal force. The unit may also comprise one or more inlets for fluids above the discs, but inlets could also be below the disc. The reactor-separator unit comprises one or more paring chambers having paring tubes which paring chambers are co-rotating with the members. The paring tubes connected to chambers will set the surface of the fluids in the chambers. The rotating members and the co-rotating chambers are arranged on the same axis as a centrifugal separator, which could be of any type and be arranged above, below or around the rotating members and the co-rotating chambers. The rotating member and the co-rotating chamber can be centred on the same axis as a centrifugal bowl having a stack of separating discs within a centrifugal rotor. The centrifugal rotor, the stack of separating discs can be centred below or above the member on the same axis. The stack of separating discs and centrifugal rotor are co-rotating with the member and the paring chambers. At least one of the paring tubes or paring passages can be connected between at least one of the paring chambers and the centrifugal rotor leading fluids into the centrifugal rotor.
The present invention relates further to an extractor unit comprising at least one member having a surface, which surface is rotating with the member, and the member being selected from the group consisting of T-discs, Y-discs, Z-discs, and Δ-discs. The member of the extractor is rotating around an axis making the unit operate under centrifugal force. The extractor unit comprises one or more paring chambers having paring tubes which paring chambers are co-rotating with the members. Inlets for fluids and gas, or liquids, are arranged that the flows are co-current of counter-current through the unit. A centrifugal rotor may have a centrifugal bowl and a stack of separating discs on the same axis as the rotating member and co-rotating chambers. The centrifugal rotor may surround the rotating member, be on top of the rotating member or below. The separating discs could thus surround the rotating member and the co-rotating chamber, or the separating discs could be below or above the rotating member. A paring tube or a paring disc could transfer fluids into the centrifugal bowl from the rotating member having the co-rotating chamber.
The above mentioned units may have a plate or a shroud centred on the axis of the member attached to cover the surface of the member or attached coextensive to the surface of the member leaving a gap between the plate or the shroud and the rotating member. The plate or the shroud could be stationary or could be rotating with a different number of revolutions than the rotating member, and the plate or shroud could be co-rotating with the rotating member or be counter-rotating with the rotating member. The shroud or plate could be heat exchanged by heat exchanging fluids. A paring disc could be discharging the fluids through the outlet in the axis of the stationary plate or the stationary shroud, or a pump could be connected to the inlet for pumping the fluids out through the outlet in the axis.
The above mentioned rotating members, i.e. the discs, of the invention could be covered by a housing, and the housing could be provided with inlets and outlets for fluids, such as liquid fluids, sols, gases, fluidised particles etc. The housing could be sealed to contain a gaseous media. The units could also be hermetically sealed. Gas tight gaskets could seal the parts and the rotating axis at the transition places between the different parts.
At least one surface of the members or at least a part of the surface of the members of the present invention could be coated with one or more catalyst.
In the following the present invention will be described with the aid of figures. FIGS. 1 to 15 are only examples of the inventions explaining the invention and are not intended to limit the scope of invention.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows a spinning module according to the invention
FIG. 2 shows a T-disc according to the invention
FIG. 3 shows a T-disc with a stator according to the invention
FIG. 4 shows an inlet to a T-disc having channels according to the invention.
FIG. 5 shows another view of the T-disc having channels.
FIG. 6 shows yet another view of the T-disc having channels.
FIG. 7 shows a membrane or filter unit according to the invention.
FIG. 8 shows a Δ-disc within a centrifugal separator according to the invention.
FIG. 9 shows another Δ-disc within a centrifugal separator according to the invention.
FIG. 10 shows a Δ-disc unit according to the invention.
FIG. 11 shows a hermetic unit according to the invention.
FIG. 12 shows another hermetic unit according to the invention.
FIG. 13 shows a Z-disc according to the invention.
FIG. 14 shows a Y-disc according to the invention.
FIG. 15 shows detailed drawing of a paring tube located under a T-disc according to the invention.
DETAILED DESCRIPTION
FIG. 1 shows a multifunctional module having four units 1 , the units can have different sizes, be for different types of operations etc. A module could have units 1 selected from units having rotating members, i.e. the discs, of the invention, static separators, high sped separators or decanter centrifuges. In FIG. 1 the units are under a hood 2 on a foundation 3 . A feed 4 into the module and a product line 5 out of the module are shown in the figure illustrating that the process module is continuous. How the units are configured in the modules depends on space, type of operations and sequence of operations, the units could be connected in series and thus the units may put in a row or the units could be placed in a square which is shown in the figure. A combination of units connected in series and parallel to each other is one alternative to the module shown in FIG. 1 , another could be that all units are connected parallel. All units in a module could be “spinning” or have parts which rotate around an axis, or some of the units may be stationary units.
FIG. 2 shows two equipments according to the invention, in FIG. 2 two different arrangements are illustrated in the figure one on each side of the axis 6 A+B. A and B represent two different types of equipments, but A and B represent also two different feed inlets of reactants which will react with each other and form a product C. On the A side of the equipment a stator 7 is arranged above a T-disc 8 . Stator 7 and T-disc 8 are arranged that a gap is made between stator 7 and T-disc 8 to facilitate room for reactions. Fluid motion created by stator 7 and disc 8 can facilitate better fluid motion for better reaction between different components in the inlet feeds. On the B side of the equipment there is no stator leaving the reaction surface open. Feeds of reactants A and B are inlet at the centre of the T-disc 8 , but reactants could also be let in within a part of radial distance from the centre, the reactants start to react and mix and form a film or layer on the disc surface. Reactants and products are transported by centrifugal force to the edge of the disc where a chamber 9 collects the material. The number of revolutions the disc rotates with depends on different properties such as viscosity of reaction mixture, reaction time etc. Chamber 9 is co-rotating with T-disc 8 . In FIG. 2 the disc is represented by a disc attached to a shaft 10 , but according to the invention it is also included that disc 8 is not attached to a shaft instead the disc is mounted on chamber 9 which chamber is connected to the driving force of the motor according to this alternative, this alternative is not shown in the figure. A paring tube 11 is connected from below the disc to chamber 9 for transportation of product mixture C out from chamber 9 . According to this placement of paring tube 11 it is possible to transport C by gravity from chamber 9 . The dynamic pressure forces the fluids out of the chamber.
FIG. 3 shows a unit having a T-disc with a co-rotating chamber for products. The process mixture is transported by paring disc 12 from the co-rotating chamber according to this alternative of the invention, and the process mixture is then pumped out through stator shaft 13 . A housing 14 is closing the disc from the surrounding that gas could be added. FIG. 3 shows also how heat to and from the units is transferred by heat exchanger fluids. The heat exchanger fluids are transported in channels 15 through rotating shaft 16 from below opposite to the process surface of disc 8 . Disc 8 is according to this alternative not attached to rotating shaft 16 instead disc 8 is mounted to the co-rotating chamber. A stator 7 , which could be paring disc but not necessary, is attached to stator shaft 13 .
FIGS. 4 , 5 and 6 show a T-disc having integrated process channels 17 . Inlets 18 are feeding process fluids into channels 17 . In FIG. 4 a paring tube 19 secures the surface level in a process fluid path 20 connected to channels 17 . FIG. 6 shows outlet tubes 21 leading out process products from the co-rotating chambers within the disc, which are not shown in details in FIG. 6 .
FIG. 7 shows a filter or membrane unit according to the invention. Process fluids are lead into chamber 22 wherein a filter 23 or a membrane 23 is dividing chamber 22 into two compartments. The process fluids are separated through the filter or the membrane and both concentrate and filtrate, or permeate are transported by centrifugal force to be collected in co-rotating chambers, not shown in details in FIG. 7 . A paring tube 24 is transferring concentrate from co-rotating chamber intended for collecting concentrate up through a stator shaft 13 . The filtrate or the permeate is transferred by paring tube 25 up through stator shaft 13 . A paring tube or paring disc will pump both concentrate and filtrate/permeate through the stator shaft. Paring discs could exchange one or both paring tubes 24 and 25 according to one alternative.
FIG. 8 shows a Δ-disc 26 within a centrifugal bowl 27 according to the invention. This alternative is without an extractor. Inlets 28 for process fluids are centred on a stator shaft feeding process fluids into a space between Δ-disc 26 and a rotor body 29 . The process fluids are reacted and the product mixture is transported on the surface of Δ-disc 26 to be collected in a co-rotating chamber 30 which is according to this embodiment a centrifugal bowl 27 . Within the centrifugal bowl is a stack of separating discs 31 . Separating discs 31 provide an enhanced surface to the separating equipment. The product mixture is separated and the different fractions of the product mixture are pumped out of the centrifugal bowl by one or more paring discs 32 . Heat exchanger fluids are feed from inlet 33 a into Δ-disc 26 thus leading heat to and from the process reactions. The heat exchanged fluids are collected in a chamber 34 and transferred out by paring tube 35 .
FIG. 9 shows an alternative Δ-disc with an extractor. According to this alternative can gas be feed trough an inlet or outlet through shaft 33 c into or out from space 36 between Δ-disc 26 and rotor body 29 and be connected with outlet or inlet 33 b and the unit will act as an extractor.
FIG. 10 shows a Δ-disc having a paring tube 37 or a paring disc 37 at the bottom of the disc transporting process fluids from chamber 38 . The fluids are transported up through the stator shaft 39 . As an alternative could a paring disc be transporting fluids from chamber 38 through rotating shaft 40 , not shown in FIG. 10 . Feed inlets 41 are feeding the process fluids into the Δ-disc and the fluids are transferred by centrifugal force down to chamber 38 where the fluids are collected before further transportation.
FIG. 11 shows a hermetic unit having a T-disc 44 . According to this version of the present invention process fluids are feed up through rotation shaft 43 to the above surface of the stator 42 . The process fluids will be pumped down from the surface of T-disc 44 through rotating shaft 43 from the chamber. Heat exchanger fluids are also transported up and down through rotation shaft 43 for heat transfer to and from T-disc 44 . A housing 45 is sealing the T-disc from the surrounding environment. FIG. 12 shows also a hermetic T-disc unit. According to this alternative the process fluids are feed through inlet 46 in housing 45 . The process fluids are let out through outlet 47 in the housing. A heat exchanger 48 is centred on the rotating shaft to heat exchange the heat exchanging fluids internally to and from the T-disc.
FIG. 13 shows a Z-disc having two horizontal surfaces 49 and 50 separated by a plurality of walls 51 and 52 . Walls 51 and 52 surround the axis of rotation and divergently extend from one horizontal surface towards the opposite horizontal surface.
FIG. 14 shows a Y-disc 53 according to the invention. Process fluids are feed through inlet 54 from above the Y-disc. The process fluids are let out at the bottom surface of the Y-disc. By centrifugal force are the fluids forced up on the surface of the y-disc and collected in chamber 55 . A paring disc 56 or a paring tube 56 is transferring the fluids from chamber 55 . The Y-disc is cold or heated by heat exchanger fluids, which are let in and out through shaft 57 into a space 58 between the Y-disc and rotor 59 .
FIG. 15 shows a more detailed figure of an unit having a paring tube 60 located under a T-disc 61 for transportation of fluids out from a paring chamber 62 , there may be more than one paring tube 60 located under the disc. In this figure it is shown how paring tube 60 sets fluids surface 63 on a predetermined level depending on the position of paring tube 60 in chamber 62 . In this figure T-disc 61 is mounted on a rotor body 64 . The figure shows also that paring chamber 62 is attached to rotor body 64 by one or more bolts 65 . A stator 66 , according to this alternative, is placed over T-disc 61 leaving a gap 67 for fluids, which fluids are feed through inlet 68 in the stator shaft. According to another alternative, not shown in FIG. 15 , can the stator be redundant leaving the rotating fluid surface open under housing cover 69 . According to another alternative, not shown in FIG. 15 , can stator 66 be a paring disc, but then may paring tube 60 be redundant in some applications, but not necessary. In case of a paring disc then T-disc 61 is mounted in such way that chamber 62 will cover T-disc 61 and the paring disc. According to this alternative will the fluids from chamber 62 be pumped up through housing cover 69 by the paring disc. FIG. 15 shows inlets 70 a and outlets 70 b for heat exchanger fluids, which are arranged in rotating shaft 71 letting the heat exchanger fluids be pumped to channels 72 under T-disc 61 to heat or to cool the disc. The shape of the disc according to the alternative, which is shown in FIG. 15 , is T-disc 61 in form of a plate mounted on a rotor body 64 , but according to other alternatives may the shape of the disc be a T-disc, Y-disc, Z-disc, or a Δ-disc. The shape of the disc is dependent on the purpose of the unit and FIG. 15 shows a T-disc but the invention is not limited to this version. When a T-disc, Y-disc, Z-disc, or a Δ-disc is used, all of these types of the discs are mounted on rotor body 64 and not on a rotating shaft, of course can the discs be mounted on a rotating shaft but not according to the alternatives of FIG. 15 . Therefore, the Y-disc will be a cone shaped bowl with the smaller end in downward direction, the Δ-disc will also have a cone shape but in this alternative is the smaller end in the upward direction. The Z-disc could be turned both ways since there is symmetry in the disc. Paring chamber 62 is mounted together with the selected disc on rotor body 64 covering the disc and the rotor body according to these alternatives of the invention. Depending on which disc is used paring chamber 62 have different sizes to be able to cover both disc and rotor body. Housing cover 69 can have one or more feed inlets and/or one or more feed outlets, none of these are shown in FIG. 15 except feed inlet 68 which is one alternative. As another alternative, not seen in FIG. 15 , can a centrifugal rotor having a centrifugal bowl and a stack of separating discs be centred on the same axis as the disc and paring chamber 62 . The centrifugal rotor may surround the disc, or be on top of the disc or below the disc. The separating discs could thus surround the disc, or the separating discs could be below or above disc 61 . A paring tube or a paring disc could transfer fluids into the centrifugal bowl from chamber 62 when the centrifugal bowl is below disc 61 . When the centrifugal bowl is above disc 61 then a paring disc could pump fluids from paring chamber 62 into the centrifugal bowl. According to the alternatives of the invention presented in FIG. 15 the selection of disc 61 is flexible allowing the unit to be put together depending on the purpose of the unit. The unit is thus very flexible and adaptable.
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The present invention relates to a multifunctional module comprising one or more units selected from the group consisting of reactor units, filter units, membrane units, reactor-separator units, clarificator units, purificator units, extractor units, and mixer units. The units are connected parallel or in series or both to each other, and each unit has at least one member having a surface, which surface is rotating with the member. The member is rotating around an axis making the unit operate under centrifugal force. One or more chambers for fluids are co-rotating with the rotating member. The present invention relates further to units which could be used in a spinning multifunctional module, and use of a spinning multifunctional module.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of U.S. Provisional Patent Application No. 61/577,831, filed Dec. 20, 2011, which is incorporated herein by reference in its entirety.
BACKGROUND
[0002] Laundry treating appliances, such as clothes washers, may include a perforate rotatable drum or basket positioned within an imperforate tub. The drum may at least partially define a treating chamber in which a laundry load may be received for treatment according to a selected cycle of operation. During at least one phase of the selected cycle, the drum and laundry load may be spun about a rotational axis at a predetermined high speed, sufficient to centrifugally force and hold the laundry load against the perimeter of the treating chamber, causing liquid to be removed from the laundry load. This speed may be referred to as the “satellization” speed.
[0003] Known methodologies may provide an estimate of satellization speed based upon a determination of laundry load inertia or mass, or the employment of an iterative process of drum rotation. However, these methods may be inaccurate, or inefficient. It would be advantageous to efficiently determine the satellization speed accurately for a selected laundry load.
BRIEF DESCRIPTION OF THE INVENTION
[0004] According to an embodiment of the invention, a method of operating a laundry treating appliance is disclosed. The laundry treating appliance may include a rotatable treating chamber for receiving a laundry load for treatment, and a motor for rotating the treating chamber. The method may include accelerating the rotational speed of the treating chamber from a non-satellizing speed to a satellizing speed by increasing the rotational speed of the motor; generating a first torque signal indicative of the motor torque over time for at least a portion of the accelerating; comparing the shape of the first torque signal to the shape of a second torque signal indicative of rotating the treating chamber when the laundry load is satellized within the treating chamber; and determining the laundry load is satellized when the shape of the first torque signal matches the shape of the second torque signal.
[0005] According to another embodiment of the invention, a laundry treating appliance for automatically treating a laundry load according to at least one cycle of operation is disclosed. The laundry treating appliance may include a rotatable treating chamber for receiving the laundry load for treatment; a motor for rotating the treating chamber; a speed sensor outputting a speed signal indicative of the rotational speed of the motor; a torque sensor outputting a torque signal indicative of the torque of the motor; and a controller operably coupled to the motor and receiving the speed signal and torque signal. The controller may provide an acceleration signal to the motor to increase the rotational speed of the motor to accelerate the rotational speed of the treating chamber from a non-satellizing speed to a satellizing speed. The controller may also determine that the treating chamber has reached the satellizing speed by determining when the shape of at least a portion of the torque signal matches a corresponding portion of a reference torque signal, which is indicative of the torque when the laundry load is satellized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] In the drawings:
[0007] FIG. 1 is a vertical sectional view of a laundry treating appliance in accordance with an exemplary embodiment of the invention.
[0008] FIG. 2 is a schematic view of a control system comprising a part of the laundry treating appliance illustrated in FIG. 1 .
[0009] FIGS. 3A-C are schematic views of the rotation of a laundry load in a rotating drum for increasing drum rotation speeds, where the motion of the laundry changes from tumbling ( FIG. 3A ) to satellized ( FIG. 3C ).
[0010] FIGS. 4A-B are graphical representations of a sinusoidal reference torque curve and an actual torque curve for a rotating laundry load at an increasing drum rotation speed.
[0011] FIGS. 5A-C are graphical representations of a reference torque curve and an actual torque curve in raw form, in reference, scaled, and biased form, and in reference, scaled, biased, and shifted form.
[0012] FIGS. 6A-C are graphical representations of a reference torque curve and an actual torque curve in reference, scaled, biased, and shifted form, in reference, scaled, biased, shifted, and frequency adjusted form based upon 100 data samples per cycle, and in reference, scaled, biased, shifted, and frequency adjusted form based upon 200 data samples per cycle.
[0013] FIGS. 7A-B are graphical representations of an array of data points representing actual torque and an array of reference torque data points twice the number of the actual torque data points.
[0014] FIGS. 8A-C are graphical representations of a reference torque curve and an actual torque curve generated during an exemplary 4 th drum revolution ( FIG. 8A ), an exemplary 5 th drum revolution ( FIG. 8B ), and an exemplary 6 th drum revolution ( FIG. 8C ), illustrating a comparison metric that decreases to a value below a threshold value as the reference torque curve and actual torque curve become coincidental.
DETAILED DESCRIPTION
[0015] FIG. 1 is a schematic view of a laundry treating appliance 10 according to an embodiment of the invention. The laundry treating appliance 10 may be any appliance which performs a cycle of operation to clean or otherwise treat items placed therein, non-limiting examples of which include a horizontal or vertical axis clothes washer; a combination washing machine and dryer; a tumbling or stationary refreshing/revitalizing machine; an extractor; a non-aqueous washing apparatus; and a revitalizing machine. Exemplary embodiments of the invention will be described herein in the context of a horizontal axis clothes washing machine.
[0016] The laundry treating appliance 10 is illustrated in FIG. 1 as including a structural support system comprising a cabinet 12 defining a housing within which a laundry holding system may reside. The cabinet 12 may be a housing having a chassis and/or a frame, defining an interior enclosing components typically found in a conventional washing machine, such as motors, pumps, fluid lines, valves, controls, sensors, transducers, and the like. Such components will not be described further herein except as necessary for a complete understanding of the invention.
[0017] The laundry holding system may comprise a tub 14 supported within the cabinet 12 by a suitable suspension system 16 , and a drum 18 provided within the tub 14 defining at least a portion of a laundry treating chamber 20 . The drum 18 may include a plurality of perforations 22 such that liquid may flow between the tub 14 and the drum 18 through the perforations 22 . A plurality of baffles 24 may be disposed on an inner surface of the drum 18 to lift a laundry load 26 received in the treating chamber 20 while the drum 18 rotates. It is also within the scope of the invention for the laundry holding system to comprise only a tub, with the tub defining the laundry treating chamber.
[0018] Other known components may include a door 28 which may be movably mounted to the cabinet 12 to selectively close both the tub 14 and the drum 18 . A bellows 30 may couple an open face of the tub 14 with the cabinet 12 , with the door 28 sealing against the bellows 30 when the door 28 closes the tub 14 .
[0019] The suspension system 16 may include one or more suspension elements, such as springs, dampers, lifters, cushions, bumpers, and the like, for dynamically suspending the laundry holding system within the structural support system.
[0020] The laundry treating appliance 10 may also include a wash aid dispensing system 32 , a liquid distribution system 34 , a liquid recycling/disposal system 36 , and a drum drive system 40 , which will be described further only as necessary for a complete understanding of the invention.
[0021] The drum drive system 40 , for rotating the drum 18 within the tub 14 may include a motor 42 , which may be directly coupled with the drum 18 through a drive shaft 44 to rotate the drum 18 about a rotational axis during a cycle of operation. The motor 42 may be a brushless permanent magnet (BPM) motor. Other motors, such as an induction motor or a permanent split capacitor (PSC) motor, may also be used. The motor 42 may rotate the drum 18 at various speeds in either rotational direction.
[0022] The laundry treating appliance 10 may include a control system 50 for controlling the operation of the laundry treating appliance 10 to implement one or more cycles of operation. The control system 50 may include a controller 52 located within the cabinet 12 and a user interface 54 that is operably coupled with the controller 52 . The user interface 54 may include one or more knobs, dials, switches, displays, touch screens and the like for communicating with the user, such as to receive input and provide output. The user may enter different types of information including, without limitation, cycle selection and cycle parameters, such as cycle options. The controller 52 may control the operation of the laundry treating appliance 10 utilizing a selected motor-control process, such as a closed loop speed control process.
[0023] As illustrated in FIG. 2 , the controller 52 may be provided with a memory 56 and a central processing unit (CPU) 58 . The memory 56 may be used for storing the control software that is executed by the CPU 58 in completing a cycle of operation using the laundry treating appliance 10 and any additional software, plus motor torque signals and reference torque signals. Examples, without limitation, of cycles of operation include: wash, heavy duty wash, delicate wash, quick wash, pre-wash, refresh, rinse only, and timed wash. The memory 56 may also be used to store information, such as a database or table, and to store data received from one or more components of the laundry treating appliance 10 that may be communicably coupled with the controller 52 . The database or table may be used to store the various operating parameters for the one or more cycles of operation, including factory default values for the operating parameters and any adjustments to them by the control system or by user input.
[0024] The controller 52 may be operably coupled with one or more components of the laundry treating appliance 10 for communicating with and controlling the operation of the components to complete a cycle of operation. For example, the controller 52 may be operably coupled with the wash aid dispensing system 32 , the liquid distribution system 34 , the liquid recycling/disposal system 36 , the drum drive system 40 , valves, diverter mechanisms, flow meters, and the like, to control the operation of these and other components to implement one or more of the cycles of operation.
[0025] One or more sensors and/or transducers, which are known in the art, may be provided in one or more of the systems of the laundry treating appliance 10 , and coupled with the controller 52 , which may receive input from the sensors/transducers. Non-limiting examples of sensors that may be communicably coupled with the controller 52 include a treating chamber temperature sensor, a moisture sensor, a load sensor 60 , a wash aid sensor, and a position sensor, which may be used to determine a variety of system and laundry characteristics, such as laundry load inertia or mass. Motor speed and motor torque may be represented by outputs provided by the motor 42 , or may be provided by a motor speed sensor 62 and motor torque sensor.
[0026] A summary of the disclosed method may be described as follows. During a cycle of operation, the drum 18 may be accelerated one or more times to remove liquid from the laundry load 26 . During the acceleration of the drum 18 , the motor torque may be sampled over each drum revolution and compared to one period of a reference sine wave. A metric may be developed that quantifies a variation in a torque sample buffer relative to the reference sine wave signal. The metric may be devised to be a function of the variation, such that a change in the variation, results in a change in the metric. For simplicity, it is contemplated that an increase in the variation will result in an increase in the metric. The speed at which the laundry load 26 becomes completely satellized may be determined by monitoring the metric for each drum revolution, and comparing it to a preselected threshold metric value. Load satellization may be indicated once the metric drops below the threshold value.
[0027] At drum rotational speeds lower than the satellization speed, as illustrated in FIG. 3A , some or all of the laundry load 26 may be tumbling. At this speed, illustrated in FIG. 4A , the motor torque signal 66 may have high-frequency components 68 , 70 , 72 , 74 effectively superimposed on a generally sinusoidal reference drum frequency signal 76 , which may be the result of portions of the laundry load following a trajectory inside the drum 18 that is shorter than one full drum revolution ( FIG. 3A ). As the rotational speed increases, and a larger percentage of the load is forced against the interior of the drum 18 ( FIG. 3B ), the torque signal 66 may trend toward a sinusoid, e.g. between the 4th and 6th time interval or drum revolution of FIG. 4A , having a frequency approaching the drum frequency 76 , and may have fewer high-frequency components. As the drum speed reaches, and then exceeds, the satellization speed ( FIG. 3C ), the torque signal 66 may develop into a sine wave having a frequency matching the drum rotational frequency, the magnitude of which may be proportional to the degree of off-balance of the laundry load in the drum 18 .
[0028] This behavior of the torque signal 66 may be attributed to the orientation of a horizontal axis drum 18 , and an interaction between a laundry load 26 and a closed loop speed controller. When the drum 18 is stationary, a wet load may rest on the bottom of the drum 18 . A typical speed profile, illustrated in FIG. 4B , utilized to distribute laundry items about the interior of the drum 18 may be a ramp 80 accelerating at a fixed rate from about 40 RPM to about 100 RPM. As the speed increases, the combination of friction and baffles 24 along the interior perimeter of the drum 18 may catch some of the laundry load 26 and lift it up along the side of the drum 18 until portions of the load separate from the drum 18 and drop back to the bottom.
[0029] A mass of laundry along the interior perimeter of the drum wall may change the balance of the drum 18 , which may cause a somewhat reduced drum speed. In order to track a selected speed profile target as closely as possible, the speed controller may increase the motor torque. When a laundry load portion separates from the drum wall, the speed may increase slightly, leading the controller 52 to call for a reduced torque to appropriately regulate the speed. This repeated variation in torque and/or speed may cause a relatively high-frequency torque ripple that may be observed at rotational speeds less than the satellization speed.
[0030] As the selected speed profile continues, the drum 18 accelerates, and through the combined effect of the baffles 24 and drum wall friction, the laundry load may accelerate as well. The uncontrolled process of laundry load portions adhering to and separating from the interior of the drum 18 may continue until the laundry load has achieved a high enough rotational speed that centrifugal force overcomes the force of gravity at the top of the drum 18 , and the load remains distributed along the drum wall through a complete revolution of the drum 18 . Centrifugal force (CF) is a function of a mass (m) of an object, e.g. a laundry item, an angular velocity (w) of the object, and a distance, or radius (r) at which the object is located with respect to an axis of rotation (X), or a drum axis. Specifically, the equation for the centrifugal force (CF) acting on a laundry item within the drum 18 is:
[0000] CF= m*ω 2 *r
[0031] The centrifugal force (CF) acting on any single item in the laundry load may be modeled by the distance the center of gravity of that item is from the axis of rotation (X) of the drum 18 . Thus, when the laundry items are stacked upon each other, which is often the case, those items having a center of gravity closer to the axis of rotation (X) experience a smaller magnitude centrifugal force (CF) than those items having a center of gravity farther away. It is possible to control the speed of rotation of the drum 18 such that the closer items will experience a centrifugal force (CF) less than 1 G, permitting them to tumble, while the farther away items still experience a centrifugal force (CF) equal to or greater than 1 G, retaining them in a fixed position relative to the drum 18 .
[0032] Momentum may also urge the laundry load to travel a complete revolution across the top of the drum 18 at slightly lower speeds than the satellization speed. While some portions of the load may remain against the drum wall, the radius of rotation for other, tumbling portions may decrease. Thus, the tumbling portions must be rotated at a higher higher speed to overcome gravity. For example, if a 4-inch thick layer of laundry load is distributed about the inside perimeter of the drum 18 , the speed required to satellize any tumbling items may be approximately 15 RPMs higher than if the drum 18 were empty.
[0033] The following equation may define the torque, T, for a fully satellized laundry load:
[0000] T=J{dot over (ω)}+Cω+D+A cos(θ DRUM )+ B sin(θ DRUM ),
[0000] where
T: Torque, J: Inertia, C: Viscous damping coefficient, D: Coulomb friction torque, ½√{square root over (A 2 +B 2 )}: Unbalance torque amplitude, and θ DRUM : Drum position.
[0040] For a fixed speed, viscous damping coefficient, and coulomb friction coefficient, the torque equation may simplify to the following:
[0000] T=K 1 +A cos(θ DRUM )+ B sin(θ DRUM ),
[0000] where
K 1 =Cω+D, {dot over (ω)}=0, T=K 1 +√{square root over (A 2 +B 2 )}*sin(θ DRUM +π/4), T=K 1 +K 2 sin (θ DRUM +φ), and K 2 =√{square root over (A 2 +B 2 )}.
[0046] The position of the drum may be a function of time:
[0000] θ DRUM =ω*t.
[0047] Therefore, the torque may be a function of time:
[0000] T ( t )= K 1 +K 2 sin(ω* t +φ).
[0048] As may be recognized, the torque may be a sinusoid with a DC offset K 1 , amplitude K 2 , and frequency co, which is equal to the drum frequency in radians per second.
[0049] For a constant acceleration, the torque equation may include an additional speed dependency as follows:
[0000] T=J {dot over (ω)}+ Cω+D+K 2 sin(θ DRUM +φ), and
[0000] T=Cω+K 1 +K 2 sin(θ DRUM +φ),
[0000] where
[0000] K 1 =J {dot over (ω)}+ D.
[0050] In the case of constant acceleration, the drum speed and drum position are functions of time as follows:
[0000] ω( t )= t *RR+ω(0),
[0000] where
RR=ramp rate (rad/sec), ω(0)=speed at t=0, θ DRUM (t)=∫ 0 t ω(τ)dτ, θ DRUM (t)=∫ 0 t (τ*RR+ω(0))dτ, θ DRUM (t)=½t 2 *RR+ω(0)* t , and T(t)=C(t*RR+ω(0))+K 1 +K 2 sin(½t 2 *RR+ω(0)*t+φ).
[0057] The objective of the algorithm is to detect the speed at which a particular laundry load may become satellized while the drum is accelerating at a constant ramp rate. The fact that the torque signal becomes a sinusoid with a single frequency matching the drum speed at or above satellization speed may be the basis for the algorithm. The algorithm may be based upon determining how much the torque signal differs from one period of a sinusoid for each drum revolution.
[0058] The torque signal may be sampled with a fixed sampling rate and stored in a buffer memory. The length of the buffer memory may be sufficient to hold enough sampling data for one complete drum revolution at a lowest speed of interest. For example, the fixed sampling rate may be 100 Hz, and the lowest drum speed of interest may be 45 RPM. One drum revolution at 45 RPM may take 1.33333 seconds, so sampling every 0.01 second may require 134 samples. Thus, the maximum buffer length required may be 134.
[0059] The algorithm may be intended to be implemented in embedded code. Moreover, because the sine function may be unavailable to recall during data sampling, one period of a normalized sine wave may be generated from a fixed number of samples, and stored in memory ahead of time. More sampling data may enable higher resolution, but at the expense of more memory. This array of a fixed number of samples from a normalized sine wave may be referred to as a “reference signal,” and may be expressed as follows:
[0000]
Ref
(
n
)
=
sin
(
2
π
*
n
L
)
,
[0000] where
nε{0, 1, 2, 3, . . . L−1}, and L=length of reference array.
[0062] The length of the reference array may be at least twice the length of the torque buffer array to assure sufficiently high resolution when selecting the samples from the reference array to compare to each sample in the torque array.
[0063] The torque signal from the equation for T(t), above, may be in continuous time, and the process of sampling with a fixed sampling period, T s , may have the following effect on the equation:
[0000] t=k*T s ,
[0000] where
kε{0, 1, 2, 3, . . . L−1}, and T ( kT s )= C ( kT s *RR+ω(0))+ K 1 +K 2 sin G (½( kT s ) 2 *RR+ω(0)* kT s +φ).
[0066] For low speeds, the viscous damping coefficient may be very small, and over one period of the sine wave, (kT s *RR) may be a small number, so that the expression C(kT s *RR+ω(0)) may be simplified to (C*ω(0)). This term may be grouped with K 1 so that the equation may simplify to the following:
[0000] T ( kT s )=δ+ K 2 sin(( kT s *RR+ω(0))* kT s +φ),
[0000] where
δ= C *ω(0)+ K 1 .
[0068] In order to compare the torque signal to the reference signal there are 3 characteristics of the sampled torque signal that are useful to determine: a constant offset (δ), an amplitude (K 2 ), and a phase (φ). If these 3 parameters are determined, the reference signal may be scaled by K 2 , biased by δ, and shifted by φ. In the following example, δ=1, K 2 =4, and φ=π/4.
[0069] FIG. 5A illustrates a raw reference signal 82 and a torque signal 84 . FIG. 5B illustrates a scaled and biased reference signal 86 and a torque signal 88 . FIG. 5C illustrates a scaled, biased, and shifted reference signal 90 and a torque signal 92 .
[0070] FIG. 5C illustrates the torque signal 92 initially matching the reference signal 90 well, but as time progresses, the torque signal 92 may lead the reference signal 90 . This is the result of the torque sine wave frequency increasing at a constant rate as the drum speed increases at a constant rate. In this example, the ramp rate is 5 RPM per second (0.0833 Hz/s), and at the end of the cycle, the torque signal frequency is about 8% higher than the reference signal.
[0071] To account for an increasing frequency of the torque signal, the sampling data from the reference array may be selected at an increasing time interval. To determine the correct relationship, the expressions for the torque and reference array may be equated, and solved for the reference array sample, n. (For the derivation, the phase, φ, may be set to 0, and the ramp rate, RR, and initial speed, ω(0), may be converted to Hz/s and Hz, respectively.) Thus:
[0000]
[
Ref
(
n
)
=
δ
+
K
2
sin
(
2
π
*
n
L
)
]
=
[
T
(
kT
s
)
=
δ
+
K
2
sin
(
2
π
*
(
1
2
(
kT
s
)
2
*
RR
+
ω
(
0
)
*
kT
s
)
)
]
,
[
δ
+
K
2
sin
(
2
π
*
n
L
)
]
=
[
δ
+
K
2
sin
(
2
π
*
(
1
2
(
kT
s
)
2
*
RR
+
ω
(
0
)
*
kT
s
)
)
]
,
(
n
L
)
=
(
1
2
(
kT
s
)
2
*
RR
+
ω
(
0
)
*
kT
s
)
,
and
n
=
(
1
2
(
kT
s
)
2
*
RR
+
ω
(
0
)
*
kT
s
)
*
L
.
[0072] Finally, by implementing the above equation for n and select sampling data from the reference array, we may observe how the torque and reference signals line up. FIG. 6A illustrates the sampled torque signal 92 and the scaled, biased, and shifted reference signal 90 shown in FIG. 5C . FIG. 6B illustrates the sampled torque signal 96 and the scaled, biased, shifted, and frequency-adjusted reference signal 94 with a 100 point reference sampling array. FIG. 6C illustrates the same signal correlation as illustrated in FIG. 6B , but with a 200 point reference sampling array. The effect of utilizing more samples in the reference array may be observed from FIGS. 6B and 6C .
[0073] The above equation for n may enable a comparison of the torque signal to the reference signal for any combination of starting speeds and ramp rates. For example, if the ramp rate were 0, and the starting speed were 60 RPM (1 Hz):
[0000] n =(½( kT s ) 2 *RR+ω(0)* kT s )* L,
[0000] n =(1* kT s )* L
[0074] If the reference array length were 400, and the sampling period, T s were 0.01, then:
[0000]
n
=
k
(
1
100
)
*
400
,
n
=
4
k
[0075] An actual comparison may be accomplished by iterating through the entire torque array buffer, and comparing each sample to the appropriate sample from the reference array using the equation:
[0000] n =(½( kT s ) 2 *RR+ω(0)* kT s )* L.
[0000] determine the reference sample size. For example, with a torque sampling period=0.1 second, and a length of the reference array=20, then n=2 k. This is illustrated in FIGS. 7A and 7B , wherein values of k and n, respectively, may be correlated. FIG. 7A illustrates that every data point 104 on the torque array 102 may be utilized. FIG. 7B illustrates that every other element 108 from the reference array 106 may be ignored.
[0076] As a loop through the array from k=0 to k=N−1 progresses, a magnitude of the difference between the two points, i.e. torque array data point 104 and reference array element 108 , may be calculated:
[0000] 2 √{square root over (( T ( k )−Ref( n )) 2 )}{square root over (( T ( k )−Ref( n )) 2 )},
[0000] where
kε{0, 1, 2, 3, . . . N−1}, n =(½)(kT s ) 2 *RR+ω(0)*kT s )*L, Metric=Σ k=0 N−1 2 √{square root over ((T(k)−Ref(n)) 2 )}{square root over ((T(k)−Ref(n)) 2 )}, and n=(½(kT s ) 2 *RR+ω(0)*kT s )*L.
[0081] The magnitude of the difference at each point may be summed for the entire array, then divided by the length of the torque buffer array. As an example, assuming each point in the array differs by 1, and the length of the torque array is 100, then Metric=1.
[0082] FIGS. 8A , 8 B, and 8 C illustrate additional analyses of the drum revolutions 4 , 5 , and 6 , respectively, illustrated in FIG. 4A . The shaded area 110 , 112 , 114 in each figure may essentially represent the metric. In FIG. 8A , for example, the shaded area 110 , i.e. the degree to which the torque curve 72 deviates from the reference curve 76 , is also represented by a bar graph 116 . An empirical threshold value 122 established for a selected laundry treating appliance running a selected cycle of operation for a selected laundry load is also represented with the bar graph 116 .
[0083] As the laundry load becomes satellized, the area 110 , 112 , 114 between the curves may be reduced, and the associated metric 116 , 118 , 120 may reflect this reduction, as illustrated in FIGS. 8A , 8 B, and 8 C. When the metric 120 , i.e. the difference between the torque curve and the reference curve, decreases to a value less than the empirical threshold value 122 , as illustrated in FIG. 8C , the laundry load may be said to be satellized. For example, in FIG. 8C , after completing revolution 6 , the metric 120 is less than the threshold value 122 , and the laundry load is therefore satellized. FIG. 8C indicates a satellization speed of approximately 60 RPM.
[0084] Selected equal-length intervals, or “windows,” of time may be established, and a torque signal may be generated for each selected interval. Data associated with each interval may be collected and evaluated. The intervals may advance forward in time as acceleration proceeds and satellization develops. The metric, or difference between the torque signal and the reference torque signal, may be determined as a difference in the amplitudes of the torque and reference torque signals. Alternatively, the difference between the signals may be the difference between a running average of the amplitudes of the torque signal and the reference signal. The running average may be a moving running average, which may be determined from a window of data points of fixed length advancing in time.
[0085] The embodiment of the invention described herein provides a method for readily determining a satellization speed for a selected laundry treating appliance running a selected cycle of operation for a selected laundry load. Thus, the satellization speed can be efficiently reached for effective liquid extraction while minimizing vibration and energy usage.
[0086] While the invention has been specifically described in connection with certain specific embodiments thereof, it is to be understood that this is by way of illustration and not of limitation. Reasonable variation and modification are possible within the scope of the forgoing disclosure and drawings without departing from the spirit of the invention which is defined in the appended claims.
|
A laundry treating appliance may include a rotatable treating chamber for receiving a laundry load for treatment, and a motor for rotating the treating chamber, and may be operated such that during the acceleration of the laundry load toward a satellizing speed, the satellizing of the laundry load may be detected, whereby subsequent operation of the laundry treating appliance may be controlled based on the detection.
| 3
|
This is a divisional application of U.S. patent application Ser. No. 895,082, filed Apr. 10, 1978.
BACKGROUND OF THE INVENTION
This invention relates to 1,4-bis-(substituted aminoalkylamino)-anthraquinones, and more particularly to the same as anti-neoplastic agents against animal neoplasms. 1,4-bis-substituted anthraquinones have long been known in the prior art as dyes. For example, U.S. Pat. No. 2,050,661 teaches a process for preparing 1,4-diaminoanthraquinone which is suitable for use for dying cellulose esters and ethers or for coloring fats, oils, waxes, and the like. U.S. Pat. No. 1,199,176 teaches the use of 1,4-bis-(alpha, beta-diphenolethylamino) anthraquinone and the like for dying wool and other animal fibers.
A method for the production of 1,4-bis-(substitued aminoalkylamino)-anthraquinones is also known in the art ("The reaction of leucoquinizarines with alkylenediamines", Greenhalgh and Hughs, J. Chem. Society (C), page 1284 (1968)).
Certain naturally occurring substituted anthraquinones, namely, 2,6-bis-substituted and 2,7-bis-substituted anthraquinones, have been found to give indications of possible anti-neoplastic inhibitory effects. Generally, these have been reported as inhibitions of DNA polymerases by intercalation between base pairs of DNA double helix. The intercalation theory has been used as a working hypothesis to explain the activity of many anti-cancer drugs including actinomycin D, daunorubicin, adriamycin, anthramycin, and coralyne. However, certain of these drugs, even though recognized as very promising and definitely showing good inhibitory activity against leukemia as well as solid tumors, have the disadvantage that they or their metabolites cause severe and irreversible cardio toxicity which could be fatal if the accumulated dose of these drugs exceeds a limited amount. Additionally, they are all naturally produced.
Certain in vivo testing systems and protocols have been developed by the National Cancer Institute for testing compounds to determine their suitability as antineoplastic agents. These have been reported in Cancer Chemotherapy Reports, Part III, Vol. 3, No. 2, (1972), Deran, Greenberg, MacDonald, Schumacher and Abbott. These protocols have established standardized screening test which are generally followed in the field of testing for antineoplastic agents. Three of these systems are particularly significant to the present invention. These are lymphoid leukemia L1210, lymphocytic leukemia P388 and melanotic melanoma B16. All of these neoplasms are found in mice. Initial screening is usually done with P388 leukemia and B16 melanoma if the initial tests appear promising. Generally, good antineoplastic activity shown in these protocols by a percentage increase of mean survival times of the test animals over the control animals is predictive of similar results in human leukemias. A mean survival time ratio of test over control (with the control group representing 100%) of 125% is considered necessary to demonstrate antineoplastic activity by the substance being tested. Further detailed description of these protocols is presented hereinbelow in the detailed description of the invention.
OBJECTS OF THE INVENTION
It is a primary object of the invention to provide new compounds for treating animal neoplasms in an animal neoplasm-bearing host including humans.
It is a further object of the present invention to provide as the primary object, a synthetically-made substance.
It is a still further object of the present invention to provide for the primary object a substance having lower toxicity and fewer side effects.
It is yet a further object of the present invention to provide novel 1,4-bis-(substituted aminoalkylamino)-anthraquinones.
Still another object of the present invention is to provide effective compounds for treating the highly predictive P388 leukemia in mice, the highly predictive B16 melanoma in mice.
The above and other objects are achieved in accordance with the present invention by anti-neoplastic 1,4-bis-substituted anthracenediones having the formula ##STR2## wherein W, X, Y and Z are each independently selected from the group consisting of hydrogen, OH, NH 2 , OCH 3 , N(CH 3 ) 2 , F, Cl, Br, I, alkyl groups containing from 1-8 carbon atoms, glucosides, phenyl and substituted phenyl, and R is selected from the group consisting of alkylamino groups containing from 1-8 carbon atoms, alkylaminoalkyl groups containing from 1-8 carbon atoms, substituted alkylaminoalkyl groups containing from 1-8 carbon atoms, and substituted aminoaryl groups.
Some of the above groups have been found to be especially effective. These include the compounds in Table 1.
TABLE 1______________________________________W X Y Z R______________________________________a. OH H H OH (CH.sub.2).sub.2NH(CH.sub.2).sub.2OHb. H H H H (CH.sub.2).sub.2 NH(CH.sub.2).sub.2 OHc. H H H H (CH.sub.2).sub.2 NHCH.sub.2 CH.sub.3d. H H H H (CH.sub.2).sub.2 NHCH.sub.3e. H H H H (CH.sub.2).sub.2 NH.sub.2f. H H H H ##STR3##g. H H H H (CH.sub.2).sub.3 NH(CH.sub.2).sub.2 OH______________________________________
DETAILED DESCRIPTION OF THE INVENTION
Generally, the method of preparation of the 1,4-bis (substituted aminoalkylamino) anthraquinones was based on that described by Greenhalgh and Hughes, J. Chem. Society (C), Page 1284, 1968. This involves condensation of leucoquinizarins (II) with an excess amount of the appropriate amines at 50° to 55° C. followed by air oxidation of the dihydro intermediates (III) to the desired products (IV). ##STR4##
Since the intermediates III and products IV have distinct and different UV absorption in ethanol (III are usually green, with λ max at 465 and 490 nm, whereas the bright blue IV have λ max at 580 and 630 nm) the absorption change of the reaction mixture is used to monitor the course of the reaction and to estimate the purity of the products. The products, which are soluble in water, strongly stain skin, fiber, and even plastic material. The intense dark color of solutions of these compounds often affect purification processes.
Oxidation of the dihydro intermediates III to the aminoanthraquinones IV proceeded readily in most cases and sometimes can even be realized during recrystallization of the crude dihydro intermediates III or upon standing of III in solution. Hence, attempts to isolate the pure dihydro intermediates III, even under nitrogen, proved to be difficult. For example, attempted isolation of the dihydro intermediate of 1,4-bis (hydroxyethyl-aminoethylamino) anthraquinone gave an 80% yield of a crude compound, melting point of about 130°-132° C. It was, understandably, still contaminated with the final product. At a higher reaction temperature of about 100° C., the product readily cyclized to form compound V. ##STR5## For the preparation of many target compounds, therefore, the reaction temperature must be kept below 55° C., preferably at 50° C.
Some difficulties were encountered during the preparation of the dihydro intermediate 1,4-bis (2-aminoethylamino) anthraquinone because of the presence of a primary amine function on the side chains and the insolubility of the intermediate in the particular reaction solvents used (ethanol and CH 3 CN). The dihydro intermediate was eventually obtained but subsequent oxidation by air in CH 3 CN yielded a high-melting solid, melting point about 308°-310° C., which was only sparingly soluble in common organic solvents such as ethanol or CHCl 3 . Elemental analysis indicated the presence of only three nitrogen atoms in the molecule and suggested VI as one of the possible structures of the product. ##STR6## Apparently compound VI was formed by an intramolecular condensation of the two terminal chains with the elimination of NH 3 . The desired compound e (Table I), melting point of 174°-176° C., was obtained in 23% yield by repeated recrystallizations of the dihydro intermediate from CH 3 CN according to the method noted above of Greenhalgh and Hughes.
EXAMPLE 1
Preparation of 1,4-dihydroxy-5,8-bis[[2-(hydroxyethyl)amino]ethyl]amino-9,10-anthracenedione.
The preparation of 1,4-dihydroxy-5, 8-bis[[2-(hydroxyethyl) amino]ethyl]amino-9,10-anthracenedione (compound a, Table I) was carried out as follows: To 10 g (0.036 mole) of 5,8-dihydroxyleucoquinizarin (commercially available from [Bayer AG, 509 Leverkusen, Beyerwerk, West Germany], purified by continuous extraction with dioxane under nitrogen) was added dropwise, under nitrogen with cooling and stirring, 38 g (0.36 mole) of 2-(2-aminoethylamino)ethanol. When a homogeneous paste was obtained, the reaction mixture was heated at 50°-55° C. in an oil bath for two hours. It was allowed to stir overnight. The mechanical stirring rod was replaced (the stirring rod was rinsed with 4×50 ml of ethanol, the ethanol washings were added to the mixture) by a glass sparge tube and dry air (passed through a tube containing Drierite) was bubbled through the reaction mixture (the entire system was under a slightly reduced pressure) by connecting the top of the condenser to a water aspirator. This mold oxidation reaction was carried out at 55°-60° C. for approximately 2-3 hours. The color of the syrup gradually changed from purple to a bright blue. The mixture was then allowed to stand overnight at room temperature. The resulting dark blue solid was collected by filtration through a sintered glass funnel. The solid product washed with ethanol (2×20 ml), petroleum ether (3×50 ml) and dried to give 4.6 g (20% yield) of Compound a, m/p/ 158°-160° C. An analytical sample was prepared by recrystallization of the crude product from a mixture of ethanol and petroleum ether, m.p. 160°-162° C. λ max EtOH 244 (log ε4.64), 279 (4.31), 525 (3.70), 620 (4.37) and 660 nm (4.38).
Anal. Calculated for C 22 H 28 N 4 O 6 : C, 59.50; H, 6.34; N, 12.61. Found: C, 59.55; H, 6.56; N, 12.33
EXAMPLE II
Preparation of 1,4-Bis[[2-(ethylamino)ethyl]amino]-9,10-anthracenedione ##STR7##
A mixture of 4 g (0.9165 mole) of 1, 4, 9, 10-tetrahydroxyanthrancene (leucoquinizarin) VII and 23 g (0.26 mole) of N-(2-aminoethyl)ethylamine VIII was heated to 50° C. under N 2 for ninety minutes. The mixture was cooled and allowed to stand overnight. To it was added 100 ml of methanol. A stream of dry air was bubbled through the mixture at 50° C. for two hours. Blue crystals, which separated from the reaction mixture after standing, were collected by filtration and washed with 10 ml of ethyl acetate followed by 10 ml of hexane. The product was purified by recrystallization from a mixture of chloroform, and heptane to give 3.5 g (56% yield) of IX, m.p. 118°-120° C.
Anal: Calculated for C 22 H 28 N 2 O 4 .2H 2 O: C, 63.44; H, 7.74; N, 13.45. Found C, 63.61; H, 7.79; N, 13.68.
EXAMPLE III
Preparation of 1,4-Bis[[2-methylamino)ethyl]amino]-9,10 anthracenedione ##STR8##
Twenty-two grams (0.29 mole) of N-(2-aminoethyl) methylamine (X) was added dropwise into 10.0 g (0.045 mole) of VII under nitrogen with stirring in 15 min. After the addition was complete, the mixture was stirred for an additional 30 min., then heated at 50°-55° C. for three hours. It was then cooled and 100 ml of ethanol was added. Dry air was bubbled through the mixture at 45°-50° C. for three hours. It was allowed to stand overnight and to it was added 40 ml of ethanol and 20 ml of Skelly solve F (petroleum ether, bp 35°-60° C.). The mixture was stirred for thirty minutes and the solid product was collected by filtration. It was washed successively with ethanol (2×5 ml) and Skelly solve F (2×50 ml) and dried to give 8.2 g (52% yield) of XI, mp 120° C. An analytical sample was prepared by recrystallization of 1.2 g of XI from 50 ml of chloroform and 100 ml of Skelly solve F, mp 119°-121° C. Anal. Calculated for C 20 H 24 N 4 O 2 . 1/2H 2 O: C, 66.46; H, 7.06; N, 15.50. Found: C, 66.29; H, 7.11; N, 15.31
EXAMPLE IV
Preparation of 1,4-bis[2-aminoethyl)amino]-9,10-anthracenedione ##STR9##
A mixture of 14.5 g (0.06 mole) of VII and 150 ml of ethylenediamine (XII) was heated under N 2 for one hour at 50° C. Dry air was bubbled through the mixture at 50° C. for forty-five minutes. The mixture, after standing overnight, deposited XIII which was collected by filtration, washed successively with acetonitrile (3×30 ml) and diethyl ether (2×50 ml) and dried to give 17 g of crude XIII, mp 165°-168° C.
Its ultraviolet absorption spectrum showed the presence of dihydro derivatives. Three recrystallizations from acetonitrile gave 5.9 g (23% yield) of purified XIII, mp 174°-176° C.
Anal. Calculated for C 18 H 20 N 4 O 2 : C, 66.65; H, 6.21; N, 17.27. Found: C, 66.45; H 6.36; N, 17.10.
The antineoplastic activity of the various compounds was determined in in vivo testing following the protocols developed by the National Cancer Institute reported by Deran et al in Cancer Chemotherapy Reports, part 3, Vol. 3, No. 2, (1972). These specific test systems were lymphoid leukemia L1210, lymphocytic leukemia P388 and melanotic melanoma B16. The key test result noted is the mean survival time ratio of test animals over control animals which is hereinafter noted as percentage increase of life span of test over control (percent ILS). As noted above, a percent ILS of 125% is considered to show good antineoplastic activity.
Activity against lymphocytic leukemia P388 is tested by implanting ascitic fluid in BDF 1 mice. Treatment with the compound begins twenty-four hours after the implant. As noted above, the results are expressed as a percent increase in life span or survival time. The innoculum site for screening is ip and the compound is administered ip daily for nine days. The implant size is 0.1 ml of diluted ascitic fluid containing 10 6 cells. The number of survivors of the test group on day 6 is checked. All deaths of test animals after day 6 are not considered to be due solely to drug toxicity. Testing ends on day 30. The mean animal weight difference between the test group and the control group is computed between days 1 and 5. At the completion of testing the percent ILS is computed for all test groups with greater than 65% survivors on day 5. A percent ILS value of less than 85% indicates a toxic test, a percent ILS of greater than 125% is considered to demonstrate antineoplastic activity. Any survivor of the test group on the day of evaluation (day 30) is recorded as a cure.
Activity against lymphoid leukemia L1210 is tested by implanting ascitic fluid into BDF 1 mice. Treatment begins twenty-four hours after the implant. The results are expressed as a percentage of increased life span of the test animals over the control animals. The inoculum site is ip and the compound is administered ip. The implant size is 0.1 ml of diluted ascitic fluid containing 10 5 cells. As with P388, the toxicity check date is day 6 and the experiment is run for thirty days. Mean animal weight is also checked between days 1 and 5 and the percent ILS is computed at the end of the experiment. Any survivors of the test group on day thirty are considered to be cures.
Activity against melanotic melanoma B16 is tested by implanting a tumor homogenate ip in BDF 1 mice. The treatment begins twenty-four hours after the ip implant and the results are expressed as a increased percentage of life span of the test animals over the control animals. The drug is administered ip daily for nine days. To prepare the homogenate, 1 gram of tumor is mixed with 10 ml of cold balanced salt solution and homogenized. 0.5 ml of the tumor homogenate is implanted ip. The check date for compound toxicity is day 5 and the experiment runs until day 60.
All dosages are in milligrams per kilogram of body weight of test animal per injection. The mean survival time of the test animals is computed and ratioed with the mean survival time of the control animals and the result is expressed as a percentage (%ILS). Other specific information regarding the animal selection and animal care, randomization of animals in the testing, specific preparation and administration of test materials, selection of doses, propagation of tumor lines, tumor quality control, specific techniques of tumor transplantation, and the exact calculational method for test evaluation can be found in the above noted reference to Deran et al, which is incorporated herein by reference.
ANTINEOPLASTIC TESTING EXAMPLES
In addition to the compounds listed in Table 1, the following compounds with noted structure are presented:
TABLE II______________________________________W X Y Z R______________________________________h. H H H H (CH.sub.2).sub.2 NH(CH.sub.2).sub.2 CH.sub.3i. H H H H ##STR10##j. H H H H (CH.sub.2).sub.2 NH(CH.sub.2).sub.2 NH(CH.sub.2 ).sub.2 OHk. H H H H (CH.sub.2).sub.2 S(CH.sub.2).sub.2 OHl. H H H H (CH.sub.2).sub.5 OHm. H H H H ##STR11##______________________________________
The following results were obtained testing for activity against lymphocytic leukemia P388:
TABLE III______________________________________ACTIVITY AGAINST P388 Dose Wt. Diff.Compound mg/kg Survival gm % ILS Cures______________________________________a 2 6/6 -0.6 280 5/6 1 5/6 -0.6 277 3/6 0.5 6/6 -2.0 299 4/6 0.25 6/6 -2.3 280 2/6 0.12 6/6 -1.4 200 0.06 6/6 -1.7 208b 32 6/6 -5.9 81 16 6/6 -3.9 275 3/6 8 6/6 -2.0 276 4/6 4 6/6 0 275 3/6c 25 11/12 -4.8 132 1/12 12.5 5/6 -2.8 168 6.25 6/6 -2.2 149 3.13 6/6 -2.3 142d 12.5 6/6 -1.9 200e 25 6/6 -2.6 215 12.5 6/6 -1.1 174 6.25 6/6 -1.1 159 3.13 6/6 -019 107 1.56 6/6 -1.6 137 0.78 6/6 -1.3 150f 50 10/12 -217 134 25 12/12 -1.0 137 12.5 12/12 -1.1 117 6.25 6/6 -0.4 125g 100 11/12 -2.6 98 1/12 50 12/12 -2.1 133 25 11/12 -2.1 130 12.5 6/6 -1.4 117 6.25 6/6 0.9 101h 100 6/6 -2.6 124 50 6/6 -1.7 125 25 6/6 -0.8 118i 100 12/12 -4.5 128 50 12/12 -2.9 110 25 6/6 -3.6 104j 100 15/18 -2.6 120 50 18/18 -1.3 112 25 18/18 -1.6 110k 100 6/6 -2.2 94 50 6/6 -1.4 86 25 6/6 -1.6 95l 100 6/6 -4.0 88 50 6/6 -1.5 78 25 6/6 -1.4 88m 400 6/6 -2.9 91 200 6/6 -3.2 101 100 6/6 -1.7 86______________________________________
Certain of these compounds were tested against Melanotic Melanoma B16 and Lymphoid Leukemia L1210, the data being presented in Tables IV and V respectively:
TABLE IV______________________________________ACTIVITY AGAINST B16Compound Dose % ILS Cures______________________________________e 16 281 8/10 8 280 6/10 4 280 6/10a 1 503 7/10 0.5 466 4/10______________________________________
TABLE V______________________________________ACTIVITY AGIANST L1210Compound Dose % ILS______________________________________b 125 272 12.5 227 6.25 156______________________________________
As can be seen from the data in Table III, all of the 1,4-bis(substituted aminoalkylamino) anthraquinones showed at least some antineoplastic activity against P388. A %ILS of greater than 125 is considered good antineoplastic activity.
Some of the results are especially noteworthy. Namely, with the absence of the second amino group (compounds pounds k, l, and m) no activity was evidenced. Apparently, the nitrogen atom in center of the side chain plays an important role in antileukemic activity. No activity is noted when this nitrogen atom is replaced by a methylene unit (even though compound 1 retains the same chain length) or by a sulphur atom. The insertion of an additional ethyl amino unit into the side chain as in compound j, drastically reduces the activity below the marginal level. The distance between the nitrogen atoms appears to have significance which is apparent in the comparison between the results of compound g and compound b. Further importance of the nitrogen atom in the center of the side chain is demonstrated by changing the original secondary amino function to a tertiary amino function. Compound i is only marginally active when compared with compound b. The activity of compound f is slightly there above probably due to the presence of the binding terminal. On the other hand, compound e, which contains primary amino groups at the end of both side chains, still remains good, although not as high as compound b.
Suprisingly excellant antileukemic activity is obtained in compound a (note the extremely low dosage levels both for activity against P388 and activity against B16). This compound is more soluble in water than compound b and appears to require less than one-tenth of the optimum dose of compound b to produce good activity. Compound e additionally shows excellent activity against B16 with a high rate of cures (survivors at the end of day 30 of the test group.)
It should now be apparent that the objects initially set forth have been successfully achieved. Moreover, while there is shown and described present examples of the invention, it is to be distinctly understood that the invention is not limited thereto but may be otherwise variously embodied and practiced within the scope of the following claims. Accordingly, what we claim is pounds k, l, and m) no activity was evidenced. Apparently, the nitrogen atom in center of the side chain plays an important role in antileukemic activity. No activity is noted when this nitrogen atom is replaced by a methylene unit (even through compound 1 retains the same chain length) or by a sulphur atom. The insertion of an additional ethyl amino unit into the side chain as in compound j, drastically reduces the activity below the marginal level. The distance between the nitrogen atoms appears to have significance which is apparent in the comparison between the results of compound g and compound b. Further importance of the nitrogen atom in the center of the side chain is demonstrated by changing the original secondary amino function to a tertiary amino function. Compound i is only marginally active when compared with compound b. The activity of compound f is slightly there above probably due to the presence of the binding terminal. On the other hand, compound e, which contains primary amino groups at the end of both side chains, still remains good, although not as high as compound b.
Surprisingly excellent antileukemic activity is obtained in compound a (note the extremely low dosage levels both for activity against P388 and activity against B16). This compound is more soluble in water than compound b and appears to require less than one-tenth of the optimum dose of compound b to produce good activity. Compound e additionally shows excellent activity against B16 with a high rate of cures (survivors at the end of day 30 of the test group).
Since these compounds show good results against P388, L1210, and B16 which, as noted, are predictive of good results in humans, the compounds disclosed herein should be operative against human leukemias and the like.
It should now be apparent that the objects initially set forth have been successfully achieved. Moreover, while there is shown and described present examples of the invention, it is to be distinctly understood that the invention is not limited thereto but may be otherwise variously embodied and practices within the scope of the following claims.
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An antineoplastic 1,4-bis-substituted-9-10-anthracenedione having the formula ##STR1## wherein W, X, Y and Z are each independently selected from the group consisting of hydrogen, OH, NH 2 , OCH 3 , N(CH 3 ) 2 , F, Cl, Br, I, alkyl groups containing from 1-8 carbon atoms, glucosides, phenyl and substituted phenyl, and R is selected from the group consisting of alkyl amino groups containing from 1-8 carbon atoms, alkylaminoalkyl groups containing from 1-8 carbon atoms, substituted alkylamino-alkyl groups containing from 1-8 carbon atoms, and substituted aminoaryl groups.
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